KR20240088777A - Prepreg, laminate and printed wiring board - Google Patents

Abstract

(assignment)
The present invention provides prepregs, laminated boards, and printed wiring boards that can reduce skew and transmission loss.
(Solution)
It is a prepreg in which a resin composition containing a thermosetting compound is impregnated or applied to a glass fiber base, and the ratio of the resin composition to the total amount of the prepreg is within the range of 81% by volume to 98% by volume. Skew can be reduced by setting the ratio of the resin composition to 81% by volume or more. On the other hand, when the proportion of the resin composition exceeds 98% by volume, warpage after curing increases. The relative dielectric constant at 10 GHz after curing is 3.3 or less, and the dielectric loss tangent is 0.004 or less.

Description

Prepreg, laminate and printed wiring board

The present invention relates to prepreg, a laminated board using the prepreg, and a printed wiring board.

Recently, the speed and capacity of data communications used in information and communications are rapidly increasing. Therefore, printed wiring boards that can respond to high frequencies are required for information and communication electronic devices. As an insulating material used in printed wiring boards, for example, prepreg, which is glass fiber impregnated or coated with resin, is widely used. However, because the dielectric properties of glass fiber and resin are different, the delay time (transmission speed) of the signal becomes uneven due to the compactness of the glass fiber. As the transmission speed increases, the influence of propagation delay time difference (SKEW) that occurs between differential wiring increases, and the skew causes transmission characteristics to deteriorate. Additionally, in order to respond to high frequencies, it is necessary to reduce transmission loss.

Patent Document 1: International Publication No. 2019/230945

The present invention was made based on this problem, and its purpose is to provide prepregs, laminated boards, and printed wiring boards that can reduce skew and transmission loss.

Additionally, Patent Document 1 describes a prepreg aimed at reducing the unevenness of signal delay time. However, the prepreg described in Patent Document 1 reduces the influence of the high dielectric constant of glass fiber on the impedance of the conductor wiring by inserting hexagonal boron nitride between the glass fiber and the conductor wiring, thereby reducing the skew. Therefore, the specific configuration is different from that of the present invention.

The present invention is as follows.

[One]

A prepreg in which a resin composition containing a thermosetting compound is impregnated or applied to a glass fiber base, wherein the ratio of the resin composition to the total amount of the prepreg is within the range of 81 volume% to 98 volume%, and the A prepreg with a relative dielectric constant of 3.3 or less and a dielectric loss tangent of 0.004 or less at 10 GHz.

[2]

It is described in [1] that the glass fiber base material contains at least one type of 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. prepreg.

[3]

The prepreg according to [1], wherein the thermosetting compound contains terminally unsaturated group-modified polyphenylene ether.

[4]

The prepreg described in [3], wherein the content of the terminally unsaturated group-modified polyphenylene ether is 1 to 40 parts by mass based on 100 parts by mass of the resin solid content in the resin composition.

[5]

The prepreg according to [1], wherein the thermosetting compound includes one or more types 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 described in [6], wherein the content of the thermoplastic elastomer is 1 to 45 parts by mass based on 100 parts by mass of the resin solid content in the resin composition.

[8]

The prepreg described in [1], wherein the resin composition further contains a filler.

[9]

The prepreg described in [8], wherein the content of the filler is 50 to 1,600 parts by mass based on 100 parts by mass of the resin solid content in the resin composition.

[10]

A laminate containing a cured product of the prepreg described in [1].

[11]

A printed wiring board comprising an insulating layer and a conductor layer, wherein the insulating layer contains a cured product of the prepreg described in [1].

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

1 is a diagram showing the relationship between the ratio of the resin composition and the transmission loss.
Figure 2 is a diagram showing the relationship between the ratio of the resin composition and the skew.
Figure 3 is a diagram showing the relationship between the ratio of the resin composition and warpage.

Below, specific details for carrying out the present invention (hereinafter referred to as “this embodiment”) will be described in detail; however, the present invention is not limited thereto, and various modifications may be made without departing from the gist of the present invention. possible.

[Prepreg]

The prepreg according to this embodiment is a glass fiber base material impregnated or applied with a resin composition containing a thermosetting compound. The ratio of the resin composition to the total amount of prepreg is within the range of 81 volume% or more and 98 volume% or less. This is because skew can be reduced by setting the ratio of the resin composition to the total amount of prepreg to 81% by volume or more and can respond to high frequencies. On the other hand, if the ratio of the resin composition to the total amount of prepreg exceeds 98% by volume, warpage after curing increases, making it unsuitable for printed wiring boards. The ratio of the resin composition to the total amount of prepreg is more preferably 85% by volume or more, and even more preferably 86% by volume or more. Additionally, the ratio of the resin composition to the total amount of prepreg is more preferably 96% by volume or less, and even more preferably 95% by volume or less.

The relative dielectric constant at 10 GHz after curing of the prepreg is 3.3 or less. This is because a lower relative dielectric constant can speed up the signal speed and respond to high frequencies. It is more preferable that the relative dielectric constant at 10 GHz after curing of the prepreg is less than 3.2. Additionally, the lower limit of the relative dielectric constant at 10 GHz after curing of the prepreg is not particularly limited, but can be, for example, 2.6 or more. Additionally, 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 support high frequencies. The lower limit of the dielectric loss tangent at 10 GHz after curing of the prepreg is not particularly limited, but 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 it (B-staged) by drying it at 120 to 220°C for about 2 to 15 minutes. The ratio of the resin composition to the total amount of prepreg is the ratio after semi-curing, and the resin composition also includes a cured product of the resin composition. As will be described later, the resin composition also includes a filler.

<Glass fiber base material>

The glass fiber base material preferably contains at least one type of glass fiber selected from the group consisting of, for example, E glass, D glass, S glass, T glass, Q glass, L glass, NE glass and HME glass. . The form of the fiber base is not particularly limited and includes woven fabric, non-woven fabric, roving, chopped strand mat (CSM), surfacing mat, etc. Among them, from the viewpoint of dimensional stability, woven fabrics that have been subjected to super-opening treatment or glazing treatment are preferable, and from the viewpoint of moisture absorption and heat resistance, woven fabrics that have been surface treated with silane coupling agents such as epoxysilane treatment or aminosilane treatment, etc. is desirable. The thickness of the glass fiber base material 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 may contain terminally unsaturated group-modified polyphenylene ether as a thermosetting compound. Terminal unsaturated group-modified polyphenylene ether is represented by general formula (1).

_In general formula _{( 1 )} , It represents a nyl group or an alkynyl group, n ₂ represents an integer of 1 to 100, n ₁ represents an integer of 1 to 6, and n ₃ represents an integer of 1 to 4.

By containing terminal unsaturated group-modified polyphenylene ether, excellent low dielectric constant and low dielectric dissipation properties can be obtained, and moldability can be improved. The terminal unsaturated group-modified polyphenylene ether preferably has a number average molecular weight of 1000 or more and 7000 or less. By setting the number average molecular weight to 7000 or less, fluidity during molding can be secured. In addition, by setting the number average molecular weight to 1000 or more, excellent dielectric properties (low dielectric constant, low dielectric loss tangent) and heat resistance inherent to polyphenylene ether resin can be obtained. Among them, in order to obtain better fluidity, heat resistance and dielectric properties, the number average molecular weight of the terminally unsaturated group-modified polyphenylene ether should be 1,100 or more and 5,000 or less. More preferably, the number average molecular weight of the terminally unsaturated group-modified polyphenylene ether is 4500 or less, and even more preferably, the number average molecular weight of the terminally unsaturated group-modified polyphenylene ether is 3000 or less. The number average molecular weight is measured using gel permeation chromatography according to a specified method.

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

The terminally 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, an aryl group, a halogen atom, or a hydrogen atom having 6 or less carbon atoms.

The polymer may further contain at least one type of 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 or phenyl group having 6 or less carbon atoms. R ₄₀₈ , R ₄₀₉ , and R ₄₁₀ each independently represent a hydrogen atom, an alkyl group with 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 with 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), it is preferable that the above general formulas (2), (3), and (4) are -(Y—O)- of general formula (1). ―(Y―O)― has repeating units of n ₂ numbers (1 to 100).

_In General Formula _{( 1 )} , represents an atom, an alkyl group, an alkenyl group, or an alkynyl group, n ₂ represents an integer from 1 to 100, n ₁ represents an integer from 1 to 6, and n ₃ represents an integer from 1 to 4. Preferably, n ₁ may be an integer of 1 to 4, more preferably n ₁ may be 1 or 2, and ideally n ₁ may be 1. Also preferably, n ₃ is an integer of 1 to 3, more preferably n ₃ is 1 or 2, and ideally n ₃ is 2.

As the aryl group in X in General Formula (1), an aromatic hydrocarbon group can be used. Specifically, from one type of ring structure selected from a benzene ring structure, a biphenyl structure, an indenyl ring structure, and a naphthalene ring structure, a group excluding n ₃ hydrogen atoms (for example, a phenyl group, a biphenyl group, an indenyl group, and A naphthyl group) can be used, preferably a biphenyl group. Here, the aryl group may include a diphenyl ether group in which the aryl group is bonded to an oxygen atom, a benzophenone group bonded to a carbonyl group, or a 2,2-diphenylpropane group bonded to an alkylene group. good night. Additionally, the aryl group may be substituted by a common substituent such as an alkyl group (preferably an alkyl group with 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 portion with an oxygen atom in between, the limit on the number of substituents generally depends on the number of polyphenylene ether portions.

As terminal unsaturated group-modified polyphenylene ether, it is especially preferable to include a compound represented by the structure of the following general formula (5).

In _General Formula (5) _, ―(Y―O)n ₂ ― and n ₂ have the same meaning as in General Formula (1). n ₂ may contain multiple types of compounds with different values.

X in general formulas (1) and (5) is preferably general formula (6), general formula (7), or general formula (8), and In ―(Y―O)n _2― , 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, is better. desirable.

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 straight-chain, branched, or cyclic divalent hydrocarbon group having 20 or less carbon atoms.

The method for producing the terminally unsaturated group-modified polyphenylene ether having the structure represented by the general formula (5) is not particularly limited, and for example, a bifunctional phenolic compound obtained by oxidatively coupling a difunctional phenolic compound and a monofunctional phenolic compound. It can be produced by vinylbenzyl etherifying the terminal phenolic hydroxyl group of the phenylene ether oligomer. Additionally, such terminally unsaturated group-modified polyphenylene ether can be used as a commercial product, for example, OPE-2St1200 and OPE-2St2200 manufactured by Mitsubishi Gas Chemical Co., Ltd. (MITSUBISHI GAS CHEMICAL COMPANY, INC.) can be suitably used.

The content of the terminally unsaturated group-modified polyphenylene ether in the resin composition, when contained, is preferably 1 part by mass or more, more preferably 5 parts by mass or more, with respect to 100 parts by mass of the resin solid content of the resin composition, and 10 It is more preferable that it is 15 parts by mass or more, and it is still more preferable that it is 20 parts by mass or more. Additionally, the upper limit of this 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. By setting it within this range, there is a tendency to effectively achieve low dielectric constant, low dielectric loss tangent, and good formability. The resin composition may contain only one type of terminal unsaturated group-modified polyphenylene ether or may contain two or more types. When two or more types are included, it is preferable that the total amount falls within the above range.

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

(maleimide compound)

The resin composition may contain a maleimide compound as a thermosetting compound. The maleimide compound contains one or more (preferably 2 to 12, more preferably 2 to 6, further preferably 2 to 4, even more preferably 2 or 3, even more preferably 2) compounds in the molecule. There is no particular limitation as long as it is a compound having a maleimide group. Specific examples thereof include N-phenylmaleimide, N-hydroxyphenylmaleimide, bis(4-maleimidephenyl)methane, 4,4'-diphenylmethanebismaleimide, and bis(3,5-dimethyl). -4-maleimidephenyl)methane, bis(3,5-diethyl-4-maleimidephenyl)methane, phenylmethanemaleimide, o-phenylenebismaleimide, m-phenylenebismaleimide, p-phenyl Lenbismaleimide, o-phenylenebiscitraconimide, m-phenylenebiscitraconimide, p-phenylenebiscitraconimide, 2,2-bis(4-(4-maleimide phenoxy )-phenyl)propane, 3,3'-diethyl-5,5'-dimethyl-4,4'-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6 -Bismaleimide-(2,2,4-trimethyl)hexane, 4,4'-diphenyletherbismaleimide, 4,4'-diphenylsulfonebismaleimide, 1,3-bis(3-maleimide) Phenoxy) benzene, 1,3-bis (4-maleimide phenoxy) benzene, 4,4'-diphenylmethane biscitraconimide, 2,2-bis [4- (4-citraconimide phenok) Si) phenyl] propane, bis (3,5-dimethyl-4-citraconimide phenyl) methane, bis (3-ethyl-5-methyl-4-citraconimide phenyl) methane, bis (3,5- Diethyl-4-citraconimide phenyl) methane, represented by formula (11), formula (12), formula (13), formula (14), formula (15) and formula (16) Maleimide compounds, etc. can be mentioned.

In general formula (11), R ₅₁ and R ₅₂ each independently represent a hydrogen atom or a methyl group, and are preferably hydrogen atoms. Furthermore, 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 7, and more preferably is 5. The compound represented by general formula (11) may contain two or more types of compounds with different n ₄ .

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 and a carbon number. It represents an alkyl group with a value of 1 to 8 (for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, etc.) or phenyl group. Among these, it is preferable that it is a group selected from the group consisting of a hydrogen atom, a methyl group and a phenyl group, more preferably one of a hydrogen atom and a methyl group, and even more preferably a hydrogen atom.

Also, in General Formula (12), it is an integer of _1≤n5≤10 . From the viewpoint of further excellent solvent solubility, n ₅ is preferably 4 or less, more preferably 3 or less, and even more preferably 2 or less. The compound represented by general formula (12) may contain two or more types of compounds with different n ₅ .

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. From the viewpoint of further excellent low dielectric constant and low dielectric dissipation property, R ₇₁ , R ₇₂ , R ₇₃ , and R ₇₄ are preferably methyl or ethyl groups. Examples of such compounds include 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. From the viewpoint of further excellent low dielectric constant and low dielectric dissipation property, R ₉₁ and R ₉₂ are preferably methyl groups. Examples of such compounds include 2,2-bis(4-(4-maleimidephenoxy)-phenyl)propane.

In General Formula (15), n ₆ represents an integer of 1 or more. The compound represented by general formula (15) may contain two or more types of compounds with different n ₆ .

In general formula (16), R ^M1 , R ^M2 , R ^M3 and R ^M4 each independently represent a hydrogen atom or an organic group. R ^M5 and R ^M6 each independently represent a hydrogen atom or an alkyl group. Ar ^M represents a divalent aromatic group. A is an alicyclic group with a 4- to 6-membered ring. R ^M7 and R ^M8 are each independently an alkyl group. mx is 1 or 2, and lx is 0 or 1. R ^M9 and R ^M10 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 between 1 and 20. The compound represented by general formula (16) may contain two or more types of 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 with 1 to 12 carbon atoms, even more preferably an alkyl group with 1 to 6 carbon atoms, even more preferably a methyl group, ethyl group, propyl group, or butyl group, and among them, a methyl group is particularly preferred. desirable. R ^M1 and R ^M3 are each independently preferably an alkyl group, and R ^M2 and R ^M4 are preferably hydrogen atoms.

R ^M5 and R ^M6 each independently represent a hydrogen atom or an alkyl group, and an alkyl group is preferable. The alkyl group here is preferably an alkyl group with 1 to 12 carbon atoms, more preferably an alkyl group with 1 to 6 carbon atoms, more preferably a methyl group, ethyl group, propyl group, or butyl group, and among them, a methyl group is particularly preferable.

Ar ^M represents a divalent aromatic group, and is preferably a phenylene group, naphthalenediyl group, phenanthrenediyl group, or anthracenediyl group, more preferably a phenylene group, and 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 with 1 to 12 carbon atoms, even more preferably an alkyl group with 1 to 6 carbon atoms, and even more preferably a methyl group, an ethyl group, a propyl group, or a butyl group. preferred, and a methyl group is particularly preferred. Among them, it is preferable that Ar ^M is unsubstituted.

A is a 4- to 6-membered alicyclic group, and a 5-membered alicyclic group (preferably a group that forms an indane ring together with a benzene ring) is more preferable. R ^M7 and R ^M8 each independently represent an alkyl group, preferably an alkyl group with 1 to 6 carbon atoms, more preferably an alkyl group with 1 to 3 carbon atoms, and particularly preferably a methyl group. mx is 1 or 2, and is preferably 2. lx is 0 or 1, and is preferably 1.

R ^M9 and R ^M10 each independently represent a hydrogen atom or an alkyl group, and an alkyl group is preferable. The alkyl group here is preferably an alkyl group with 1 to 12 carbon atoms, more preferably an alkyl group with 1 to 6 carbon atoms, more preferably a methyl group, ethyl group, propyl group, or butyl group, and among them, a methyl group is particularly 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 with 1 to 12 carbon atoms, even more preferably an alkyl group with 1 to 6 carbon atoms, even more preferably a methyl group, ethyl group, propyl group, or butyl group, and among them, a methyl group is particularly preferred. desirable. 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 between 1 and 20.

The compound represented by 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. R ^M25 and R ^M26 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 between 1 and 20.

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 with 1 to 12 carbon atoms, even more preferably an alkyl group with 1 to 6 carbon atoms, even more preferably a methyl group, ethyl group, propyl group, or butyl group, and particularly preferably a methyl group. do. R ^M21 and R ^M23 are preferably alkyl groups, and R ^M22 and R ^M24 are preferably hydrogen atoms.

R ^M25 and R ^M26 each independently represent a hydrogen atom or an alkyl group, and an alkyl group is preferable. The alkyl group here is preferably an alkyl group with 1 to 12 carbon atoms, more preferably an alkyl group with 1 to 6 carbon atoms, more preferably a methyl group, ethyl group, propyl group, or butyl group, and among them, a methyl group is particularly preferable.

R ^M27 , R ^M28 , R ^M29 and R ^M30 each independently represent a hydrogen atom or an organic group, and a hydrogen atom is preferable. The organic group here is preferably an alkyl group, more preferably an alkyl group with 1 to 12 carbon atoms, even more preferably an alkyl group with 1 to 6 carbon atoms, even more preferably a methyl group, ethyl group, propyl group, or butyl group, and particularly preferably a methyl group. do.

R ^M31 and R ^M32 each independently represent a hydrogen atom or an alkyl group, and an alkyl group is preferable. The alkyl group here is preferably an alkyl group with 1 to 12 carbon atoms, more preferably an alkyl group with 1 to 6 carbon atoms, more preferably a methyl group, ethyl group, propyl group, or butyl group, and among them, a methyl group is particularly 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 with 1 to 12 carbon atoms, even more preferably an alkyl group with 1 to 6 carbon atoms, even more preferably a methyl group, ethyl group, propyl group, or butyl group, and particularly preferably a methyl group. do.

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, and an alkyl group is preferable. The alkyl group here is preferably an alkyl group with 1 to 12 carbon atoms, more preferably an alkyl group with 1 to 6 carbon atoms, more preferably a methyl group, ethyl group, propyl group, or butyl group, and among them, a methyl group is particularly preferable.

nx represents an integer between 1 and 20.

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

In General Formula (18), nx represents an integer between 1 and 20.

The molecular weight of the compound represented by General Formula (16) is preferably 500 or more, more preferably 600 or more, and still more preferably 700 or more. By exceeding the above lower limit, dielectric properties and low water absorption tend to be further improved. Furthermore, the molecular weight of the compound represented by the general formula (16) is preferably 10,000 or less, more preferably 9,000 or less, more preferably 7,000 or less, even more preferably 5,000 or less, and even more preferably 4,000 or less. By setting it below the above upper limit, heat resistance and handleability tend to further improve.

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, a maleimide compound represented by general formula (11) is “BMI-2300” manufactured by Daiwakasei Industry Co., Ltd., general formula As a maleimide compound represented by (12), “MIR-3000” manufactured by Nippon Kayaku Co., Ltd., and as a maleimide compound represented by general formula (13) manufactured by K.I Chemical Co., Ltd. ( “BMI-70” manufactured by K.I Chemical Industry Co., Ltd., a maleimide compound represented by the general formula (14), and “BMI-80” manufactured by K.I Chemical Industry Co., Ltd., a maleimide compound represented by the general formula (15) As a compound, “MIR-5000” manufactured by Nippon Kayaku Co., Ltd., and as a maleimide compound represented by general formula (16), “X9-450”, “X9-470”, and “NE-” manufactured by DIC Corporation. “X-9470S” can be used suitably.

The content of the maleimide compound in the resin composition can be appropriately set depending on the desired characteristics and is not particularly limited. When containing the maleimide compound, the content is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and still more preferably 10 parts by mass or more, based on 100 parts by mass of the resin solid content in the resin composition. The upper limit is preferably 90 parts by mass or less, more preferably 60 parts by mass or less, further preferably 50 parts by mass or less, and may be 40 parts by mass or less. By setting it within this range, high heat resistance and low water absorption tend to be exhibited more effectively. Only one type of maleimide compound may be used, or two or more types may be used. When using two or more types, it is preferable that the total amount falls within the above range.

(cyanic acid ester compound)

The resin composition may contain a cyanate ester compound as a thermosetting compound. The cyanate ester compound contains at least one compound in the molecule (preferably 2 to 12, more preferably 2 to 6, further preferably 2 to 4, even more preferably 2 or 3, even more preferably 2). There is no particular limitation as long as the resin has an aromatic moiety substituted by a cyanato group (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 each independently represent a phenylene group which may have a substituent, a naphthylene group which may have a substituent, or a biphenylene group which may have a substituent. R ₁₀₁ and R ₁₀₂ are each independently a hydrogen atom, an alkyl group of 1 to 6 carbon atoms which may have a substituent, an aryl group of 6 to 12 carbon atoms which may have a substituent, and a carbon number of 1 to 4 which may have a substituent. An aralkyl group that may have a substituent in which an alkoxy group, an alkyl group with 1 to 6 carbon atoms and an aryl group with 6 to 12 carbon atoms are bonded, or an alkylaryl group that may have a substituent in which an alkyl group with 1 to 6 carbon atoms is bonded to an aryl group with 6 to 12 carbon atoms. It is selected from any one of the following groups. n ₇₁ represents the number of cyanato groups bonded to Ar ₁ and is an integer of 1 to 3. n ₇₂ represents the number of cyanato groups bonded to Ar ₂ and is an integer of 1 to 3.

n ₇₃ represents the number of R ₁₀₁ bonded to Ar ₁ , and is 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 bonded to Ar ₂ , and is 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. n ₈ represents the average number of repetitions and is an integer of 0 to 50. The cyanate ester compound may be a mixture of compounds having different n ₈ values. Z is each independently a single bond, a divalent organic group having 1 to 50 carbon atoms (the hydrogen atom may be substituted with a hetero atom), a divalent organic group having 1 to 10 nitrogen atoms (—N—R—N—, etc.), Carbonyl group (—CO—), carboxyl group (—C(＝O)O—), carbonyl dioxide group (—OC(＝O)O—), sulfonyl group (—SO ₂ —), and divalent sulfur atom or divalent It is selected from any one type of oxygen atom.

The alkyl groups for R ₁₀₁ and R ₁₀₂ in the general formula (19) may have a straight-chain structure, a branched-chain structure, or a cyclic structure (cycloalkyl group, etc.). In addition, the hydrogen atom in the alkyl group in the general formula (19) and the aryl group in R ₁₀₁ and R ₁₀₂ is 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. It may be substituted.

Specific examples of alkyl groups include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, 1-ethylpropyl group, 2,2-dimethylpropyl group, and cyclo. Pentyl group, hexyl group, cyclohexyl group, trifluoromethyl group, etc. are mentioned.

Specific examples of the aryl group include phenyl group, xylyl group, mesityl group, naphthyl group, phenoxyphenyl group, ethylphenyl group, o-, m- or p-fluorophenyl group, dichlorophenyl group, dicyanophenyl group, trifluorophenyl group, and mesyl group. Toxyphenyl group, o-, m-, or p-tolyl group can be mentioned.

Specific examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, and tert-butoxy group.

Specific examples of the divalent organic group in Z in general formula (19) include methylene group, ethylene group, trimethylene group, cyclopentylene group, cyclohexylene group, trimethylcyclohexylene group, biphenylylmethylene group, and dimethyl. Examples include methylene-phenylene-dimethylmethylene group, fluorenediyl group, and phthalide diyl group. The hydrogen atom in the divalent organic group may be substituted by 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 in the general formula (19) include an imino group and a polyimide group.

Additionally, Z in the general formula (19) includes those having a structure represented by the general formula (20) or (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 are each independently a hydrogen atom, an alkyl group with 1 to 6 carbon atoms, an aryl group with 6 to 12 carbon atoms, and an aryl substituted by at least one of a trifluoromethyl group and a phenolic hydroxy group. It is selected from any one of the following groups. R ₁₀₅ and R ₁₀₆ are each independently selected from a hydrogen atom, an alkyl group with 1 to 6 carbon atoms, an aryl group with 6 to 12 carbon atoms, an alkoxy group with 1 to 4 carbon atoms, and a hydroxy group. n ₉ represents an integer of 0 to 5, but the cyanate ester compound may be a mixture of compounds having groups with different n ₉ from each other.

In general formula (21), Ar ₄ is selected from a phenylene group, a naphthylene group, or a biphenylene group. R ₁₀₉ and R ₁₁₀ are each independently a hydrogen atom, an alkyl group with 1 to 6 carbon atoms, an aryl group with 6 to 12 carbon atoms, a benzyl group, an alkoxy group with 1 to 4 carbon atoms, and a hydroxy group, a trifluoromethyl group, and a cyanato group. It is selected from any one type of aryl group substituted by at least one aryl group. n ₁₀ represents an integer of 0 to 5, but the cyanate ester compound may be a mixture of compounds in which n ₁₀ has different groups.

Moreover, as Z in general formula (19), a divalent group represented by the formula below can be mentioned.

In the formula, n ₁₁ represents an integer of 4 to 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 in formula (20) and Ar ₄ in formula (21) include 1,4-phenylene group, 1,3-phenylene group, 4,4'-biphenylene group, and 2,4'-bi. Phenylene 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, etc. The alkyl groups and aryl groups 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 in General Formula (19).

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

Specific examples of the cyanate ester compound represented by 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-cyanatophenyl)-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, cyanato Nitrobenzene, 1-cyanato-4-nitro-2-ethylbenzene, 1-cyanato-2-methoxy-4-allylbenzene (cyanate of eugenol), 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-acetoaminobenzene, 4-cyanatobenzophenone, 1-cyanato-2,6-di-tert-butylbenzene, 1,2-DC Anatobenzene, 1,3-dicyanatobenzene, 1,4-dicyanatobenzene, 1,4-dicyanato-2-tert-butylbenzene, 1,4-dicyanato-2,4-dimethyl Benzene, 1,4-dicyanato-2,3,4-dimethylbenzene, 1,3-dicyanato-2,4,6-trimethylbenzene, 1,3-dicyanato-5-methylbenzene, 1 -Cyanato or 2-cyanathonaphthalene, 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-dicy. Anatodinaphthalene, 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) 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-cyanato) Phenyl)-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-cyanatophenyl)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-cyanato) Phenyl)-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-dicyanato Benzophenone, 1,3-bis(4-cyanatophenyl)-2-propen-1-one, bis(4-cyanatophenyl)ether, bis(4-cyanatophenyl)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)-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-cyanatophenyl)-4,4'-oxydiphthalimide, bis(N-4-cyanato-2-methylphthalimide)- 4,4'-(hexafluoroisopropylidene)diphthalimide, tris(3,5-dimethyl-4-cyanatobenzyl)isocyanurate, 2-phenyl-3,3-bis(4-cyanurate) Natophenyl)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 novolak resin or cresol novolak resin (reacted by a known method with phenol, alkyl-substituted phenol, or halogen-substituted phenol, and a formaldehyde compound such as formalin or paraformaldehyde in an acidic solution), trisphenolol Rockfish resin (reacted between hydroxybenzaldehyde and phenol in the presence of an acidic catalyst), fluorene novolac resin (reacted between fluorenone compounds and 9,9-bis(hydroxyaryl)fluorene in the presence of an acidic catalyst) phenol aralkyl resin, cresol aralkyl resin, naphthol aralkyl resin or biphenyl aralkyl resin (by a known method, bihalogenomethyl as represented by Ar ₅ -(CH ₂ Z') ₂ A compound obtained by reacting a phenol compound with an acidic catalyst or without a catalyst, a bis(alkoxymethyl) compound represented by Ar ₅ —(CH ₂ OR) ₂ or a bis(alkoxymethyl) compound represented by Ar ₅ —(CH ₂ OH) ₂ hydroxymethyl) compound and phenol compound reacted in the presence of an acidic catalyst, or aromatic aldehyde compound, aralkyl compound, and phenol compound polycondensation), phenol-modified xylene formaldehyde resin (xylene formaldehyde resin by a known method Formaldehyde resin and a phenol compound reacted in the presence of an acidic catalyst), modified naphthalene formaldehyde resin (naphthalene formaldehyde resin and a hydroxy-substituted aromatic compound reacted in the presence of an acidic catalyst according to a known method), Phenol-modified dicyclopentadiene resin, phenol resin having a polynaphthylene ether structure (by a known method, a polyhydric hydroxynaphthalene compound having two or more phenolic hydroxy groups per molecule is dehydrated in the presence of a basic catalyst) Condensed phenolic resins, etc., cyanic acid esterified by the same method as above, but are not particularly limited. These cyanate ester compounds may be used individually, or two or more types may be used in combination.

Among these, phenol novolak type cyanate ester compound, naphthol aralkyl type cyanate ester compound, naphthylene ether type cyanate ester compound, bisphenol A type cyanate ester compound, bisphenol M type cyanate ester compound, diallyl bisphenol type cyanate. Ester compounds are preferred, and naphthol aralkyl type cyanate ester compounds are particularly preferred. The cured product of the resin composition using these cyanate ester compounds has characteristics such as excellent low dielectric properties (low dielectric constant, low dielectric loss tangent).

The content of the cyanate ester compound in the resin composition can be appropriately set depending on the desired properties and is not particularly limited. Specifically, the content of the cyanate ester compound, when contained, is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, and even more preferably 1 part by mass or more, based on 100 parts by mass of the resin solid content in the resin composition. It is preferable and may be 3 parts by mass or more and 5 parts by mass or more. Moreover, the upper limit of this content is preferably 90 parts by mass or less, more preferably 80 parts by mass or less, more preferably less than 70 parts by mass, still more preferably 60 parts by mass or less, 50 parts by mass or less, and 40 parts by mass or less. Anything below is fine. By setting it within this range, it is possible to provide better low dielectric constant and low dielectric loss tangent. Only one type of cyanate ester compound may be used, or two or more types may be used. When using two or more types, it is preferable that the total amount falls within the above range.

(epoxy resin)

The resin composition may include an epoxy resin as a thermosetting compound. As an epoxy resin, one or more (preferably 2 to 12, more preferably 2 to 6, further preferably 2 to 4, even more preferably 2 or 3, even more preferably 2) per molecule. There is no particular limitation as long as it is a compound or resin having an epoxy group, and examples include bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolak type epoxy resin, and bisphenol A epoxy resin. Rock-type epoxy resin, glycidyl ester-type epoxy resin, aralkyl novolak-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 novolac 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 resins, phosphorus-containing epoxy resins, compounds obtained by epoxidizing double bonds of glycidylamine, glycidyl ester, butadiene, etc., compounds obtained by the reaction of hydroxyl group-containing silicone resins with epichlorohydrin, etc. You can. These epoxy resins may be used individually, or two or more types may be used together. Among these, from the viewpoint of further improving flame retardancy and heat resistance, biphenyl aralkyl type epoxy resin, naphthylene ether type epoxy resin, polyfunctional phenol type epoxy resin, and naphthalene type epoxy resin are preferable.

(Phenolic resin)

The resin composition may contain a phenol resin as a thermosetting compound. As a phenol resin, one or more (preferably 2 to 12, more preferably 2 to 6, further preferably 2 to 4, even more preferably 2 or 3, even more preferably 2) per molecule. It is not particularly limited as long as it is a compound or resin having a phenolic hydroxy group, and examples include bisphenol A-type phenol resin, bisphenol E-type phenol resin, bisphenol F-type phenol resin, bisphenol S-type phenol resin, phenol novolak resin, and bisphenol A resin. Rock-type phenol resin, glycidyl ester-type phenol resin, aralkyl novolak-type phenol resin, biphenyl aralkyl-type phenol resin, cresol novolak-type phenol resin, multifunctional phenol resin, naphthol resin, naphthol novolak resin, multifunctional naphthol Resin, anthracene type phenol 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 Resins, phosphorus-containing phenol resins, etc. can be mentioned. These phenol resins may be used individually, or two or more types may be used in combination. Among these, from the viewpoint of further improving flame resistance, at least one selected from the group consisting of biphenyl aralkyl type phenol resin, naphthol aralkyl type phenol resin, and phosphorus-containing phenol resin is preferable.

(thermoplastic elastomer)

The resin composition may include a thermoplastic elastomer. Thermoplastic elastomers contain styrene monomer units. By including a styrene monomer unit, the solubility of the thermoplastic elastomer in the resin composition is improved. As styrene monomers, styrene, α-methylstyrene, p-methylstyrene, divinylbenzene (vinylstyrene), N,N-dimethyl-p-aminoethylstyrene, N,N-diethyl-p-aminoethylstyrene, etc. Among these, styrene, α-methylstyrene, and p-methylstyrene are preferred from the viewpoint of availability and productivity. Among these, styrene is particularly preferable.

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, and 15 to 40% by mass of the total monomer units. A range is more desirable. If the content of the styrene monomer unit is 50% by mass or less, the adhesion and adhesion to the substrate and the like become better. In addition, if it is 10% by mass or more, it is preferable because the increase in adhesion can be suppressed, residues and stop marks are unlikely to form, and the easy peelability between adhesive surfaces tends to improve.

The thermoplastic elastomer may contain only one type of styrene monomer unit, or may contain two or more types. When two or more types are included, it is preferable that the total amount is within the above range.

The method for measuring the content of the styrene monomer unit in the thermoplastic elastomer of this embodiment can take into account what is described in International Publication No. 2017/126469, and the content is incorporated into this specification. The same applies to the conjugated diene monomer unit, etc., which will be described later.

The thermoplastic elastomer contains conjugated diene monomer units. By including a conjugated diene monomer unit, the solubility of the thermoplastic elastomer in the resin composition is improved. The conjugated diene monomer is not particularly limited as long as it is a diolefin having one 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- Examples include 1,3-pentadiene, 1,3-hexadiene, and farnesene, 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 thermoplastic elastomer, the mass ratio of the styrene monomer unit and the conjugated diene monomer unit is preferably in the range of styrene monomer unit/conjugated diene monomer unit = 5/95 to 80/20, and in the range of 7/93 to 77/23. It is more preferable that it is in the range of 10/90 to 70/30. If the mass ratio of the styrene monomer unit and the conjugated diene monomer unit is in the range of 5/95 to 80/20, the increase in adhesion can be suppressed, the adhesive force can be maintained high, and the easy peelability between adhesive surfaces becomes good.

The thermoplastic elastomer may or may not contain other monomer units in addition to the styrene monomer unit and the conjugated diene monomer unit. Examples of other monomer units include aromatic vinyl compound units other than styrene monomer units.

The thermoplastic elastomer preferably has a total of styrene monomer units and conjugated diene monomer units of 90% by mass or more, more preferably 95% by mass or more, more preferably 97% by mass or more, and 99% by mass or more of the total monomer units. It is more desirable.

As described above, the thermoplastic elastomer may contain only one type of styrene monomer unit and a conjugated diene monomer unit, or may contain two or more types of styrene monomer unit. When two or more types are included, it is preferable that the total amount falls within the above range.

The thermoplastic elastomer used in this embodiment may be a block polymer or a random polymer. Additionally, the conjugated diene monomer unit may be a hydrogenated elastomer to which hydrogen has been added, an unhydrogenated elastomer to which no hydrogen has been added, or a partially hydrogenated elastomer to which hydrogen has been partially added.

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

When the resin composition contains a thermoplastic elastomer, the content is preferably 1 part by mass or more, more preferably 3 parts by mass or more, more preferably 5 parts by mass or more, and 8 parts by mass based on 100 parts by mass of the resin solid content. It is more preferable that it is more than 10 parts by mass, and it is even more preferable that it is 10 parts by mass or more. By exceeding the above 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, more preferably 35 parts by mass or less, and even more preferably 32 parts by mass or less, based on 100 parts by mass of the resin solid content. And, it is further more preferable that it is 28 parts by mass or less. By setting it below the above upper limit, heat resistance tends to further improve.

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, it is preferable that the total amount falls within the above range.

(filling)

The resin composition may contain a filler in order to improve low dielectric constant and low dielectric dissipation property. As a filler, a known filler can be suitably used, and its type is not particularly limited, and a filler generally used in the industry can be suitably used. Specifically, silica 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, agglomerated boron nitride, silicon nitride, Aluminum nitride, barium sulfate, aluminum hydroxide, heat-treated aluminum hydroxide products (heat-treated aluminum hydroxide to reduce a portion of the crystal water), metal hydrates such as boehmite and magnesium hydroxide, molybdenum oxide and molybdenum Molybdenum compounds such as zinc acid, 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 fibers (including glass fine powders such as E-glass, T-glass, D-glass, S-glass, Q-glass, etc.), hollow glass In addition to inorganic fillers such as spherical glass, organic fillers such as rubber powders such as styrene type, butadiene type, and acrylic type, core-shell type rubber powder, silicone resin powder, silicone rubber powder, and silicone composite powder can be mentioned. These fillers may be used individually, or two or more types may be used together.

Among these, one or two or more types selected from the group consisting of silica, aluminum hydroxide, boehmite, magnesium oxide, and magnesium hydroxide are preferable. By using these fillers, properties such as thermal expansion characteristics, dimensional stability, and flame retardancy of the resin composition are improved.

The content of the filler in the resin composition can be appropriately set depending on the desired characteristics and is not particularly limited, but when contained, it is preferably 50 parts by mass or more based on 100 parts by mass of the resin solid content in the resin composition. As an upper limit, 1600 parts by mass or less is preferable, 500 parts by mass or less is more preferable, and 300 parts by mass or less is particularly preferable. Alternatively, the filler may be added in an amount of 75 to 250 parts by mass, or 100 to 200 parts by mass. By keeping the content of the filler within this range, the moldability of the resin composition becomes good. The resin composition may contain only one type of filler or may contain two or more types of filler. When two or more types are included, it is preferable that the total amount falls within the above range.

Additionally, when using a filler, it is preferable to use at least one type selected from the group consisting of a silane coupling agent and a wetting and dispersing agent in combination. As the silane coupling agent, those generally used for surface treatment of inorganic materials can be suitably used, and their type is not particularly limited. Specifically, aminosilanes such as γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-( Epoxy silanes such as 3,4-epoxycyclohexyl)ethyltrimethoxysilane, vinyl silanes such as γ-methacryloxypropyltrimethoxysilane and vinyl-tri(β-methoxyethoxy)silane, N- Cationic silanes such as β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride, phenyl silanes, etc. are included. The silane coupling agent may be used individually, or two or more types may be used together. Additionally, as the wetting and dispersing agent, those generally used for paints can be suitably used, and their type is not particularly limited. Preferably, a copolymer-based wetting and dispersing agent is used, and specific examples thereof include Disperbyk-110, 111, 161, 180, 2009, 2152, BYK-W996, BYK-, manufactured by BYK Japan KK. Examples include W9010, BYK-W903, BYK-W940, etc. Wetting and dispersing agents may be used individually, or two or more types may be used in combination.

The content of the silane coupling agent is not particularly limited, and may be about 1 part by mass to 5 parts by mass based on 100 parts by mass of the resin solid content in the resin composition. The content of the dispersant (in particular, the wetting dispersant) 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 styrene oligomer. The styrene oligomer according to the present embodiment is made by polymerizing at least one member selected from the group consisting of styrene, styrene derivatives, and vinyl toluene, and its number average molecular weight is 178 to 1600, the average number of aromatic rings is 2 to 14, and the number of aromatic rings is 178 to 1600. It is a non-branched compound with a total amount of 2 to 14 of 50% by mass or more and a boiling point of 300°C or more. By including styrene oligomer, low dielectric constant and low dielectric loss tangent can be improved. Additionally, the “styrene oligomer” used in this embodiment is different from the “thermoplastic elastomer” described above.

Examples of styrene oligomers include styrene polymer, vinyltoluene polymer, α-methylstyrene polymer, vinyltoluene-α-methylstyrene polymer, and styrene-α-styrene polymer. As the styrene polymer, a commercially available product may be used, for example, Picolastic A5 (produced by Eastman Chemical), Picolastic A-75 (produced by Eastman Chemical), Picotex 75 (produced by Eastman Chemical), FTR-8100 (produced by Mitsui Chemicals) (manufactured by Mitsui Chemicals, Inc.) and FTR-8120 (manufactured by Mitsui Chemicals, Inc.). Additionally, examples of the vinyltoluene-α-methylstyrene polymer include Picotex LC (manufactured by Eastman Chemical). In addition, as α-methylstyrene polymers, Crystalex 3070 (manufactured by Eastman Chemical), Crystalex 3085 (manufactured by Eastman Chemical), Crystalex 3100, Crystalex 5140 (manufactured by Eastman Chemical), and FMR-0100 (manufactured by Mitsui Chemicals Co., Ltd.) , FMR-0150 (manufactured by Mitsui Chemicals Co., Ltd.). Additionally, examples of styrene-α-styrene polymer include FTR-2120 (manufactured by Mitsui Chemicals Co., Ltd.). These styrene oligomers may be used individually, or two or more types may be used in combination.

The content of styrene oligomer in the resin composition, when 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 low dielectric constant, low dielectric constant and chemical resistance. It is preferable that it is 5 parts by mass or more, and especially preferably 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. When two or more types are included, it is preferable that the total amount falls within the above range.

(flame retardant)

The resin composition may contain a flame retardant to improve flame resistance. As the flame retardant, known ones can be used, for example, brominated epoxy resin, brominated polycarbonate, brominated polystyrene, brominated styrene, brominated phthalimide, tetrabromobisphenol A, pentabromobenzyl (meth)acrylate, pentabro. Halogen-based flame retardants such as motoluene, tribromophenol, hexabromobenzene, decabromodiphenyl ether, bis-1,2-pentabromophenylethane, chlorinated polystyrene, chlorinated paraffin, red phosphorus, tricresyl phosphate, tri Phenyl phosphate, cresyl diphenyl phosphate, trixylenyl phosphate, trialkyl phosphate, dialkyl phosphate, tris(chloroethyl) phosphate, phosphazene, 1,3-phenylenebis(2,6-dicxylenyl phosphate), Phosphorus-based flame retardants such as 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, aluminum hydroxide, magnesium hydroxide, partial boehmite, boehmite, zinc borate, Examples include inorganic flame retardants such as antimony trioxide, and silicone-based flame retardants such as silicone rubber and silicone resin. These flame retardants may be used individually, or two or more types may be used in combination. Among these, phosphorus-based flame retardants are preferable, and 1,3-phenylenebis (2,6-dicylenyl phosphate) is particularly preferable because it is difficult to impair low dielectric properties. The phosphorus content in the resin composition is preferably 0.1 mass% to 5 mass%.

The content of the flame retardant, when contained, is preferably 1 part by mass or more, and more preferably 5 parts by mass or more, based on 100 parts by mass of the resin solid content in the resin composition. Moreover, the upper limit of this 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 type of flame retardant may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount falls within the above range.

(Other ingredients)

In addition, the resin composition is a polyphenylene ether compound other than the terminal unsaturated group-modified polyphenylene ether, an oxetane resin, a benzoxazine compound, or a thermoplastic elastomer that does not contain a styrene monomer unit, within the range that can obtain the desired properties. (hereinafter referred to as “other thermoplastic elastomers”), a curing accelerator, an organic solvent, etc. may be contained. By using these together, desired characteristics such as low dielectric properties can be improved. In the resin composition, the total amount of polyphenylene ether compounds other than the polyphenylene ether compound and other thermoplastic elastomers is preferably 3% by mass or less, more preferably 1% by mass or less, of the resin solid content. By using this configuration, the effect of the present invention is exhibited more effectively.

(Oxetane Resin)

The oxetane resin is not particularly limited, and examples include oxetane and alkyloxetane (e.g., 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, 3,3-dimethyloxetane). cetane, etc.), 3-methyl-3-methoxymethyloxetane, 3,3-di(trifluoromethyl)perfluoxetane, 2-chloromethyloxetane, 3,3-bis(chloromethyl)oxetane, Biphenyl-type oxetane, OXT-101 (produced by TOAGOSEI CO., LTD.), OXT-121 (produced by TOAGOSEI CO., LTD.), etc. can be mentioned. These oxetane resins may be used individually, or two or more types may be used together.

(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, for example, bisphenol A benzoxazine BA-BXZ (Konishi Chemical Co., Ltd.) Ind. Co., Ltd.), bisphenol F-type benzoxazine BF-BXZ (Konishi Chemical Industry Co., Ltd. product), bisphenol S-type benzoxazine BS-BXZ (Konishi Chemical Industry Co., Ltd. product), etc. I can hear it. These benzoxazine compounds may be used individually, or two or more types may be used in combination.

(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, from the viewpoint of better compatibility with polyphenylene ether compounds, at least one selected from the group consisting of polyisoprene, polybutadiene, butyl rubber, and ethylene propylene rubber is more preferable.

(hardening accelerator)

The resin composition may contain a curing accelerator to appropriately adjust the curing speed. Examples of the curing accelerator include those commonly used as curing accelerators for maleimide compounds, epoxy resins, etc., and organic metal salts (e.g., zinc octylate, zinc naphthenate, cobalt naphthenate, copper naphthenate, iron acetylacetone). , 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.), imidazoles (e.g., 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-hydroxy methylimidazole, etc.), derivatives such as carboxylic acids of these imidazoles or adducts of their acid anhydrides, and amines (e.g., dicyandiamide, benzyldimethylamine, 4-methyl-N,N-dimethylbenzyl) amines, 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) oxide, p-chlorobenzoyl peroxide, di-t-butyl peroxide, diisopropyl peroxycarbonate, di-2-ethylhexyl peroxycarbonate, etc.), azo compounds (e.g. azobisisobutyronitrile, etc.) ) can be mentioned. The curing accelerator may be used individually, or two or more types may be used in combination. The content of the curing accelerator may usually be about 0.005 parts by mass to 10 parts by mass based on 100 parts by mass of the resin solid content in the resin composition.

The resin composition may contain various polymer compounds such as thermosetting resins, thermoplastic resins, and oligomers thereof, and various additives other than the above components. Additives include ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescent whitening agents, photosensitizers, dyes, pigments, thickeners, flow regulators, lubricants, defoamers, dispersants, leveling agents, brighteners, polymerization inhibitors, etc. These additives may be used individually, or two or more types may be used together.

<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 dissolved in 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 the polar organic solvent 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, isoamyl acetate, methyl lactate, methyl methoxypropionate, methyl hydroxyisobutyrate, etc.), amides (e.g., dimethoxyacetamide, dimethylformamide, etc.), Examples of nonpolar organic solvents include aromatic hydrocarbons (eg, toluene, xylene, etc.). These organic solvents may be used individually, or two or more types may be used together.

[Usage]

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

[Laminate]

The laminated board is obtained by heating and pressing a laminate containing one or more sheets of prepreg according to the present embodiment and curing the prepreg, and is a layer formed from the prepreg according to the present embodiment, that is, the layer formed by the prepreg according to the present embodiment. It contains a cured product of prepreg. The forming method and conditions for forming the laminated board are not particularly limited, and general methods and conditions can be used. For example, during molding, a multi-stage press machine, a multi-stage vacuum press machine, a continuous molding machine, an autoclave molding machine, etc. can be used. In molding (lamination molding), the temperature is generally in the range of 100°C to 300°C, the pressure is in the range of 2kgf/cm2 to 100kgf/cm2, and the heating time is generally in the range of 0.05 to 5 hours. Additionally, post-curing may be performed at a temperature of 150°C to 300°C if necessary. In particular, when using a multi-stage press, from the viewpoint of sufficiently promoting curing of the prepreg, a temperature of 200°C to 250°C, a pressure of 10kgf/cm2 to 40kgf/cm2, and a heating time of 80 minutes to 130 minutes are preferable, and a temperature of 215°C is preferable. ~235℃, pressure 25kgf/cm2~35kgf/cm2, and heating time 90~120 minutes are more preferable.

[Printed wiring board]

The printed wiring board is provided with an insulating layer and a conductor layer, and the insulating layer contains a layer formed of 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 normal method, and the manufacturing method is not particularly limited. Below, an example of a method for manufacturing a printed wiring board is shown. First, a metal clad laminate such as a copper clad laminate is prepared by stacking one or more sheets of prepreg and placing metal foil on one or both sides of the prepreg. Next, an inner layer substrate is manufactured by etching the surface of the metal clad laminate to form an inner layer circuit. The surface of the inner layer circuit of this inner layer substrate is subjected to surface treatment to increase the adhesive strength as necessary. Then, the desired number of prepregs described above are stacked on the surface of the inner layer circuit, and a metal foil for the outer layer circuit is placed on the outside. They are laminated, heated and pressed, and integrally molded. In this way, a multi-layer laminate is manufactured in which an insulating layer made of a cured prepreg is formed between the metal foil for the inner layer circuit and the outer layer circuit. Subsequently, after performing punching processing for through holes and via holes on this multi-layer laminate, a plated metal film is formed on the wall of this hole to conduct the metal foil for the inner layer circuit and the outer layer circuit, and then again for the outer layer circuit. A printed wiring board is manufactured by etching a metal foil to form an outer layer circuit.

In this way, according to this embodiment, since the ratio, relative dielectric constant, and dielectric loss tangent of the resin composition are adjusted, skew and transmission loss can be reduced, and the signal speed can be increased. Therefore, it can respond to high frequencies.

(Example)

(Synthesis Example 1) Synthesis of naphthol aralkyl type cyanate ester compound (SNCN)

300 g (1.28 mol of OH group conversion) of 1-naphthol aralkyl resin (Nippon Steel & Sumikin Chemical Co., Ltd.) and 194.6 g (1.92 mol) of triethylamine (1 mol of hydroxy group) 1.5 mol) was dissolved in 1800 g of dichloromethane, and this was used as 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 stirred at a liquid temperature of -2°C. Solution 1 was added dropwise over 30 minutes while maintaining -0.5°C. After completing the dropwise addition of Solution 1, stirring at the same temperature for 30 minutes, a solution of 65 g (0.64 mol) of triethylamine (0.5 mol for 1 mol of hydroxyl group) dissolved in 65 g of dichloromethane (Solution 2) was stirred for 10 minutes. It was dripped over. After completing the dropwise addition of Solution 2, the reaction was completed by stirring at the same temperature for 30 minutes.

Afterwards, the reaction solution was left standing to separate the organic phase and the water phase. The obtained organic phase was washed 5 times with 1300 g of water. The electrical conductivity of the wastewater after the 5th washing with water was 5 μS/cm, confirming that the ionic compounds to be removed were sufficiently removed by washing with water.

The organic phase after washing with water was concentrated under reduced pressure, and finally concentrated to dryness at 90°C for 1 hour to obtain 331 g of the target naphthol aralkyl type cyanate ester compound (SNCN) (orange viscous substance). The weight average molecular weight (Mw) of the obtained SNCN was 600. Additionally, the IR spectrum of SNCN showed absorption at 2250 cm ^-1 (cyanic acid ester group) and did not show absorption of the hydroxy group.

(Example 1)

As the resin solid content of the resin composition, in the general formula (11), R ₅₁ and R ₅₂ are hydrogen atoms, and n ₄ is 1 to 3. A maleimide compound (BMI-2300, manufactured by Daiwa Kasei Industry Co., Ltd.) 15 mass Part _, 35 parts by mass of cyanate ester compound (SNCN) obtained in Synthesis Example 1, where in the general formula (5), 10 parts by mass of terminally unsaturated group-modified polyphenylene ether (OPE-2St1200, manufactured by Mitsubishi Gas Chemical Co., Ltd., number average molecular weight 1187, vinyl group equivalent: 590g/eq), in which structural units are polymerized, terminally unsaturated group-modified poly As the second component of phenylene ether, in _general formula (5), Unsaturated group-modified polyphenylene ether (OPE-2St2200, manufactured by Mitsubishi Gas Chemical Co., Ltd., number average molecular weight 2200, vinyl equivalent: 1100 g/eq), 10 parts by mass, styrene-isoprene-styrene elastomer (SEPTON 2104, manufactured by Mitsubishi Gas Chemical Co., Ltd.) 10 parts by mass of α-methylstyrene polymer (Crystalex 3085, manufactured by Eastman Chemical) were prepared. 100 parts by mass of this resin solid were mixed with 150 parts by mass of spherical silica (SC2500MB, manufactured by ADMATECHS COMPANY LIMITED, Inc., average particle diameter 0.5㎛) as a filler, and diluted with methyl ethyl ketone, an organic solvent, to form a varnish. got it This varnish was impregnated and applied to a glass fiber-based low-dielectric glass cloth with a thickness of 32㎛, and dried at 165°C for 5 days using a dryer (explosion-proof steam dryer, manufactured by TAKASUGI MFG. Co. Ltd.). By heating and drying for several minutes, a prepreg was obtained. The ratio of the resin composition (in Example 1, resin solid content + filler) to the total amount of prepreg was 87.6% by volume.

(Example 2)

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

(Example 3)

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

(Example 4)

As the resin solid content of the resin composition, 40 parts by mass of a maleimide compound (MIR-5000, manufactured by Nippon Kayaku Co., Ltd.) represented by the general formula (15), where in the general formula (5), ―(Y―O)n ₂ ― is a terminally unsaturated group-modified polyphenylene ether (OPE-2St2200, manufactured by Mitsubishi Gas Chemical Co., Ltd., number average molecular weight 2200, vinyl Group equivalent weight: 35 parts by mass of 1100 g/eq) and 25 parts by mass of styrene-butadiene block copolymer (TR2250, manufactured by JSR Co., Ltd., styrene ratio 52%) were prepared. This resin solid content was mixed and diluted with methyl ethyl ketone, an organic solvent, to obtain varnish. This varnish was impregnated and applied to a glass fiber-based, low-dielectric glass cloth with a thickness of 14 μm, and heated and dried at 165°C for 3 minutes using a dryer (explosion-proof steam dryer, manufactured by Takasugi Manufacturing Co., Ltd.) to obtain a 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)

As a glass fiber base material, a low-dielectric glass cloth with a thickness of 9 μm was used, and the ratio of the resin composition (resin solid content in Example 5) to the total amount of prepreg was set to 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, in the general formula (11), R ₅₁ and R ₅₂ are hydrogen atoms, and n ₄ is 1 to 3. A maleimide compound (BMI-2300, manufactured by Daiwa Kasei Industry Co., Ltd.) 10 mass Part _, 30 parts by mass of cyanate ester compound (SNCN) obtained in Synthesis Example 1, where in the general formula (5), 60 parts by mass of a polyphenylene ether compound (OPE-2St1200, manufactured by Mitsubishi Gas Chemical Co., Ltd., number average molecular weight 1187, vinyl equivalent: 590 g/eq), in which structural units were polymerized, was prepared. 100 parts by mass of this resin solid content, 100 parts by mass of spherical silica (SC2500MB, manufactured by Admatex Co., Ltd., average particle diameter 0.5 μm) as a filler, and 0.1 parts by mass of zinc octylate as a curing accelerator were mixed, and methyl as an organic solvent was mixed. Varnish was obtained by diluting with ethyl ketone. This varnish was impregnated and applied to a glass fiber-based low-dielectric glass cloth with a thickness of 32 ㎛, and heated and dried at 165°C for 5 minutes using a dryer (explosion-proof steam dryer, manufactured by Takasugi Manufacturing Co., Ltd.) to obtain a prepreg. . The ratio of the resin composition (in Example 6, resin solid content + filler + curing accelerator) to the total amount of prepreg was 87.6% by volume.

(Comparative Example 1)

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

(Comparative Example 2)

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

(Comparative Example 3)

As a glass fiber base material, a low-dielectric glass cloth with a thickness of 43 μm was used, and the ratio of the resin composition (in Comparative Example 3, resin solid content + filler) to the total amount of prepreg was set to 80.9% by volume. A prepreg was produced 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㎛ thick copper foil (3EC-M3-VLP, manufactured by Mitsui Mining & SMELTING CO., LTD.) using a bar coater. , a copper-adhered resin sheet was obtained. Using a dryer (pressure-resistant explosion-proof steam dryer, manufactured by Takasugi Co., Ltd.), the obtained copper-coated resin sheet was heated and dried at 130°C for 5 minutes to obtain a semi-cured copper-coated resin sheet with a resin thickness of 25 μm. The ratio of the resin composition (in Comparative Example 4, resin solid content + filler) to the total amount of the resin sheet is 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 Metal Mining 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 Co., Ltd.), the obtained copper-coated resin sheet was heated and dried at 130°C for 5 minutes to obtain a semi-cured copper-coated resin sheet with a resin thickness of 25 μm. The ratio of the resin composition (resin solid content in Comparative Example 5) to the total amount of the resin sheet is 100% by volume.

(Comparative Example 6)

As the resin solid content of the resin composition, 65 parts by mass of 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 Co., Ltd.) 30 parts by weight of product) and 5 parts by weight of naphthalene skeleton epoxy resin (HP-4032D, epoxy equivalent: 140 g/eq, manufactured by DIC Co., Ltd.) were prepared. 100 parts by mass of this resin solid content, 100 parts by mass of spherical silica (SC2500MB, manufactured by Admatex Co., Ltd., average particle diameter 0.5 μm) as a filler, and 0.1 parts by mass of zinc octylate as a curing accelerator were mixed, and methyl as an organic solvent was mixed. Varnish was obtained by diluting with ethyl ketone. This varnish was impregnated and applied to E glass cloth with a thickness of 32 μm, which is a glass fiber base, and heated and dried at 165°C for 4 minutes using a dryer (explosion-proof steam dryer, manufactured by Takasugi Co., Ltd.) to obtain a prepreg. The ratio of the resin composition (in Comparative Example 6, resin solid content + filler + curing accelerator) to the total amount of prepreg was 87.6% by volume.

(Production of samples for evaluation)

With respect to 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 both sides were coated with copper foil (3EC-M3-VLP, Mitsui Metal Mining Co., Ltd. ) product, thickness 12㎛) was placed and vacuum pressed (heat cured) at a pressure of 30kgf/cm2 and a temperature of 210°C for 150 minutes to obtain copper-clad laminates with the thickness of the prepreg layer being 0.1mm and 0.4mm. .

Additionally, with respect to the semi-cured copper-coated resin sheets obtained in Comparative Examples 4 and 5, two semi-cured copper-coated resin sheets were heated and laminated so that the resin surfaces were in contact. After that, the copper foil was peeled off, and the top and bottom were again placed so that the resin surfaces were in contact. By repeating heating and laminating two semi-cured copper-attached resin sheets and peeling off the copper foil once or seven times, semi-cured resin sheets with a thickness of 0.1 mm and 0.4 mm of the resin layer with copper foil laminated on both sides are formed. got it 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/cm2 and a temperature of 210°C for 150 minutes to obtain a copper-clad laminate with a resin layer thickness of 0.1 mm and 0.4 mm. .

(Evaluation of relative permittivity (Dk) and dielectric loss tangent (Df))

Using samples from which the copper foil of the copper-clad laminate with a thickness of 0.4 mm obtained in each example and each comparative example was removed by etching, a relative permittivity of 10 GHz was obtained using a perturbation method cavity resonator (Agilent Technologies product, Agilent 8722ES). and dielectric loss tangent were measured. The obtained results are shown in Table 1 and Table 2.

(Evaluation of skew)

Only one side of the copper-clad laminate with a thickness of 0.1 mm obtained in each example and each comparative example was etched to form 15 microstrip lines with a circuit length of 10 cm. The transmission speed of 15 conductor wires (impedance 50Ω) was measured from 10GHz to 20GHz, and the difference between the maximum and minimum values was calculated as skew (SKEW). The obtained results are shown in Table 1, Table 2, and Figure 2.

(Evaluation of transmission loss)

A wiring board on which a microstrip line with a circuit length of 10 cm was formed was produced by etching only one side of the copper clad laminate with a thickness of 0.1 mm obtained in each example and each comparative example, and the transmission characteristics were evaluated. A high-frequency signal was transmitted using a network analyzer N5227B from Keysight Technologies, and the transmission loss at 20 GHz was measured. The obtained results are shown in Table 1, Table 2, and Figure 1.

(Evaluation of bending)

The upper and lower copper foils of the copper clad laminates with a thickness of 0.1 mm obtained in each Example and each Comparative Example were processed using a laser processing machine, and predetermined vias were formed by chemical copper plating. Subsequently, the wiring pattern was etched to form a conductor layer, thereby obtaining a substrate panel (size: 500 mm x 400 mm). Then, the amount of warpage at a total of four corners of the obtained panel was measured with a curved scale, and the average value was taken as “warpage.” The obtained results are shown in Table 1, Table 2, and Figure 3.

As shown in Tables 1 and 2 and Figures 1 to 3, it can be seen that if the ratio of the resin composition to the total amount of prepreg is 81% by volume or more, the skew can be reduced and the relative dielectric constant can be reduced. there was. Additionally, it was found that when the ratio of the resin composition to the total amount of prepreg was 98% by volume or less, the warpage could be sufficiently reduced. That is, it was found that the ratio of the resin composition to the total amount of prepreg is preferably within the range of 81 volume% or more and 98 volume% or less.

Furthermore, according to this embodiment, the relative dielectric constant at 10 GHz after curing of the prepreg can be set to 3.3 or less, and the dielectric loss tangent at 10 GHz after curing of the prepreg can be set to 0.004 or less.

Claims (11)

A prepreg in which a resin composition containing a thermosetting compound is impregnated or applied to a glass fiber base,
The ratio of the resin composition to the total amount of the prepreg is within the range of 81 volume% to 98 volume%,
A prepreg with a relative dielectric constant of 3.3 or less and a dielectric loss tangent of 0.004 or less at 10 GHz after curing.
According to paragraph 1,
A prepreg wherein the glass fiber base material contains at least one type of 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.
According to paragraph 1,
A prepreg in which the thermosetting compound contains terminally unsaturated group-modified polyphenylene ether.
According to paragraph 3,
A prepreg in which the content of the terminally unsaturated group-modified polyphenylene ether is 1 to 70 parts by mass based on 100 parts by mass of the resin solid content in the resin composition.
According to paragraph 1,
A prepreg in which the thermosetting compound contains at least one type selected from the group consisting of maleimide compounds, cyanate ester compounds, epoxy compounds, and phenol compounds.
According to paragraph 1,
A prepreg in which the resin composition further contains a thermoplastic elastomer.
According to clause 6,
A prepreg in which the content of the thermoplastic elastomer is 1 to 45 parts by mass based on 100 parts by mass of the resin solid content in the resin composition.
According to paragraph 1,
A prepreg in which the resin composition further contains a filler.
According to clause 8,
A prepreg in which the content of the filler is 50 to 1,600 parts by mass based on 100 parts by mass of the resin solid content in the resin composition.
A laminate comprising a cured product of the prepreg of claim 1.
A printed wiring board comprising an insulating layer and a conductor layer, wherein the insulating layer contains a cured product of the prepreg of claim 1.

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