WO2023054518A1

WO2023054518A1 - Prepreg, laminate and printed wiring board

Info

Publication number: WO2023054518A1
Application number: PCT/JP2022/036277
Authority: WO
Inventors: 勇太田原; 孝史久保; 将太古賀; 環伊藤; 政伸十亀
Original assignee: 三菱瓦斯化学株式会社; Ｍｇｃエレクトロテクノ株式会社
Priority date: 2021-09-30
Filing date: 2022-09-28
Publication date: 2023-04-06
Also published as: TW202317678A; CN118043384A; JPWO2023054518A1

Abstract

[Problem] The present invention provides: a prepreg which is capable of reducing skew and transmission loss; a laminate; and a printed wiring board. [Solution] The present invention provides a prepreg which is obtained by impregnating or coating a glass fiber base material with a resin composition that contains a thermosetting compound, wherein the proportion of the resin composition with respect to the total amount of the prepreg is within the range from 81% by volume to 98% by volume. The skew is able to be reduced by setting the proportion of the resin composition to 81% by volume or more. Meanwhile, if the proportion of the resin composition exceeds 98% by volume, warp after curing becomes large. After the curing, the relative dielectric constant at 10 GHz is 3.3 or less, and the dielectric loss tangent is 0.004 or less.

Description

Prepregs, laminates and printed wiring boards

The present invention relates to prepregs, and laminates and printed wiring boards using them.

In recent years, there has been rapid progress in increasing the speed and capacity of data communications used in information communications. Therefore, electronic devices for information and communication require printed wiring boards that are compatible with high frequencies. As an insulating material used for printed wiring boards, for example, a prepreg obtained by impregnating or applying a resin to glass fiber is widely used. However, since the glass fiber and the resin have different dielectric properties, variations in the signal delay time (transmission speed) occur due to the density of the glass fiber. As the transmission speed increases, the influence of the propagation delay time difference (skew; SKEW) occurring between the differential wirings increases, and the skew causes the deterioration of the transmission characteristics. In addition, it is necessary to reduce transmission loss in order to cope with high frequencies.

International Publication No. 2019/230945

The present invention has been made based on such problems, and aims to provide a prepreg, a laminate, and a printed wiring board that can reduce skew and transmission loss.

Note that Patent Document 1 describes a prepreg for the purpose of reducing variations in signal delay time. However, the prepreg described in Patent Document 1 reduces the influence of the high dielectric constant of the glass fiber on the impedance of the conductor wiring by interposing hexagonal boron nitride between the glass fiber and the conductor wiring, thereby This is intended to reduce skew, and the specific configuration differs from that of the present invention.

The present invention is as follows.
[1]
A prepreg in which a glass fiber substrate is impregnated or coated with a resin composition containing a thermosetting compound, wherein the ratio of the resin composition to the total amount of the prepreg is 81% by volume or more and 98% by volume or less. A prepreg having a relative permittivity of 3.3 or less at 10 GHz and a dielectric loss tangent of 0.004 or less after curing.
[2]
The glass fiber base material contains at least one glass fiber selected from the group consisting of E glass, D glass, S glass, T glass, Q glass, L glass, NE glass, and HME glass [1] The prepreg described in .
[3]
The prepreg according to [1], wherein the thermosetting compound contains terminal unsaturated group-modified polyphenylene ether.
[4]
The prepreg according to [3], wherein the content of the terminal unsaturated group-modified polyphenylene ether is 1 to 40 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition.
[5]
The prepreg according to [1], wherein the thermosetting compound contains one or more selected from the group consisting of maleimide compounds, cyanate ester compounds, epoxy compounds, and phenol compounds.
[6]
The prepreg according to [1], wherein the resin composition further contains a thermoplastic elastomer.
[7]
The prepreg according to [6], wherein the content of the thermoplastic elastomer is 1 to 45 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition.
[8]
The prepreg according to [1], wherein the resin composition further contains a filler.
[9]
The prepreg according to [8], wherein the content of the filler is 50 to 1600 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition.
[10]
A laminate comprising a cured product of the prepreg according to [1].
[11]
A printed wiring board having an insulating layer and a conductor layer, wherein the insulating layer contains the cured prepreg of [1].

According to the present invention, skew and transmission loss can be reduced. Therefore, high frequencies can be handled.

It is a figure showing the relationship between the ratio of a resin composition, and a dielectric constant. It is a figure showing the relationship between the ratio and skew of a resin composition. It is a figure showing the relationship between the ratio and curvature of a resin composition.

Hereinafter, a mode for carrying out the present invention (hereinafter referred to as "this embodiment") will be described in detail, but the present invention is not limited to this, and various modifications can be made without departing from the scope of the invention. is possible.

[Prepreg]
The prepreg according to the present embodiment is obtained by impregnating or coating a glass fiber base material with a resin composition containing a thermosetting compound. The ratio of the resin composition to the total amount of prepreg is in the range of 81% by volume or more and 98% by volume or less. This is because skew can be reduced by setting the ratio of the resin composition to the total amount of the prepreg to be 81% by volume or more, and it is possible to cope with high frequencies. On the other hand, if the ratio of the resin composition to the total amount of the prepreg exceeds 98% by volume, the warp after curing becomes large, which is not suitable for printed wiring boards. The ratio of the resin composition to the total amount of the prepreg is more preferably 85% by volume or more, and even more preferably 86% by volume or more. Also, the ratio of the resin composition to the total amount of the prepreg is more preferably 96% by volume or less, and even more preferably 95% by volume or less.

The dielectric constant at 10 GHz after curing of the prepreg is 3.3 or less. This is because the lower the dielectric constant, the higher the signal speed and the higher the frequency. More preferably, the dielectric constant at 10 GHz after curing of the prepreg is less than 3.2. Although the lower limit of the dielectric constant at 10 GHz after curing the prepreg is not particularly limited, it can be set to 2.6 or more, for example. In addition, the dielectric loss tangent at 10 GHz after curing of the prepreg is 0.004 or less. This is because a smaller dielectric loss tangent can reduce transmission loss and can cope with high frequencies. Although the lower limit of the dielectric loss tangent at 10 GHz after curing the prepreg is not particularly limited, it can be, for example, 0.002 or more.

This prepreg can be obtained, for example, by impregnating or applying a resin composition to a glass fiber base material, and then semi-curing (to B-stage) by drying at 120 to 220°C for about 2 to 15 minutes. The ratio of the resin composition to the total amount of the prepreg is the ratio after semi-curing, and the resin composition includes a cured product of the resin composition. As will be described later, the resin composition also contains a filler.

<Glass fiber base material>
The glass fiber base material contains, for example, at least one glass fiber selected from the group consisting of E glass, D glass, S glass, T glass, Q glass, L glass, NE glass, and HME glass. is preferred. The form of the fiber base material is not particularly limited, and examples thereof include woven fabrics, nonwoven fabrics, rovings, chopped strand mats, surfacing mats, and the like. Among them, from the viewpoint of dimensional stability, woven fabrics subjected to super-opening treatment and stuffing treatment are preferable, and from the viewpoint of moisture absorption and heat resistance, woven fabrics surface-treated with a silane coupling agent such as epoxysilane treatment and aminosilane treatment. Cloth is preferred. The thickness of the glass fiber substrate is not particularly limited, and can be, for example, 9 μm to 32 μm.

<Resin composition>
(Terminal unsaturated group-modified polyphenylene ether)
The resin composition can contain a terminal unsaturated group-modified polyphenylene ether as a thermosetting compound. A terminal unsaturated group-modified polyphenylene ether is represented by general formula (1).

In general formula (1), X represents an aryl group, —(Y—O)n ₂ — represents a polyphenylene ether moiety, and R ₁ , R ₂ , and R ₃ each independently represent a hydrogen atom, an alkyl group, an alkenyl or an alkynyl group, _n2 is an integer of 1-100, _n1 is an integer of 1-6, and _n3 is an integer of 1-4.

By containing the terminal unsaturated group-modified polyphenylene ether, excellent low dielectric constant and low dielectric loss tangent can be obtained, and moldability can be improved. The terminal unsaturated group-modified polyphenylene ether preferably has a number average molecular weight of 1,000 or more and 7,000 or less. By setting the number average molecular weight to 7000 or less, fluidity during molding can be ensured. Moreover, by setting the number average molecular weight to 1000 or more, excellent dielectric properties (low dielectric constant and low dielectric loss tangent) and heat resistance intrinsic to polyphenylene ether resin can be obtained. Among them, the number average molecular weight of the terminal unsaturated group-modified polyphenylene ether is preferably 1,100 or more and 5,000 or less in order to obtain more excellent fluidity, heat resistance, and dielectric properties. More preferably, the unsaturated terminal group-modified polyphenylene ether has a number average molecular weight of 4,500 or less, and even more preferably, the terminal unsaturated group-modified polyphenylene ether has a number average molecular weight of 3,000 or less. Number average molecular weights are measured using gel permeation chromatography according to standard methods.

The terminal unsaturated group-modified polyphenylene ether preferably has a minimum melt viscosity of 50000 Pa·s or less. By setting the minimum melt viscosity to 50,000 Pa·s or less, fluidity can be secured, and multi-layer molding becomes possible. Although the lower limit of the lowest melt viscosity is not particularly defined, it may be, for example, 1000 Pa·s or more.

The terminal unsaturated group-modified polyphenylene ether preferably contains a polymer of structural units represented by the following general formula (2).

In general formula (2), R ₄₀₁ , R ₄₀₂ , R ₄₀₃ and R ₄₀₄ each independently represent an alkyl group having 6 or less carbon atoms, an aryl group, a halogen atom or a hydrogen atom.

The polymer may further contain at least one structural unit selected from the group consisting of structural units represented by general formulas (3) and (4).

In general formula (3), R ₄₀₅ , R ₄₀₆ , R ₄₀₇ , R ₄₁₁ and R ₄₁₂ each independently represent an alkyl group having 6 or less carbon atoms or a phenyl group. R ₄₀₈ , R ₄₀₉ and R ₄₁₀ each independently represent a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.

In general formula (4), R ₄₁₃ , R ₄₁₄ , R ₄₁₅ , R ₄₁₆ , R ₄₁₇ , R ₄₁₈ , R ₄₁₉ , and R ₄₂₀ 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 having 20 or less carbon atoms.
In relation to general formula (1), the above general formulas (2), (3) and (4) are preferably -(YO)- in general formula (1). -(YO)- has _n2 number (1 to 100) repeating units.

In general formula (1), X represents an aryl group (aromatic group), —(Y—O)n ₂ — represents a polyphenylene ether moiety, and R ₁ , R ₂ and R ₃ each independently represent a hydrogen atom. , an alkyl group, an alkenyl group or an alkynyl group, _n2 is an integer of 1 to 100, _n1 is an integer of 1 to 6, and _n3 is an integer of 1 to 4. Preferably, _n1 is an integer of 1 or more and 4 or less, more preferably _n1 is 1 or 2, and ideally _n1 is 1. Also, _n3 is preferably an integer of 1 or more and 3 or less, more preferably ₁ or 2, and ideally _n3 is 2.

An aromatic hydrocarbon group can be used as the aryl group for X in the general formula (1). Specifically, a group obtained by removing n _three hydrogen atoms from one ring structure selected from a benzene ring structure, a biphenyl structure, an indenyl ring structure, and a naphthalene ring structure (e.g., a phenyl group, a biphenyl group, indenyl group and naphthyl group) can be used, preferably a biphenyl group. Here, the aryl group includes a diphenyl ether group in which the above aryl group is bonded via an oxygen atom, a benzophenone group in which the aryl group is bonded via a carbonyl group, and a 2,2-diphenylpropane group bonded via an alkylene group. It's okay. In addition, the aryl group may be substituted with a general substituent such as an alkyl group (preferably an alkyl group having 1 to 6 carbon atoms, especially a methyl group), an alkenyl group, an alkynyl group or a halogen atom. However, since the "aryl group" is substituted on the polyphenylene ether moiety through an oxygen atom, the limit on the number of general substituents depends on the number of polyphenylene ether moieties.

The terminal unsaturated group-modified polyphenylene ether particularly preferably contains a compound represented by the structure of the following general formula (5).

In general formula (5), X is an aryl group (aromatic group), -(Y-O)n ₂ - each represents a polyphenylene ether moiety, and n ₂ each represents an integer of 1 to 100. show. —(YO)n ₂ — and n ₂ have the same meanings as in general formula (1). It may contain a plurality of different compounds of _n2 .

X in general formula (1) and general formula (5) is preferably general formula (6), general formula (7), or general formula (8), and general formula (1) and general formula (5) -(YO)n ₂ - in is a structure in which general formula (9) or general formula (10) is arranged, or a structure in which general formula (9) and general formula (10) are arranged randomly more preferred.

In general formula (7), R ₄₂₁ , R ₄₂₂ , R ₄₂₃ and R ₄₂₄ each independently represent a hydrogen atom or a methyl group. -B- is a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.

In general formula (8), -B- is a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.

The method for producing a terminal unsaturated group-modified polyphenylene ether having a structure represented by the general formula (5) is not particularly limited, for example, by oxidative coupling of a bifunctional phenol compound and a monofunctional phenol compound. It can be produced by vinylbenzyl etherifying the terminal phenolic hydroxyl group of the bifunctional phenylene ether oligomer obtained. Moreover, such terminal unsaturated group-modified polyphenylene ethers can be commercially available products, for example, OPE-2St1200 and OPE-2st2200 manufactured by Mitsubishi Gas Chemical Company, Inc. can be preferably used.

The content of the terminal unsaturated group-modified polyphenylene ether in the resin composition, when it is contained, is preferably 1 part by mass or more, and is 5 parts by mass or more with respect to 100 parts by mass of the resin solid content of the resin composition. is more preferably 10 parts by mass or more, still more preferably 15 parts by mass or more, and even more preferably 20 parts by mass or more. The upper limit of the content is preferably 70 parts by mass or less, more preferably 65 parts by mass or less, and may be 60 parts by mass or less. Such a range tends to effectively achieve a low dielectric constant, a low dielectric loss tangent and good moldability. The resin composition may contain only one type of terminal unsaturated group-modified polyphenylene ether, or may contain two or more types thereof. When two or more types are included, the total amount is preferably within the above range.

In the present invention, unless otherwise specified, the term "resin solid content in the resin composition" refers to the components of the resin composition excluding fillers, curing accelerators, and additives, and the resin solid content 100 parts by mass means that the total amount of components excluding fillers, curing accelerators, and additives in the resin composition is 100 parts by mass.

(maleimide compound)
The resin composition can contain a maleimide compound as a thermosetting compound. The maleimide compound is a compound having one or more (preferably 2 to 12, more preferably 2 to 6, still more preferably 2 to 4, still more preferably 2 or 3, still more preferably 2) maleimide groups in the molecule. If so, it is not particularly limited. Specific examples include N-phenylmaleimide, N-hydroxyphenylmaleimide, bis(4-maleimidophenyl)methane, 4,4′-diphenylmethanebismaleimide, bis(3,5-dimethyl-4-maleimidophenyl) Methane, bis(3,5-diethyl-4-maleimidophenyl)methane, phenylmethanemaleimide, o-phenylenebismaleimide, m-phenylenebismaleimide, p-phenylenebismaleimide, o-phenylenebiscitraconimide, m-phenylenebis Citraconimide, p-phenylenebiscitraconimide, 2,2-bis(4-(4-maleimidophenoxy)-phenyl)propane, 3,3'-diethyl-5,5'-dimethyl-4,4'-diphenylmethanebis Maleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, 4,4'-diphenyletherbismaleimide, 4,4'-diphenylsulfonebismaleimide , 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene, 4,4'-diphenylmethanebiscitraconimide, 2,2-bis[4-(4-citraconimide phenoxy)phenyl]propane, bis(3,5-dimethyl-4-citraconimidophenyl)methane, bis(3-ethyl-5-methyl-4-citraconimidophenyl)methane, bis(3,5-diethyl-4- Citraconimidophenyl)methane, maleimide compounds represented by general formula (11), general formula (12), general formula (13), general formula (14), general formula (15), and general formula (16), etc. is mentioned.

In general formula (11), R ₅₁ and R ₅₂ each independently represent a hydrogen atom or a methyl group, preferably a hydrogen atom. Further, in general formula (11), n ₄ represents an integer of 1 or more, the upper limit of n ₄ is usually 10, and from the viewpoint of solubility in organic solvents, the upper limit of n ₄ is preferably is 7, more preferably 5. The compound represented by the general formula (11) may contain two or more compounds with different _n4 .

In general formula (12), R ₆₀₁ , R ₆₀₂ , R ₆₀₃ , R ₆₀₄ , R ₆₀₅ , R ₆₀₆ , R ₆₀₇ , R ₆₀₈ , R ₆₀₉ , R ₆₁₀ , R ₆₁₁ and R ₆₁₂ are each independently a hydrogen atom; an alkyl group having 1 to 8 carbon atoms (e.g., methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, etc.), or a phenyl group; show. Among these, a group selected from the group consisting of a hydrogen atom, a methyl group and a phenyl group is preferred, one of a hydrogen atom and a methyl group is more preferred, and a hydrogen atom is even more preferred.
Moreover, it is an integer of 1<= _n5 <=10 in general formula (12). _n5 is preferably 4 or less, more preferably 3 or less, and even more preferably 2 or less from the viewpoint of further excellent solvent solubility. The compound represented by the general formula (12) may contain two or more compounds with different _n5 .

In general formula (13), R ₇₁ , R ₇₂ , R ₇₃ and R ₇₄ each independently represent a hydrogen atom, a methyl group or an ethyl group, and R ₈₁ and R ₈₂ each independently represent a hydrogen atom or a methyl group. R ₇₁ , R ₇₂ , R ₇₃ , and R ₇₄ are preferably methyl groups or ethyl groups from the standpoint of even better low dielectric constant and low dielectric loss tangent properties. Such compounds include, for example, 3,3'-diethyl-5,5'-dimethyl-4,4'-diphenylmethanebismaleimide.

In general formula (14), R ₉₁ and R ₉₂ each independently represent a hydrogen atom, a methyl group or an ethyl group. R ₉₁ and R ₉₂ are preferably methyl groups from the standpoint of further superior low dielectric constant and low dielectric loss tangent properties. Such compounds include, for example, 2,2-bis(4-(4-maleimidophenoxy)-phenyl)propane.

In general formula (15), _n6 represents an integer of 1 or more. The compound represented by the general formula (15) may contain two or more compounds with different _n6 .

In general formula (16), R ^M1 , R ^M2 , R ^M3 and R ^M4 each independently represent a hydrogen atom or an organic group. ^RM5 and ^RM6 each independently represent a hydrogen atom or an alkyl group. Ar ^M represents a divalent aromatic group. A is a 4- to 6-membered alicyclic group. ^RM7 and ^RM8 are each independently an alkyl group. mx is 1 or 2 and lx is 0 or 1. ^RM9 and ^RM10 each independently represent a hydrogen atom or an alkyl group. R ^M11 , R ^M12 , R ^M13 and R ^M14 each independently represent a hydrogen atom or an organic group. nx represents an integer of 1 or more and 20 or less. The compound represented by the general formula (16) may contain two or more compounds with different nx.

R ^M1 , R ^M2 , R ^M3 and R ^M4 in general formula (16) each independently represent a hydrogen atom or an organic group. The organic group here is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, a methyl group, an ethyl group, a propyl group, a butyl group. More preferred, and a methyl group is particularly preferred. R ^M1 and R ^M3 are each independently preferably an alkyl group, and R ^M2 and R ^M4 are preferably hydrogen atoms.
^RM5 and ^RM6 each independently represent a hydrogen atom or an alkyl group, preferably an alkyl group. The alkyl group here is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and especially a methyl group. preferable.
Ar 1 ^M represents a divalent aromatic group, preferably a phenylene group, a naphthalenediyl group, a phenanthenediyl group or an anthracenediyl group, more preferably a phenylene group, still more preferably an m-phenylene group. Ar ^M may have a substituent, and the substituent is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, a methyl group, Ethyl group, propyl group and butyl group are more preferred, and methyl group is particularly preferred. Among them, Ar 2 ^M is preferably unsubstituted.
A is a 4- to 6-membered alicyclic group, more preferably a 5-membered alicyclic group (preferably a group forming an indane ring in combination with a benzene ring). R ^{1 M7} and R ^{1 M8} are each independently an alkyl group, preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group. mx is 1 or 2, preferably 2; lx is 0 or 1, preferably 1;
R ^M9 and R ^M10 each independently represent a hydrogen atom or an alkyl group, preferably an alkyl group. The alkyl group here is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and especially a methyl group. preferable.
R ^M11 , R ^M12 , R ^M13 and R ^M14 each independently represent a hydrogen atom or an organic group. The organic group here is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, a methyl group, an ethyl group, a propyl group, a butyl group. More preferred, and a methyl group is particularly preferred. R ^M12 and R ^M13 are each independently preferably an alkyl group, and R ^M11 and R ^M14 are preferably hydrogen atoms.
nx represents an integer of 1 or more and 20 or less.

The compound represented by the general formula (16) is preferably a compound represented by the following general formula (17).

In general formula (17), R ^M21 , R ^M22 , R ^M23 and R ^M24 each independently represent a hydrogen atom or an organic group. ^RM25 and ^RM26 each independently represent a hydrogen atom or an alkyl group. R ^M27 , R ^M28 , R ^M29 and R ^M30 each independently represent a hydrogen atom or an organic group. R ^M31 and R ^M32 each independently represent a hydrogen atom or an alkyl group. R ^M33 , R ^M34 , R ^M35 and R ^M36 each independently represent a hydrogen atom or an organic group. R ^M37 , R ^M38 and R ^M39 each independently represent a hydrogen atom or an alkyl group. nx represents an integer of 1 or more and 20 or less.

R ^M21 , R ^M22 , R ^M23 and R ^M24 in general formula (17) each independently represent a hydrogen atom or an organic group. The organic group here is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, a methyl group, an ethyl group, a propyl group, a butyl group. More preferably, a methyl group is particularly preferred. R ^M21 and R ^M23 are preferably alkyl groups, and R ^M22 and R ^M24 are preferably hydrogen atoms.
^RM25 and ^RM26 each independently represent a hydrogen atom or an alkyl group, preferably an alkyl group. The alkyl group here is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and especially a methyl group. preferable.
R ^M27 , R ^M28 , R ^M29 and R ^M30 each independently represent a hydrogen atom or an organic group, preferably a hydrogen atom. The organic group here is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, a methyl group, an ethyl group, a propyl group, a butyl group. More preferably, a methyl group is particularly preferred.
R ^M31 and R ^M32 each independently represent a hydrogen atom or an alkyl group, preferably an alkyl group. The alkyl group here is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and especially a methyl group. preferable.
R ^M33 , R ^M34 , R ^M35 and R ^M36 each independently represent a hydrogen atom or an organic group. The organic group here is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, a methyl group, an ethyl group, a propyl group, a butyl group. More preferably, a methyl group is particularly preferred.
R ^M33 and R ^M36 are preferably hydrogen atoms, and R ^M34 and R ^M35 are preferably alkyl groups.
R ^M37 , R ^M38 and R ^M39 each independently represent a hydrogen atom or an alkyl group, preferably an alkyl group. The alkyl group here is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and especially a methyl group. preferable.
nx represents an integer of 1 or more and 20 or less.

The compound represented by the general formula (17) is preferably a compound represented by the following general formula (18).

In general formula (18), nx represents an integer of 1 or more and 20 or less.

The molecular weight of the compound represented by general formula (16) is preferably 500 or more, more preferably 600 or more, and even more preferably 700 or more. When the content is equal to or higher than the lower limit, dielectric properties and low water absorption tend to be further improved. Further, the molecular weight of the compound represented by the general formula (16) is preferably 10,000 or less, more preferably 9,000 or less, further preferably 7,000 or less, and even more preferably 5,000 or less. , 4000 or less. By adjusting the content to the above upper limit or less, heat resistance and handleability tend to be further improved.

Among these, the maleimide compound preferably contains at least one compound represented by general formulas (11), (12), (13), (14), (15) and (16). This is because low thermal expansion and heat resistance can be improved. A commercially available maleimide compound may be used, for example, "BMI-2300" manufactured by Daiwa Kasei Kogyo Co., Ltd. as a maleimide compound represented by the general formula (11), and a maleimide compound represented by the general formula (12). "MIR-3000" manufactured by Nippon Kayaku Co., Ltd., "BMI-70" manufactured by K-I Kasei Co., Ltd. as the maleimide compound represented by the general formula (13), and the maleimide compound represented by the general formula (14) "BMI-80" manufactured by K.I. Kasei Co., Ltd., as the maleimide compound represented by the general formula (15), "MIR-5000" manufactured by Nippon Kayaku Co., Ltd., and as the maleimide compound represented by the general formula (16), DIC "X9-450", "X9-470" and "NE-X-9470S" manufactured by the company can be preferably used.

The content of the maleimide compound in the resin composition can be appropriately set according to the desired properties, and is not particularly limited. When the content of the maleimide compound is contained, it is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and 10 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition. It is more preferable that it is above. The upper limit is preferably 90 parts by mass or less, more preferably 60 parts by mass or less, even more preferably 50 parts by mass or less, and may be 40 parts by mass or less. By setting it as such a range, there exists a tendency for high heat resistance and low water absorption to be exhibited more effectively. Only one type of maleimide compound may be used, or two or more types may be used. When two or more kinds are used, the total amount is preferably within the above range.

(Cyanate ester compound)
The resin composition can contain a cyanate ester compound as a thermosetting compound. The cyanate ester compound has one or more (preferably 2 to 12, more preferably 2 to 6, more preferably 2 to 4, still more preferably 2 or 3, still more preferably 2) cyanato groups ( The resin is not particularly limited as long as it has an aromatic portion substituted with a cyanate ester group) in the molecule. Examples of cyanate ester compounds include compounds represented by general formula (19).

In general formula (19), Ar ₁ and Ar ₂ are each independently a phenylene group optionally having a substituent, a naphthylene group optionally having a substituent or a biphenylene group optionally having a substituent represents R ₁₀₁ and R ₁₀₂ each independently represent a hydrogen atom, an optionally substituted C 1-6 alkyl group, an optionally substituted C 6-12 aryl group, or a substituted an alkoxy group having 1 to 4 carbon atoms which may be substituted, an aralkyl group which may have a substituent in which an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 12 carbon atoms are bonded, or an aralkyl group having 1 to 6 carbon atoms. and an aryl group having 6 to 12 carbon atoms, which may have a substituent. n ₇₁ represents the number of cyanato groups bonded to Ar ₁ and is an integer of 1-3. n ₇₂ represents the number of cyanato groups attached to Ar ₂ and is an integer of 1-3.
n ₇₃ represents the number of R ₁₀₁ bonded to Ar ₁ , 4-n ₇₁ when Ar ₁ is a phenylene group, 6-n ₇₁ when it is a naphthylene group, and 8-n ₇₁ when it is a biphenylene group. n ₇₄ represents the number of R ₁₀₂ bound to Ar ₂ , 4-n ₇₂ when Ar ₂ is a phenylene group, 6-n ₇₂ when it is a naphthylene group, and 8-n ₇₂ when it is a biphenylene group. _n8 represents the average repetition number and is an integer from 0 to 50. The cyanate ester compound may be a mixture of compounds with different _n8 . Each Z is independently 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 (-N -RN- etc.), carbonyl group (-CO-), carboxy group (-C(=O)O-), carbonyl dioxide group (-OC(=O)O-), sulfonyl group (-SO ₂ -), and any one of a divalent sulfur atom or a divalent oxygen atom.

The alkyl group for R ₁₀₁ and R ₁₀₂ in formula (19) may have a linear structure, a branched chain structure, or a cyclic structure (such as a cycloalkyl group). Further, the hydrogen atom in the alkyl group in the general formula (19) and the aryl group in R ₁₀₁ and R ₁₀₂ is 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, a cyano group, or the like. may have been
Specific examples of alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, 1-ethylpropyl and 2,2-dimethylpropyl. group, cyclopentyl group, hexyl group, cyclohexyl group, trifluoromethyl group and the like.
Specific examples of aryl groups include phenyl, xylyl, mesityl, naphthyl, phenoxyphenyl, ethylphenyl, o-, m- or p-fluorophenyl, dichlorophenyl, dicyanophenyl and trifluorophenyl. group, methoxyphenyl group, o-, m- or p-tolyl group, and the like.
Specific examples of alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy and tert-butoxy groups.

Specific examples of the divalent organic group for Z in the general formula (19) include a methylene group, ethylene group, trimethylene group, cyclopentylene group, cyclohexylene group, trimethylcyclohexylene group, biphenylylmethylene group, dimethylmethylene- A phenylene-dimethylmethylene group, a fluorenediyl group, a phthalidodiyl group and the like can be mentioned. A hydrogen atom in the 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, a cyano group, or the like. Examples of the divalent organic group having 1 to 10 nitrogen atoms in Z of the general formula (19) include an imino group and a polyimide group.

In addition, Z in general formula (19) includes those having a structure represented by general formula (20) or general formula (21).

In general formula (20), Ar ₃ is selected from any one of a phenylene group, a naphthylene group and a biphenylene group. R ₁₀₃ , R ₁₀₄ , R ₁₀₇ and R ₁₀₈ each independently represents at least one of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a trifluoromethyl group and a phenolic hydroxy group; is selected from any one of aryl groups substituted with one. Each of R ₁₀₅ and R ₁₀₆ is 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 hydroxy group. . Although n ₉ represents an integer of 0 to 5, the cyanate ester compound may be a mixture of compounds in which n ₉ has different groups.

In general formula (21), Ar ₄ is selected from any one of a phenylene group, a naphthylene group and a biphenylene group. R ₁₀₉ and R ₁₁₀ each independently represents 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, a hydroxy group, and trifluoromethyl and an aryl group substituted with at least one of a cyanato group. Although _n10 represents an integer of 0 to 5, the cyanate ester compound may be a mixture of compounds in which _n10 has different groups.

Furthermore, Z in general formula (19) includes a divalent group represented by the following formula.

In the formula, _n11 represents an integer of 4-7. R ₁₁₁ and R ₁₁₂ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Specific examples of Ar ₃ of general formula (20) and Ar ₄ of general formula (21) include a 1,4-phenylene group, a 1,3-phenylene group, a 4,4'-biphenylene group, a 2,4'- biphenylene group, 2,2'-biphenylene group, 2,3'-biphenylene group, 3,3'-biphenylene group, 3,4'-biphenylene group, 2,6-naphthylene group, 1,5-naphthylene group, 1 ,6-naphthylene group, 1,8-naphthylene group, 1,3-naphthylene group, 1,4-naphthylene group and the like. The alkyl group and aryl group for R ₁₀₃ to R ₁₀₈ in general formula (20) and R ₁₀₉ and R ₁₁₀ in general formula (21) are the same as those described for general formula (19).

Examples of the cyanate ester compound represented by the general formula (19) include a phenol novolak-type cyanate ester compound, a naphthol aralkyl-type cyanate ester compound, a biphenyl aralkyl-type cyanate ester compound, a naphthylene ether-type cyanate ester compound, Examples include xylene resin type cyanate ester compounds, adamantane skeleton type cyanate ester compounds, bisphenol A type cyanate ester compounds, diallylbisphenol A type cyanate ester compounds, naphthol aralkyl type cyanate ester compounds, and the like.

Specific examples of the cyanate ester compound represented by the general formula (19) include cyanatobenzene, 1-cyanato-2-, 1-cyanato-3-, or 1-cyanato-4-methylbenzene, 1-cyanato -2-, 1-cyanato-3-, or 1-cyanato-4-methoxybenzene, 1-cyanato-2,3-, 1-cyanato-2,4-, 1-cyanato-2,5-, 1- Cyanato-2,6-,1-cyanato-3,4- or 1-cyanato-3,5-dimethylbenzene, cyanatoethylbenzene, cyanatobutylbenzene, cyanatooctylbenzene, cyanatononylbenzene, 2-(4 -cyanaphenyl)-2-phenylpropane (cyanate of 4-α-cumylphenol), 1-cyanato-4-cyclohexylbenzene, 1-cyanato-4-vinylbenzene, 1-cyanato-2- or 1-cyanato- 3-chlorobenzene, 1-cyanato-2,6-dichlorobenzene, 1-cyanato-2-methyl-3-chlorobenzene, cyanatonitrobenzene, 1-cyanato-4-nitro-2-ethylbenzene, 1-cyanato-2-methoxy -4-allylbenzene (eugenol cyanate), methyl (4-cyanatophenyl) sulfide, 1-cyanato-3-trifluoromethylbenzene, 4-cyanatobiphenyl, 1-cyanato-2- or 1-cyanato-4 -acetylbenzene, 4-cyanatobenzaldehyde, 4-cyanatobenzoic acid methyl ester, 4-cyanatobenzoic acid phenyl ester, 1-cyanato-4-acetaminobenzene, 4-cyanatobenzophenone, 1-cyanato-2,6- Di-tert-butylbenzene, 1,2-dicyanatobenzene, 1,3-dicyanatobenzene, 1,4-dicyanatobenzene, 1,4-dicyanato-2-tert-butylbenzene, 1,4-dicyanato- 2,4-dimethylbenzene, 1,4-dicyanato-2,3,4-dimethylbenzene, 1,3-dicyanato-2,4,6-trimethylbenzene, 1,3-dicyanato-5-methylbenzene, 1- cyanato or 2-cyanatonaphthalene, 1-cyanato-4-methoxynaphthalene, 2-cyanato-6-methylnaphthalene, 2-cyanato-7-methoxynaphthalene, 2,2′-dicyanato-1,1′-binaphthyl, 1, 3-,1,4-,1,5-,1,6-,1,7-,2,3-,2,6- or 2,7-dicyanatocinaphthalene, 2,2′- or 4, 4'-dicyanatobiphenyl, 4,4'-dicyanatooctafluorobiphenyl, 2,4'- or 4,4'-dicyanatodiphenylmethane, bis(4-cyanato-3,5-dimethylphenyl)methane, 1, 1-bis(4-cyanatophenyl)ethane, 1,1-bis(4-cyanatophenyl)propane, 2,2-bis(4-cyanatophenyl)propane, 2,2-bis(3-allyl- 4-cyanatophenyl)propane, 2,2-bis(4-cyanato-3-methylphenyl)propane, 2,2-bis(2-cyanato-5-biphenylyl)propane, 2,2-bis(4- cyanatophenyl)hexafluoropropane, 2,2-bis(4-cyanato-3,5-dimethylphenyl)propane, 1,1-bis(4-cyanatophenyl)butane, 1,1-bis(4-cyanatophenyl) anatophenyl)isobutane, 1,1-bis(4-cyanatophenyl)pentane, 1,1-bis(4-cyanatophenyl)-3-methylbutane, 1,1-bis(4-cyanatophenyl)-2 -methylbutane, 1,1-bis(4-cyanatophenyl)-2,2-dimethylpropane, 2,2-bis(4-cyanatophenyl)butane, 2,2-bis(4-cyanatophenyl)pentane , 2,2-bis(4-cyanatophenyl)hexane, 2,2-bis(4-cyanatophenyl)-3-methylbutane, 2,2-bis(4-cyanatophenyl)-4-methylpentane, 2,2-bis(4-cyanatophenyl)-3,3-dimethylbutane, 3,3-bis(4-cyanatophenyl)hexane, 3,3-bis(4-cyanatophenyl)heptane, 3, 3-bis(4-cyanatophenyl)octane, 3,3-bis(4-cyanatophenyl)-2-methylpentane, 3,3-bis(4-cyanatophenyl)-2-methylhexane, 3, 3-bis(4-cyanatophenyl)-2,2-dimethylpentane, 4,4-bis(4-cyanatophenyl)-3-methylheptane, 3,3-bis(4-cyanatophenyl)-2 -methylheptane, 3,3-bis(4-cyanatophenyl)-2,2-dimethylhexane, 3,3-bis(4-cyanatophenyl)-2,4-dimethylhexane, 3,3-bis( 4-cyanatophenyl)-2,2,4-trimethylpentane, 2,2-bis(4-cyanatophenyl)-1,1,1,3,3,3-hexafluoropropane, bis(4- anatophenyl)phenylmethane, 1,1-bis(4-cyanatophenyl)-1-phenylethane, bis(4-cyanatophenyl)biphenylmethane, 1,1-bis(4-cyanatophenyl)cyclopentane, 1,1-bis(4-cyanatophenyl)cyclohexane, 2,2-bis(4-cyanato-3-isopropylphenyl)propane, 1,1-bis(3-cyclohexyl-4-cyanatophenyl)cyclohexane, bis (4-cyanatophenyl)diphenylmethane, bis(4-cyanatophenyl)-2,2-dichloroethylene, 1,3-bis[2-(4-cyanatophenyl)-2-propyl]benzene, 1,4- Bis[2-(4-cyanatophenyl)-2-propyl]benzene, 1,1-bis(4-cyanatophenyl)-3,3,5-trimethylcyclohexane, 4-[bis(4-cyanatophenyl) ) methyl]biphenyl, 4,4-dicyanatobenzophenone, 1,3-bis(4-cyanatophenyl)-2-propen-1-one, bis(4-cyanatophenyl) ether, bis(4-cyanato phenyl) sulfide, bis(4-cyanatophenyl) sulfone, 4-cyanatobenzoic acid-4-cyanatophenyl ester (4-cyanatophenyl-4-cyanatobenzoate), bis-(4-cyanatophenyl) carbonate , 1,3-bis(4-cyanatophenyl)adamantane, 1,3-bis(4-cyanatophenyl)-5,7-dimethyladamantane, 3,3-bis(4-cyanatophenyl)isobenzofuran- 1(3H)-one (cyanate of phenolphthalein), 3,3-bis(4-cyanato-3-methylphenyl)isobenzofuran-1(3H)-one (cyanate of o-cresolphthalein), 9, 9-bis(4-cyanatophenyl)fluorene, 9,9-bis(4-cyanato-3-methylphenyl)fluorene, 9,9-bis(2-cyanato-5-biphenylyl)fluorene, tris(4- cyanatophenyl)methane, 1,1,1-tris(4-cyanatophenyl)ethane, 1,1,3-tris(4-cyanatophenyl)propane, α,α,α'-tris(4-cyanatophenyl) anatophenyl)-1-ethyl-4-isopropylbenzene, 1,1,2,2-tetrakis(4-cyanatophenyl)ethane, tetrakis(4-cyanatophenyl)methane, 2,4,6-tris(N -methyl-4-cyanatoanilino)-1,3,5-triazine, 2,4-bis(N-methyl-4-cyanatoanilino)-6-(N-methylanilino)-1,3,5-triazine, bis(N -4-cyanato-2-methylphenyl)-4,4'-oxydiphthalimide, bis(N-3-cyanato-4-methylphenyl)-4,4'-oxydiphthalimide, bis(N-4- anatophenyl)-4,4'-oxydiphthalimide, bis(N-4-cyanato-2-methylphenyl)-4,4'-(hexafluoroisopropylidene)diphthalimide, tris(3,5-dimethyl-4 -cyanatobenzyl)isocyanurate, 2-phenyl-3,3-bis(4-cyanatophenyl)phthalimidine, 2-(4-methylphenyl)-3,3-bis(4-cyanatophenyl)phthalimidine, 2 -phenyl-3,3-bis(4-cyanato-3-methylphenyl)phthalimidine, 1-methyl-3,3-bis(4-cyanatophenyl)indolin-2-one, 2-phenyl-3,3- Bis(4-cyanatophenyl)indolin-2-one, phenol novolac resin or cresol novolac resin (by a known method, phenol, alkyl-substituted phenol or halogen-substituted phenol and formaldehyde compound such as formalin or paraformaldehyde are mixed in an acidic solution. in the reaction), trisphenol novolak resin (hydroxybenzaldehyde and phenol reacted in the presence of an acidic catalyst), fluorene novolac resin (fluorenone compound and 9,9-bis (hydroxyaryl) fluorenes and in the presence of an acidic catalyst), phenol aralkyl resins, cresol aralkyl resins, naphthol aralkyl resins and biphenyl aralkyl resins (by known methods, such as represented by Ar ₅ —(CH ₂ Z′) ₂ Bishalogenomethyl compounds and phenolic compounds reacted with or without an acidic catalyst, bis(alkoxymethyl) compounds represented by Ar ₅ —(CH ₂ OR) ₂ and Ar ₅ —(CH ₂ OH) A product obtained by reacting a bis(hydroxymethyl) compound represented by ₂ with a phenol compound in the presence of an acidic catalyst, or a product obtained by polycondensing an aromatic aldehyde compound, an aralkyl compound, or a phenol compound), phenol Modified xylene formaldehyde resin (by a known method, a xylene formaldehyde resin and a phenol compound are reacted in the presence of an acidic catalyst), modified naphthalene formaldehyde resin (by a known method, a naphthalene formaldehyde resin and a hydroxy-substituted aromatic compound are reacted with an acidic reacted in the presence of a catalyst), phenol-modified dicyclopentadiene resin, phenolic resin having a polynaphthylene ether structure (by a known method, polyhydric hydroxynaphthalene having two or more phenolic hydroxy groups in one molecule A compound obtained by dehydrating and condensing a compound in the presence of a basic catalyst) and a phenolic resin obtained by cyanate esterification in the same manner as described above, but are not particularly limited. These cyanate ester compounds may be used alone or in combination of two or more.

Among these, phenol novolak-type cyanate ester compounds, naphthol aralkyl-type cyanate ester compounds, naphthylene ether-type cyanate ester compounds, bisphenol A-type cyanate ester compounds, bisphenol M-type cyanate ester compounds, diallyl bisphenol-type cyanate ester compounds is preferred, and a naphthol aralkyl-type cyanate ester compound is particularly preferred. Cured products of resin compositions using these cyanate ester compounds have excellent properties such as low dielectric properties (low dielectric constant and low dielectric loss tangent).

The content of the cyanate ester compound in the resin composition can be appropriately set according to the desired properties, and is not particularly limited. Specifically, when the content of the cyanate ester compound is contained, it is preferably 0.1 parts by mass or more, and 0.5 parts by mass or more, relative to 100 parts by mass of the resin solid content in the resin composition. is more preferably 1 part by mass or more, and may be 3 parts by mass or more, or 5 parts by mass or more. In addition, the upper limit of this content is preferably 90 parts by mass or less, more preferably 80 parts by mass or less, even more preferably less than 70 parts by mass, even more preferably 60 parts by mass or less, and 50 parts by mass. Hereinafter, it may be 40 parts by mass or less. By setting it to such a range, more excellent low dielectric constant property and low dielectric loss tangent property can be provided. Only one type of cyanate ester compound may be used, or two or more types may be used. When two or more kinds are used, the total amount is preferably within the above range.

(Epoxy resin)
The resin composition can contain an epoxy resin as a thermosetting compound. As the epoxy resin, one or more (preferably 2 to 12, more preferably 2 to 6, still more preferably 2 to 4, still more preferably 2 or 3, still more preferably 2) epoxy groups per molecule. It is not particularly limited as long as it is a compound or resin having, for example, bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, bisphenol A novolac type epoxy resin , glycidyl ester type epoxy resin, aralkyl novolac type epoxy resin, biphenyl aralkyl type epoxy resin, naphthylene ether type epoxy resin, cresol novolak type epoxy resin, polyfunctional phenol type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, naphthalene skeleton-modified novolak-type epoxy resin, phenol aralkyl-type epoxy resin, naphthol-aralkyl-type epoxy resin, dicyclopentadiene-type epoxy resin, biphenyl-type epoxy resin, alicyclic epoxy resin, polyol-type epoxy resin, phosphorus-containing epoxy resin, glycidylamine, Examples include compounds obtained by epoxidizing double bonds such as glycidyl esters and butadiene, and compounds obtained by reacting hydroxyl group-containing silicone resins with epichlorohydrin. These epoxy resins may be used alone or in combination of two or more. Among these, biphenyl aralkyl epoxy resins, naphthylene ether epoxy resins, polyfunctional phenol epoxy resins, and naphthalene epoxy resins are preferred from the viewpoint of further improving flame retardancy and heat resistance.

(Phenolic resin)
The resin composition can contain a phenolic resin as a thermosetting compound. As the phenolic resin, one or more (preferably 2 to 12, more preferably 2 to 6, still more preferably 2 to 4, still more preferably 2 or 3, still more preferably 2) phenolic hydroxy It is not particularly limited as long as it is a compound or resin having a group. , glycidyl ester type phenolic resin, aralkyl novolak phenolic resin, biphenyl aralkyl type phenolic resin, cresol novolac type phenolic resin, polyfunctional phenolic resin, naphthol resin, naphthol novolak resin, polyfunctional naphthol resin, anthracene type phenolic resin, naphthalene skeleton modified novolac type phenol resin, phenol aralkyl type phenol resin, naphthol aralkyl type phenol resin, dicyclopentadiene type phenol resin, biphenyl type phenol resin, alicyclic phenol resin, polyol type phenol resin, and phosphorus-containing phenol resins. These phenol resins may be used alone or in combination of two or more. Among these, from the viewpoint of further improving flame resistance, at least one selected from the group consisting of biphenylaralkyl-type phenolic resins, naphtholaralkyl-type phenolic resins, and phosphorus-containing phenolic resins is preferred.

(thermoplastic elastomer)
The resin composition can contain a thermoplastic elastomer. Thermoplastic elastomers contain styrene monomer units. By including styrene monomer units, the solubility of the thermoplastic elastomer in the resin composition is improved. Styrene monomers include styrene, α-methylstyrene, p-methylstyrene, divinylbenzene (vinylstyrene), N,N-dimethyl-p-aminoethylstyrene, N,N-diethyl-p-aminoethylstyrene and the like. Among these, styrene, α-methylstyrene, and p-methylstyrene are preferred from the viewpoint of availability and productivity. Among these, styrene is particularly preferred.
The content of styrene monomer units (styrene ratio) in the thermoplastic elastomer is preferably in the range of 10 to 50% by mass, more preferably in the range of 13 to 45% by mass, more preferably 15 to 40% by mass of the total monomer units. % range is more preferred. If the content of styrene monomer units is 50% by mass or less, the adhesiveness and adhesiveness to substrates and the like will be better. In addition, if it is 10% by mass or more, it is preferable because the increase in adhesion can be suppressed, adhesive residue and stop marks are less likely to occur, and the easy peeling property between the adhesive surfaces tends to be improved.
The thermoplastic elastomer may contain only one type of styrene monomer unit, or may contain two or more types. When two or more kinds are included, the total amount is preferably within the above range.
The method for measuring the content of styrene monomer units in the thermoplastic elastomer of the present embodiment can be referred to the description in WO 2017/126469, the content of which is incorporated herein. The same applies to the conjugated diene monomer unit and the like, which will be described later.

The thermoplastic elastomer contains conjugated diene monomer units. Containing the conjugated diene monomer unit improves the solubility of the thermoplastic elastomer in the resin composition. The conjugated diene monomer is not particularly limited as long as it is a diolefin having a pair of conjugated double bonds. Conjugated diene monomers are, for example, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl- 1,3-pentadiene, 1,3-hexadiene, and farnesene are included, with 1,3-butadiene and isoprene being preferred, and 1,3-butadiene being more preferred.
The thermoplastic elastomer may contain only one type of conjugated diene monomer unit, or may contain two or more types.

In the above thermoplastic elastomer, the mass ratio of styrene monomer units and conjugated diene monomer units is in the range of styrene monomer units/conjugated diene monomer units=5/95 to 80/20. , more preferably in the range of 7/93 to 77/23, and even more preferably in the range of 10/90 to 70/30. When the mass ratio of the styrene polymer unit and the conjugated diene monomer unit is in the range of 5/95 to 80/20, it is possible to suppress the increase in adhesion, maintain high adhesive strength, and easily peel the adhesive surfaces. get better.

The thermoplastic elastomer may or may not contain other monomer units in addition to the styrene monomer units and the conjugated diene monomer units. Examples of other monomer units include aromatic vinyl compound units other than styrene monomer units.
In the thermoplastic elastomer, the total amount of styrene monomer units and conjugated diene monomer units is preferably 90% by mass or more, more preferably 95% by mass or more, more preferably 97% by mass. % or more, more preferably 99 mass % or more.
As described above, the thermoplastic elastomer may contain only one kind of styrene monomer units and conjugated diene monomer units, or may contain two or more kinds thereof. When two or more types are included, the total amount is preferably within the above range.

The thermoplastic elastomer used in this embodiment may be a block polymer or a random polymer. Moreover, even if the conjugated diene monomer unit is a hydrogenated elastomer in which the conjugated diene monomer unit is hydrogenated, it may be an unhydrogenated elastomer in which it is not hydrogenated, or a partially hydrogenated elastomer in which it is partially hydrogenated. good.

Examples of commercially available thermoplastic elastomers used in this embodiment include SEPTON (registered trademark) 2104 manufactured by Kuraray Co., Ltd., DYNARON (registered trademark) 9901P, TR2250 manufactured by JSR Corporation, and the like.

When the resin composition contains a thermoplastic elastomer, the content thereof is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and 5 parts by mass or more with respect to 100 parts by mass of the resin solid content. More preferably, it is 8 parts by mass or more, and even more preferably 10 parts by mass or more. When the content is equal to or higher than the lower limit, low dielectric properties tend to be further improved. In addition, the upper limit of the content of the thermoplastic elastomer is preferably 45 parts by mass or less, more preferably 40 parts by mass or less, and 35 parts by mass or less with respect to 100 parts by mass of the resin solid content. is more preferably 32 parts by mass or less, and even more preferably 28 parts by mass or less. By making it below the said upper limit, there exists a tendency for heat resistance to improve more.
The resin composition may contain only one type of thermoplastic elastomer, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

(filler)
The resin composition may contain a filler in order to improve low dielectric constant properties and low dielectric loss tangent properties. As the filler, known fillers can be used as appropriate, and the type thereof is not particularly limited, and fillers commonly used in the art can be suitably used. Specifically, silicas such as natural silica, fused silica, synthetic silica, amorphous silica, aerosil, hollow silica, white carbon, titanium white, zinc oxide, magnesium oxide, zirconium oxide, boron nitride, aggregated boron nitride, silicon nitride , Aluminum Nitride, Barium Sulfate, Aluminum Hydroxide, Heat Treated Aluminum Hydroxide (Aluminum Hydroxide Heat Treated to Reduce Some of the Water of Crystallization), Boehmite, Metal Hydrates such as Magnesium Hydroxide, Oxides Molybdenum and molybdenum compounds such as 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, short glass fibers (including glass fine powders such as E-glass, T-glass, D-glass, S-glass, Q-glass, etc.), hollow In addition to inorganic fillers such as glass and spherical glass, organic fillers such as styrene, butadiene, and acrylic rubber powders, core-shell rubber powders, silicone resin powders, silicone rubber powders, and silicone compound powders. is mentioned. These fillers may be used alone or in combination of two or more.
Among these, one or more selected from the group consisting of silica, aluminum hydroxide, boehmite, magnesium oxide and magnesium hydroxide is suitable. By using these fillers, properties such as thermal expansion properties, dimensional stability and flame retardancy of the resin composition are improved.

The content of the filler in the resin composition can be appropriately set according to the desired properties, and is not particularly limited. It is preferably at least 1 part. The upper limit is preferably 1600 parts by mass or less, more preferably 500 parts by mass or less, and particularly preferably 300 parts by mass or less. Alternatively, the filler may be from 75 parts by weight to 250 parts by weight, or from 100 parts by weight to 200 parts by weight. By setting the content of the filler within this range, the moldability of the resin composition is improved. The resin composition may contain only one filler, or may contain two or more fillers. When two or more types are included, the total amount is preferably within the above range.

When using fillers, it is preferable to use at least one selected from the group consisting of silane coupling agents and wetting and dispersing agents. As the silane coupling agent, those generally used for surface treatment of inorganic substances can be suitably used, and the type thereof is not particularly limited. Specifically, aminosilanes such as γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-(3,4 -epoxysilanes such as epoxycyclohexyl)ethyltrimethoxysilane, vinylsilanes such as γ-methacryloxypropyltrimethoxysilane, vinyl-tri(β-methoxyethoxy)silane, N-β-(N-vinylbenzylaminoethyl)- Examples include cationic silanes such as γ-aminopropyltrimethoxysilane hydrochloride, phenylsilanes, and the like. The silane coupling agents may be used alone or in combination of two or more. As the wetting and dispersing agent, those generally used for paints can be suitably used, and the type thereof is not particularly limited. Preferably, a copolymer-based wetting and dispersing agent is used, specific examples of which include Disperbyk-110, 111, 161, 180, 2009, 2152, BYK-W996, BYK-W9010 manufactured by BYK-Chemie Japan Co., Ltd. BYK-W903, BYK-W940 and the like. Wetting and dispersing agents may 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 with respect to 100 parts by mass of the resin solid content in the resin composition. The content of the dispersant (particularly the wetting and dispersing agent) is not particularly limited, and may be, for example, about 0.5 parts by mass to 5 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition. .

(styrene oligomer)
The resin composition may contain a styrene oligomer. The styrene oligomer according to the present embodiment is obtained by polymerizing at least one selected from the group consisting of styrene, styrene derivatives, and vinyltoluene, and has a number average molecular weight of 178 to 1,600 and an average number of aromatic rings of 2 to 14. , the total amount of 2 to 14 aromatic rings is 50% by mass or more, and the boiling point is 300° C. or more and does not have a branched structure. By including a styrene oligomer, low dielectric constant and low dielectric loss tangent can be improved. The "styrene oligomer" used in this embodiment is distinguished from the above-mentioned "thermoplastic elastomer".

Examples of styrene oligomers include styrene polymers, vinyltoluene polymers, α-methylstyrene polymers, vinyltoluene-α-methylstyrene polymers, and styrene-α-styrene polymers. As the styrene polymer, commercially available products may be used. Examples include FTR-8100 (manufactured by Mitsui Chemicals, Inc.) and FTR-8120 (manufactured by Mitsui Chemicals, Inc.). Examples of the vinyltoluene-α-methylstyrene polymer include Picotex LC (manufactured by Eastman Chemical Co.). Examples of α-methylstyrene polymers include Crystalex 3070 (manufactured by Eastman Chemical Co.), Crystalex 3085 (manufactured by Eastman Chemical Co.), Crystalex (3100), Crystalex 5140 (manufactured by Eastman Chemical Co.) and FMR. -0100 (manufactured by Mitsui Chemicals, Inc.) and FMR-0150 (manufactured by Mitsui Chemicals, Inc.). Further, the styrene-α-styrene polymer includes FTR-2120 (manufactured by Mitsui Chemicals, Inc.). These styrene oligomers may be used alone or in combination of two or more.

The content of the styrene oligomer in the resin composition, when it is contained, is 1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the resin solid content of the resin composition. From the viewpoint of dielectric loss tangent and chemical resistance, it is preferably 5 parts by mass or more and 20 parts by mass or less, and may be 15 parts by mass or less. The resin composition may contain only one type of styrene oligomer, or may contain two or more types thereof. When two or more types are included, the total amount is preferably within the above range.

(Flame retardants)
The resin composition may contain a flame retardant to improve flame resistance. Known flame retardants can be used, for example, brominated epoxy resin, brominated polycarbonate, brominated polystyrene, brominated styrene, brominated phthalimide, tetrabromobisphenol A, pentabromobenzyl (meth)acrylate, pentabromo Halogen flame retardants such as toluene, tribromophenol, hexabromobenzene, decabromodiphenyl ether, bis-1,2-pentabromophenylethane, chlorinated polystyrene, chlorinated paraffin, red phosphorus, tricresyl phosphate, triphenyl phosphate , cresyl diphenyl phosphate, trixylenyl phosphate, trialkyl phosphate, dialkyl phosphate, tris(chloroethyl) phosphate, phosphazene, 1,3-phenylenebis(2,6-dixylenyl phosphate), 10-(2,5- Dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, phosphorus-based flame retardants, aluminum hydroxide, magnesium hydroxide, partial boehmite, boehmite, zinc borate, antimony trioxide, etc. Silicone-based flame retardants such as flame retardants, silicone rubbers, and silicone resins can be used. These flame retardants may be used alone or in combination of two or more. Among these, phosphorus-based flame retardants are preferred, and 1,3-phenylenebis(2,6-dixylenyl phosphate) is particularly preferred because it hardly impairs low dielectric properties. The phosphorus content in the resin composition is preferably 0.1% by mass to 5% by mass.

The content of the flame retardant, when contained, is preferably 1 part by mass or more, more preferably 5 parts by mass or more, relative to 100 parts by mass of the resin solid content in the resin composition. The upper limit of the content is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and may be 15 parts by mass or less. Only one flame retardant may be used, or two or more flame retardants may be used. When two or more are used, the total amount is preferably within the above range.

(other ingredients)
Furthermore, the resin composition contains a thermoplastic elastomer ( hereinafter referred to as "other thermoplastic elastomer"), a curing accelerator, an organic solvent, and the like. By using these together, desired properties such as low dielectric properties can be improved. In the resin composition, the total amount of the polyphenylene ether compound other than the polyphenylene ether compound and the other thermoplastic elastomer is preferably 3% by mass or less, more preferably 1% by mass or less, based on the solid content of the resin. . With such a configuration, the effects of the present invention are exhibited more effectively.

(oxetane resin)
The oxetane resin is not particularly limited, and examples thereof include oxetane, alkyloxetane (eg, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, 3,3-dimethyloxatane, etc.), 3-methyl- 3-Methoxymethyloxetane, 3,3-di(trifluoromethyl)perfluoxetane, 2-chloromethyloxetane, 3,3-bis(chloromethyl)oxetane, biphenyl type oxetane, OXT-101 (product of Toagosei Co., Ltd.) ), OXT-121 (a product of Toagosei Co., Ltd.), and the like. These oxetane resins may be used alone or in combination of two or more.

(Benzoxazine compound)
The benzoxazine compound is not particularly limited as long as it is a compound having two or more dihydrobenzoxazine rings in one molecule. Benzoxazine BF-BXZ (product of Konishi Chemical Co., Ltd.), bisphenol S-type benzoxazine BS-BXZ (product of Konishi Chemical Co., Ltd.), and the like. These benzoxazine compounds may be used alone or in combination of two or more.

(Other thermoplastic elastomers)
Other thermoplastic elastomers refer to elastomers other than the thermoplastic elastomers described above. Other thermoplastic elastomers include, for example, at least one selected from the group consisting of polyisoprene, polybutadiene, butyl rubber, ethylene propylene rubber, fluororubber, silicone rubber, hydrogenated compounds thereof, and alkyl compounds thereof. Among these, at least one selected from the group consisting of polyisoprene, polybutadiene, butyl rubber, and ethylene propylene rubber is more preferable from the viewpoint of better compatibility with the polyphenylene ether compound.

(Curing accelerator)
The resin composition may contain a curing accelerator for appropriately adjusting the curing speed. Examples of curing accelerators include those commonly used as curing accelerators such as maleimide compounds and epoxy resins. iron, nickel octylate, manganese octylate, etc.), phenolic compounds (e.g., phenol, xylenol, cresol, resorcinol, catechol, octylphenol, nonylphenol, etc.), alcohols (e.g., 1-butanol, 2-ethylhexanol, etc.), imidazole (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 such as adducts of carboxylic acids of these imidazoles or their acid anhydrides, amines (e.g., dicyandiamide, benzyldimethylamine, 4-methyl-N,N-dimethylbenzylamine, etc.), phosphorus compounds (e.g., phosphine compounds, phosphine oxide compounds, phosphonium salt compounds, diphosphine compounds, etc.), epoxy-imidazole adduct compounds , peroxides (e.g., benzoyl peroxide, p-chlorobenzoyl peroxide, di-t-butyl peroxide, diisopropyl peroxycarbonate, di-2-ethylhexyl peroxycarbonate, etc.), azo compounds (e.g., azobisiso butyronitrile, etc.). A hardening accelerator may be used independently or may use 2 or more types together. The content of the curing accelerator may generally be about 0.005 parts by mass to 10 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition.

In addition to the above components, the resin composition may contain thermosetting resins, thermoplastic resins, various polymer compounds such as oligomers thereof, and various additives. Additives include UV absorbers, antioxidants, photopolymerization initiators, fluorescent brighteners, photosensitizers, dyes, pigments, thickeners, flow control agents, lubricants, antifoaming agents, dispersants, and leveling agents. agents, brighteners, polymerization inhibitors, and the like. These additives may be used alone or in combination of two or more.

<Organic solvent>
The prepreg may contain an organic solvent. In this case, the resin composition according to the present embodiment is in a form (solution or varnish) in which at least part, preferably all of the various resin components described above are dissolved or compatible with an organic solvent. The organic solvent is not particularly limited as long as it is a polar organic solvent or a non-polar organic solvent capable of dissolving or dissolving at least part, preferably all, of the various resin components described above. Examples of polar organic solvents include ketones. (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), cellosolves (e.g., propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc.), esters (e.g., ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, acetic acid isoamyl, ethyl lactate, methyl methoxypropionate, methyl hydroxyisobutyrate, etc.) amides (e.g., dimethoxyacetamide, dimethylformamides, etc.); nonpolar organic solvents include aromatic hydrocarbons (e.g., toluene, xylene etc.). These organic solvents may be used alone or in combination of two or more.

[Use]
The prepreg according to this embodiment can be suitably used as an insulating layer of a printed wiring board.

[Laminate]
The laminate is obtained by heating and pressurizing a laminate containing one or more prepregs according to the present embodiment and curing the prepregs. A layer formed from the prepregs according to the present embodiment, that is, It includes a cured product of the prepreg. The method and conditions for molding the laminate are not particularly limited, and general methods and conditions can be used. For example, a multistage press machine, a multistage vacuum press machine, a continuous molding machine, an autoclave molding machine, or the like can be used for molding. In molding (laminate molding), the temperature is generally 100° C. to 300° C., the pressure is 2 kgf/cm ² to 100 kgf/cm ² , and the heating time is generally 0.05 to 5 hours. In addition, post-curing can be performed at a temperature of 150° C. to 300° C., if desired. Especially when a multi-stage press is used, from the viewpoint of sufficiently accelerating the curing of the prepreg, the temperature is preferably 200° C. to 250° C., the pressure is 10 kgf/cm ² to 40 kgf/cm ² , and the heating time is 80 minutes to 130 minutes. More preferably, the temperature is 215° C. to 235° C., the pressure is 25 kgf/cm ² to 35 kgf/cm ² , and the heating time is 90 minutes to 120 minutes.

[Printed wiring board]
A printed wiring board has an insulating layer and a conductor layer, and the insulating layer includes a layer formed from the prepreg according to the present embodiment, that is, a cured product of the prepreg according to the present embodiment. Such a printed wiring board can be manufactured according to a conventional method, and the manufacturing method is not particularly limited. An example of a method for manufacturing a printed wiring board is shown below. First, a metal foil-clad laminate such as a copper-clad laminate is prepared by stacking one or more prepregs and placing a metal foil on one or both sides thereof. Next, the surface of the metal foil-clad laminate is etched to form an inner layer circuit, thereby producing an inner layer substrate. The surface of the inner layer circuit of this inner layer substrate is subjected to a surface treatment to increase the adhesive strength as necessary, and then the required number of prepregs described above are laminated on the surface of the inner layer circuit, and a metal foil for the outer layer circuit is laminated on the outer side. Then, heat and pressurize to integrally mold. In this manner, a multilayer laminate is manufactured in which an insulating layer made of the cured prepreg is formed between the inner layer circuit and the metal foil for the outer layer circuit. Next, after drilling holes for through holes and via holes in this multi-layer laminate, a plated metal film is formed on the walls of the holes for conducting the inner layer circuit and the metal foil for the outer layer circuit, and further the outer layer circuit. A printed wiring board is manufactured by etching the metal foil for the purpose to form an outer layer circuit.

As described above, according to the present embodiment, the ratio of the resin composition, the dielectric constant, and the dielectric loss tangent are adjusted, so that the skew and transmission loss can be reduced, and the signal speed can be increased. can be done. Therefore, high frequencies can be handled.

(Synthesis Example 1) Synthesis of naphthol aralkyl-type cyanate ester compound (SNCN) 1-naphthol aralkyl resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) 300 g (OH group conversion 1.28 mol) and triethylamine 194.6 g (1.92 mol) ( 1.5 mol per 1 mol of hydroxy group) was dissolved in 1800 g of dichloromethane to prepare solution 1.
125.9 g (2.05 mol) of cyanogen chloride (1.6 mol per 1 mol of hydroxy group), 293.8 g of dichloromethane, 194.5 g (1.92 mol) of 36% hydrochloric acid (1.5 mol per 1 mol of hydroxy group) , and 1205.9 g of water were poured into the solution 1 over 30 minutes while maintaining the liquid temperature at -2°C to -0.5°C under stirring. After pouring solution 1, the mixture was stirred at the same temperature for 30 minutes. I ordered over. After pouring solution 2, the mixture was stirred at the same temperature for 30 minutes to complete the reaction.
After that, the reaction solution was allowed to stand to separate the organic phase and the aqueous phase. The resulting organic phase was washed 5 times with 1300 g of water. The electrical conductivity of the wastewater after the fifth washing was 5 μS/cm, and it was confirmed that the ionic compounds that could be removed were sufficiently removed by washing with water.
After washing with water, the organic phase was concentrated under reduced pressure and finally concentrated to dryness at 90° C. for 1 hour to obtain 331 g of the desired naphthol aralkyl cyanate ester compound (SNCN) (orange viscous substance). The weight average molecular weight Mw of the obtained SNCN was 600. Also, the IR spectrum of SNCN showed an absorption at 2250 cm ^-1 (cyanate ester group) and no absorption of a hydroxy group.

(Example 1)
As the resin solid content of the resin composition, a maleimide compound (BMI-2300, manufactured by Daiwa Kasei Kogyo Co., Ltd.) 15 in which R ₅₁ and R ₅₂ are hydrogen atoms and n ₄ is 1 to 3 in the general formula (11) parts by mass, 35 parts by mass of the cyanate ester compound (SNCN) obtained in Synthesis Example 1, and in general formula (5), X is general formula (6) and -(YO)n ₂ - is general formula ( 9) Terminal unsaturated group-modified polyphenylene ether (OPE-2St1200, manufactured by Mitsubishi Gas Chemical Co., Ltd., number average molecular weight 1187, vinyl group equivalent: 590 g / eq.) 10 parts by weight, terminal unsaturated group As the second component of the saturated group-modified polyphenylene ether, in the general formula (5), X is the general formula (6) and —(Y—O)n ₂ — is the structural unit of the general formula (9) polymerized. Terminal unsaturated group-modified polyphenylene ether (OPE-2St2200, manufactured by Mitsubishi Gas Chemical Co., Ltd., number average molecular weight 2200, vinyl group equivalent: 1100 g / eq.) 10 parts by mass, styrene-isoprene-styrene elastomer (SEPTON2104, stock 10 parts by mass of styrene content 65% manufactured by Kuraray Co., Ltd. and 20 parts by mass of α-methylstyrene polymer (Crystarex 3085, manufactured by Eastman Chemical Co.) were prepared. 100 parts by mass of this resin solid content and 150 parts by mass of spherical silica (SC2050-MB, manufactured by Admatechs, average particle size 0.5 μm) as a filler are mixed and diluted with an organic solvent methyl ethyl ketone to obtain a varnish. rice field. This varnish is impregnated and coated on a low-dielectric glass cloth having a thickness of 32 μm, which is a glass fiber base material, and dried by heating at 165° C. for 5 minutes using a dryer (pressure-resistant explosion-proof steam dryer, manufactured by Takasugi Seisakusho Co., Ltd.). Got the prepreg. The ratio of the resin composition (resin solid content + filler in Example 1) to the total amount of prepreg was 87.6% by volume.

(Example 2)
A low dielectric glass cloth with a thickness of 19 μm was used as the glass fiber base material, and the ratio of the resin composition (resin solid content + filler in Example 2) to the total amount of prepreg was 92.1% by volume. prepared a prepreg in the same manner as in Example 1.

(Example 3)
A low dielectric glass cloth with a thickness of 14 μm was used as the glass fiber base material, and the ratio of the resin composition (resin solid content + filler in Example 3) to the total amount of prepreg was 95.1% by volume. prepared a prepreg in the same manner as in Example 1.

(Example 4)
As the resin solid content of the resin composition, the maleimide compound (MIR-5000, manufactured by Nippon Kayaku Co., Ltd.) represented by the general formula (15) is 40 parts by mass, and in the general formula (5), X is the general formula (6). Terminal _unsaturated group-modified polyphenylene ether (OPE-2St2200, manufactured by Mitsubishi Gas Chemical Company, Inc., number average molecular weight 2200, vinyl Basic equivalent: 1100 g/eq.) 35 parts by mass, and 25 parts by mass of a styrene-butadiene block copolymer (TR2250, manufactured by JSR Corporation, styrene content: 52%) were prepared. This resin solid content was mixed and diluted with an organic solvent, methyl ethyl ketone, to obtain a varnish. This varnish is impregnated and coated on a low-dielectric glass cloth having a thickness of 14 μm, which is a glass fiber base material, and dried by heating at 165° C. for 3 minutes using a dryer (pressure-resistant explosion-proof steam dryer, manufactured by Takasugi Seisakusho Co., Ltd.). Got the prepreg. The ratio of the resin composition (resin solid content in Example 4) to the total amount of prepreg was 95.1% by volume.

(Example 5)
Except that a low dielectric glass cloth with a thickness of 9 μm was used as the glass fiber base material and the ratio of the resin composition (resin solid content in Example 5) to the total amount of prepreg was 96.7% by volume. A prepreg was produced in the same manner as in 4.

(Example 6)
As the resin solid content of the resin composition, 10 maleimide compounds (BMI-2300, manufactured by Daiwa Kasei Kogyo Co., Ltd.) in which R ₅₁ and R ₅₂ are hydrogen atoms and n ₄ is 1 to 3 in the general formula (11) parts by mass, 30 parts by mass of the cyanate ester compound (SNCN) obtained in Synthesis Example 1, and in general formula (5), X is general formula (6) and -(YO)n ₂ - is general formula ( 60 parts by mass of a polyphenylene ether compound (OPE-2St1200, manufactured by Mitsubishi Gas Chemical Co., Ltd., number average molecular weight: 1187, vinyl group equivalent: 590 g/eq.) obtained by polymerizing the structural units of 9) was prepared. 100 parts by mass of this resin solid content, 100 parts by mass of spherical silica (SC2050-MB, manufactured by Admatechs, average particle size 0.5 μm) as a filler, and 0.1 part by mass of zinc octylate as a curing accelerator. The mixture was mixed and diluted with an organic solvent, methyl ethyl ketone, to obtain a varnish. This varnish is impregnated and coated on a low-dielectric glass cloth having a thickness of 32 μm, which is a glass fiber base material, and dried by heating at 165° C. for 5 minutes using a dryer (pressure-resistant explosion-proof steam dryer, manufactured by Takasugi Seisakusho Co., Ltd.). Got the prepreg. The ratio of the resin composition (resin solid content + filler + curing accelerator in Example 6) to the total amount of prepreg was 87.6% by volume.

(Comparative example 1)
A low dielectric glass cloth with a thickness of 80 μm was used as the glass fiber base material, and the ratio of the resin composition (resin solid content + filler in Comparative Example 1) to the total amount of prepreg was set to 69.3% by volume. prepared a prepreg in the same manner as in Example 1.

(Comparative example 2)
A low dielectric glass cloth with a thickness of 49 μm was used as the glass fiber base material, and the ratio of the resin composition (resin solid content + filler in Comparative Example 2) to the total amount of prepreg was set to 78.8% by volume. prepared a prepreg in the same manner as in Example 1.

(Comparative Example 3)
A low dielectric glass cloth with a thickness of 43 μm was used as the glass fiber base material, and the ratio of the resin composition (resin solid content + filler in Comparative Example 3) to the total amount of prepreg was set to 80.9% by volume. prepared a prepreg in the same manner as in Example 1.

(Comparative Example 4)
The same varnish as in Example 1 was applied to one side of a 12 μm thick copper foil (3EC-M3-VLP, manufactured by Mitsui Mining & Smelting Co., Ltd.) using a bar coater to obtain a copper-coated resin sheet. Using a dryer (pressure-resistant explosion-proof steam dryer, manufactured by Takasugi Seisakusho Co., Ltd.), the obtained resin sheet with copper was dried by heating at 130° C. for 5 minutes to obtain a semi-cured resin sheet with copper having a resin thickness of 25 μm. rice field. The ratio of the resin composition (resin solid content + filler in Comparative Example 4) to the total amount of the resin sheet was 100% by volume.

(Comparative Example 5)
The same varnish as in Example 4 was applied to one side of a 12 μm thick copper foil (3EC-M3-VLP, manufactured by Mitsui Mining & Smelting Co., Ltd.) using a bar coater to obtain a resin sheet with copper. Using a dryer (pressure-resistant explosion-proof steam dryer, manufactured by Takasugi Seisakusho Co., Ltd.), the obtained resin sheet with copper was dried by heating at 130° C. for 5 minutes to obtain a semi-cured resin sheet with copper having a resin thickness of 25 μm. rice field. The ratio of the resin composition (resin solid content in Comparative Example 5) to the total amount of the resin sheet was 100% by volume.

(Comparative Example 6)
As the resin solid content of the resin composition, 65 parts by mass of the cyanate ester compound (SNCN) obtained in Synthesis Example 1, phenol biphenyl aralkyl type epoxy resin (NC-3000-FH, epoxy equivalent: 320 g / eq., Nippon Kayaku Yaku Co., Ltd.) and 5 parts by weight of a naphthalene skeleton type epoxy resin (HP-4032D, epoxy equivalent: 140 g/eq., manufactured by DIC) were prepared. 100 parts by mass of this resin solid content, 100 parts by mass of spherical silica (SC2050-MB, manufactured by Admatechs, average particle size 0.5 μm) as a filler, and 0.1 part by mass of zinc octylate as a curing accelerator. The mixture was mixed and diluted with an organic solvent, methyl ethyl ketone, to obtain a varnish. This varnish is impregnated and coated on an E-glass cloth having a thickness of 32 μm, which is a glass fiber base material, and dried by heating at 165 ° C. for 4 minutes using a dryer (pressure-resistant explosion-proof steam dryer, manufactured by Takasugi Seisakusho Co., Ltd.) to form a prepreg. got The ratio of the resin composition (resin solid content + filler + curing accelerator in Comparative Example 6) to the total amount of prepreg was 87.6% by volume.

(Preparation of sample for evaluation)
For the prepregs obtained in Examples 1 to 6 and Comparative Examples 1 to 3 and 6, one or four sheets were stacked for each Example and each Comparative Example, and copper foil (3EC-M3-VLP, Mitsui Kinzoku Mining Co., Ltd. Co., Ltd., thickness 12 μm) is placed, and vacuum pressing (thermosetting) is performed at a pressure of 30 kgf/cm ² and a temperature of 210° C. for 150 minutes, and a layer of copper having a thickness of 0.1 mm and 0.4 mm is formed from the prepreg. A foil clad laminate was obtained.
Further, with respect to the semi-cured resin sheets with copper obtained in Comparative Examples 4 and 5, two semi-cured resin sheets with copper were heat-laminated so that the resin surfaces were in contact, and then the copper foil was peeled off. By repeating heating and laminating two upper and lower semi-cured resin sheets with copper so that the surfaces are in contact and peeling off the copper foil, the thickness of the resin layer with the copper foil laminated on both sides is 0. Semi-cured resin sheets of 0.1 mm and 0.4 mm were obtained. This semi-cured resin sheet with a resin layer thickness of 0.1 mm and 0.4 mm was vacuum-pressed at a pressure of 30 kgf/cm ² and a temperature of 210° C. for 150 minutes to obtain a copper foil with a resin layer thickness of 0.1 mm and 0.4 mm. A tension laminate was obtained.

(Evaluation of dielectric constant Dk and dielectric loss tangent Df)
Using a sample obtained by removing the copper foil of the copper foil-clad laminate having a thickness of 0.4 mm obtained for each example and each comparative example by etching, a perturbation method cavity resonator (Agilent Technology Co., Ltd. product, Agilent 8722ES) Relative permittivity and dielectric loss tangent at 10 GHz were measured. The results obtained are shown in Tables 1 and 2 and FIG.

(Evaluation of skew)
Fifteen microstrip lines each having a circuit length of 10 cm were formed by etching only one side of the 0.1 mm-thick copper-clad laminate obtained for each example and each comparative example. The transmission speed of 10 GHz to 20 GHz of 15 conductor wirings (impedance 50Ω) was measured, and the difference between the maximum value and the minimum value was obtained as skew (SKEW). The results obtained are shown in Tables 1 and 2 and FIG.

(Evaluation of transmission loss)
Wiring boards were prepared by etching only one side of the 0.1 mm-thick copper-clad laminate obtained in each example and each comparative example to form a microstrip line with a circuit length of 10 cm, and the transmission characteristics were evaluated. A high-frequency signal was transmitted using a network analyzer N5227B manufactured by Keysight Technologies, and the transmission loss at 20 GHz was measured. The results obtained are shown in Tables 1 and 2.

(Evaluation of warpage)
The upper and lower copper foils of the 0.1 mm-thick copper-clad laminate obtained in each example and each comparative example were processed by a laser processing machine, and predetermined vias were formed by chemical copper plating. Subsequently, a wiring pattern was etched to form a conductor layer to obtain a substrate panel (size: 500 mm×400 mm). Then, the amount of warpage at a total of four points on the four corners of the obtained panel was measured with a metal rule, and the average value was defined as "warpage." The results obtained are shown in Tables 1, 2 and FIG.

As shown in Tables 1 and 2 and FIGS. 1 to 3, it was found that the skew can be reduced and the dielectric constant can be decreased by setting the ratio of the resin composition to the total amount of the prepreg to 81% by volume or more. . Moreover, it was found that warping can be sufficiently reduced by setting the ratio of the resin composition to the total amount of the prepreg to 98% by volume or less. That is, it was found that the ratio of the resin composition to the total amount of the prepreg is preferably in the range of 81% by volume or more and 98% by volume or less.

In addition, according to the present embodiment, the dielectric constant at 10 GHz after curing of the prepreg can be 3.3 or less, and the dielectric loss tangent at 10 GHz after curing of the prepreg can be 0.004 or less. can be done.

Claims

A prepreg in which a glass fiber substrate is impregnated or coated with a resin composition containing a thermosetting compound,
The ratio of the resin composition to the total amount of the prepreg is in the range of 81% by volume or more and 98% by volume or less,
A prepreg having a dielectric constant of 3.3 or less at 10 GHz and a dielectric loss tangent of 0.004 or less after curing.
2. The glass fiber base material comprises at least one glass fiber selected from the group consisting of E glass, D glass, S glass, T glass, Q glass, L glass, NE glass, and HME glass. The prepreg described in .
The prepreg according to claim 1, wherein the thermosetting compound contains terminal unsaturated group-modified polyphenylene ether.
The prepreg according to claim 3, wherein the content of the terminal unsaturated group-modified polyphenylene ether is 1 to 70 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition.
The prepreg according to claim 1, wherein the thermosetting compound contains one or more selected from the group consisting of maleimide compounds, cyanate ester compounds, epoxy compounds, and phenol compounds.
The prepreg according to claim 1, wherein the resin composition further contains a thermoplastic elastomer.
The prepreg according to claim 6, wherein the content of said thermoplastic elastomer is 1 to 45 parts by mass with respect to 100 parts by mass of resin solid content in said resin composition.
The prepreg according to claim 1, wherein the resin composition further contains a filler.
The prepreg according to claim 8, wherein the content of the filler is 50 to 1600 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition.
A laminate containing the cured prepreg according to claim 1.
A printed wiring board having an insulating layer and a conductor layer, wherein the insulating layer contains the cured product of the prepreg according to claim 1.