KR20240065287A - Resin compositions, prepregs, metal foil-clad laminates, resin composite sheets, printed wiring boards, and semiconductor devices - Google Patents

Abstract

Providing novel resin compositions with excellent moisture absorption and heat resistance while maintaining an excellent low dielectric loss tangent, as well as prepregs, metal foil-clad laminates, resin composite sheets, printed wiring boards, and semiconductor devices. It contains a thermoplastic elastomer (A), a thermoplastic elastomer (B), and a thermosetting resin (C) compatible with both (A) and (B), and the thermoplastic elastomer (A) includes a styrene monomer unit and a conjugated diene monomer. In the thermoplastic elastomer containing units and having a number average molecular weight of 50,000 or more, all of the conjugated diene bonds of the thermoplastic elastomer are hydrogenated thermoplastic elastomers, and the thermoplastic elastomer (B) includes a styrene monomer unit and a conjugated diene monomer unit. And, in the thermoplastic elastomer having a number average molecular weight of 50,000 or more, some of the conjugated diene bonds of the thermoplastic elastomer are hydrogenated and/or all of the thermoplastic elastomer is an unsaturated bond, a resin composition.

Description

Resin compositions, prepregs, metal foil-clad laminates, resin composite sheets, printed wiring boards, and semiconductor devices

The present invention relates to resin compositions, prepregs, metal foil-clad laminates, resin composite sheets, printed wiring boards, and semiconductor devices.

Recently, high integration and miniaturization of semiconductor devices used in electronic devices and communication devices, including portable terminals, are accelerating. In line with this, there is a demand for technology that enables high-density packaging of semiconductor elements, and improvements are also required for printed wiring boards, which occupy an important position.

Meanwhile, the uses of electronic devices are diversifying and continuing to expand. In response to this, the properties required for printed wiring boards, metal foil-clad laminates, and prepregs used therein have also become more diverse and stringent. In order to obtain improved printed wiring boards while considering such required characteristics, various materials and processing methods have been proposed. One of them is the improved development of the resin material constituting the prepreg.

For example, in Patent Document 1, a maleimide compound (A), a cyanate ester compound (B), a polyphenylene ether compound (C) represented by a predetermined formula and having a number average molecular weight of 1,000 or more and 7,000 or less, and a styrene skeleton. A resin composition containing a block copolymer (D) is disclosed.

Moreover, Patent Document 2 discloses a resin composition containing a polyfunctional vinyl aromatic polymer (A) and a thermosetting compound (B) and not containing a radical polymerization initiator.

International Publication No. 2019/230945 International Publication No. 2020/175537

As described above, the uses of electronic devices and the like are diversifying and continuing to expand, and new materials are being required for the resin materials constituting prepregs and the like. In particular, there is a need for additional material development for resin compositions that have excellent moisture absorption and heat resistance while maintaining an excellent low dielectric loss tangent.

The present invention aims to solve the above problems, and provides a novel resin composition excellent in moisture absorption and heat resistance while maintaining an excellent low dielectric loss tangent, and a novel resin composition for preparing prepregs, metal foil-clad laminates, resin composite sheets, printed wiring boards, and semiconductors. The purpose is to provide a device.

As a result of the study conducted by the present inventors under the above problem, the above problem was solved by using a certain hydrogenated thermoplastic elastomer and a certain partially or non-hydrogenated thermoplastic elastomer together. Specifically, the above problem was solved by the following means.

<1> A thermoplastic elastomer (A), a thermoplastic elastomer (B), and a thermosetting resin (C) compatible with both the thermoplastic elastomer (A) and the thermoplastic elastomer (B),

The thermoplastic elastomer (A) is a thermoplastic elastomer containing a styrene monomer unit and a conjugated diene monomer unit and having a number average molecular weight of 50,000 or more, wherein all of the conjugated diene bonds of the thermoplastic elastomer are hydrogenated,

The thermoplastic elastomer (B) is a thermoplastic elastomer containing a styrene monomer unit and a conjugated diene monomer unit and having a number average molecular weight of 50,000 or more, wherein a portion of the conjugated diene bond of the thermoplastic elastomer is hydrogenated, and/or, A resin composition, which is a thermoplastic elastomer with all unsaturated bonds.

<2> The resin composition according to <1>, wherein the total content of the thermoplastic elastomer (A) and the thermoplastic elastomer (B) in the resin composition is 1 to 40 parts by mass based on 100 parts by mass of the resin solid content.

<3> The resin composition according to <1> or <2>, wherein the mass ratio of the thermoplastic elastomer (A) to the thermoplastic elastomer (B) in the resin composition is 1:1 to 10.

<4> The resin composition according to any one of <1> to <3>, wherein the commonly used thermosetting resin (C) is a thermosetting resin containing an aromatic ring and a vinyl group.

<5> The commercially available thermosetting resin (C) is at least one selected from the group consisting of a polymer having a structural unit represented by formula (V), and a polyphenylene ether compound having a carbon-carbon unsaturated double bond at the terminal. The resin composition according to any one of <1> to <4> containing.

[Formula 1]

(In formula (V), Ar represents an aromatic hydrocarbon linking group. * represents the bonding position.)

<6> The resin composition according to any one of <1> to <5>, wherein the content of the commonly used thermosetting resin (C) is 10 to 90 parts by mass based on 100 parts by mass of the resin solid content.

<7> The resin according to any one of <1> to <6>, further comprising at least one other resin (D) selected from the group consisting of cyanate ester compounds, maleimide compounds, and epoxy compounds. Composition.

<8> The maleimide compound is a compound represented by the formula (M0), a compound represented by the formula (M1), a compound represented by the formula (M2), a compound represented by the formula (M3), a compound represented by the formula (M4), and The resin composition according to <7>, comprising at least one selected from the group consisting of compounds represented by formula (M5).

[Formula 2]

(In the formula (M0), R ⁵¹ each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group, R ⁵² each independently represents a hydrogen atom or a methyl group, and n ₁ is an integer of 1 or more. represents.)

[Formula 3]

(In formula (M1), 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, R ^M7 and R ^M8 are each independently an alkyl group, and lx is 0 or 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. Alkyl group with 1 to 10 carbon atoms, alkyloxy group with 1 to 10 carbon atoms, alkylthio group with 1 to 10 carbon atoms, aryl group with 6 to 10 carbon atoms, aryloxy group with 1 to 10 carbon atoms, arylthio group with 1 to 10 carbon atoms , px represents an integer of 0 to 3, and nx represents an integer of 1 to 20.

[Formula 4]

(In formula (M2), R ⁵⁴ each independently represents a hydrogen atom or a methyl group, and n ₄ represents an integer of 1 or more.)

[Formula 5]

(In formula (M3), R ⁵⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group, and n ₅ represents an integer from 1 to 10.)

[Formula 6]

(In formula (M4), R ⁵⁶ each independently represents a hydrogen atom, a methyl group, or an ethyl group, and R ⁵⁷ each independently represents a hydrogen atom or a methyl group.)

[Formula 7]

(In formula (M5), R ⁵⁸ each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group, R ⁵⁹ each independently represents a hydrogen atom or a methyl group, and n ₆ is an integer of 1 or more. represents.)

<9> The resin composition according to <7>, wherein the maleimide compound contains a compound represented by formula (M1) and/or a compound represented by formula (M3).

[Formula 8]

(In formula (M1), 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, R ^M7 and R ^M8 are each independently an alkyl group, and lx is 0 or 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. Alkyl group with 1 to 10 carbon atoms, alkyloxy group with 1 to 10 carbon atoms, alkylthio group with 1 to 10 carbon atoms, aryl group with 6 to 10 carbon atoms, aryloxy group with 1 to 10 carbon atoms, arylthio group with 1 to 10 carbon atoms , px represents an integer of 0 to 3, and nx represents an integer of 1 to 20.

[Formula 9]

(In formula (M3), R ⁵⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group, and n ₅ represents an integer from 1 to 10.)

<10> The resin composition according to any one of <1> to <9>, further comprising a flame retardant (E).

<11> The resin composition according to <10>, wherein the flame retardant (E) contains a phosphorus-based flame retardant.

<12> The resin composition according to any one of <1> to <11>, further comprising a filler (F).

<13> The filler (F) contains at least one selected from the group consisting of silica, aluminum hydroxide, aluminum nitride, boron nitride, forsterite, titanium oxide, barium titanate, strontium titanate, and calcium titanate. The resin composition described in <12>.

<14> The resin composition according to <12> or <13>, wherein the content of the filler (F) is 10 to 300 parts by mass based on 100 parts by mass of the resin solid content.

<15> The resin composition according to any one of <1> to <14>, further comprising 0.5 to 30 parts by mass of a monomer or oligomer having an ethylenically unsaturated group based on 100 parts by mass of the resin solid content.

<16> The total content of the thermoplastic elastomer (A) and the thermoplastic elastomer (B) in the resin composition is 1 to 40 parts by mass based on 100 parts by mass of the resin solid content,

In the resin composition, the mass ratio of the thermoplastic elastomer (A) and the thermoplastic elastomer (B) is 1:1 to 10,

The commercially available thermosetting resin (C) is a thermosetting resin containing an aromatic ring and a vinyl group,

The commercially available thermosetting resin (C) contains at least one member selected from the group consisting of a polymer having a structural unit represented by formula (V), and a polyphenylene ether compound having a carbon-carbon unsaturated double bond at the terminal, ,

[Formula 10]

(In formula (V), Ar represents an aromatic hydrocarbon linking group. * represents the bonding position.)

The content of the commonly used thermosetting resin (C) is 10 to 90 parts by mass based on 100 parts by mass of the resin solid content,

Additionally, it contains at least one other resin (D) selected from the group consisting of cyanate ester compounds, maleimide compounds, and epoxy compounds,

The maleimide compound contains at least one member selected from the group consisting of a compound represented by formula (M1), a compound represented by formula (M3), and a compound represented by formula (M5),

Additionally, it contains a flame retardant (E),

The flame retardant (E) includes a phosphorus-based flame retardant,

Additionally, it comprises a filler (F),

The filler (F) contains at least one member selected from the group consisting of silica, aluminum hydroxide, aluminum nitride, boron nitride, forsterite, titanium oxide, barium titanate, strontium titanate, and calcium titanate,

The content of the filler (F) is 10 to 300 parts by mass based on 100 parts by mass of the resin solid content,

Additionally, the resin composition according to any one of <1> to <15>, which contains 0.5 to 30 parts by mass of a monomer or oligomer having an ethylenically unsaturated group based on 100 parts by mass of the resin solid content.

[Formula 11]

(In formula (M1), 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, R ^M7 and R ^M8 are each independently an alkyl group, and lx is 0 or 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. Alkyl group with 1 to 10 carbon atoms, alkyloxy group with 1 to 10 carbon atoms, alkylthio group with 1 to 10 carbon atoms, aryl group with 6 to 10 carbon atoms, aryloxy group with 1 to 10 carbon atoms, arylthio group with 1 to 10 carbon atoms , px represents an integer of 0 to 3, and nx represents an integer of 1 to 20.

[Formula 12]

(In formula (M3), R ⁵⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group, and n ₅ represents an integer from 1 to 10.)

[Formula 13]

(In formula (M5), R ⁵⁸ each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group, R ⁵⁹ each independently represents a hydrogen atom or a methyl group, and n ₆ is an integer of 1 or more. represents.)

<17> A prepreg formed from a base material and the resin composition according to any one of <1> to <16>.

<18> <17> A metal foil-clad laminate comprising at least one layer formed from the prepreg according to item and metal foil disposed on one side or both sides of the layer formed from the prepreg.

<19> A resin composite sheet comprising a support and a layer formed of the resin composition according to any one of <1> to <16> disposed on the surface of the support.

<20> A printed wiring board comprising an insulating layer and a conductor layer disposed on a surface of the insulating layer, wherein the insulating layer is formed of the resin composition according to any one of <1> to <16> and <17> A printed wiring board comprising at least one of the layers formed from the prepreg described in .

<21> A semiconductor device including the printed wiring board according to <20>.

The present invention makes it possible to provide a novel resin composition having excellent moisture absorption and heat resistance while maintaining an excellent low dielectric loss tangent, as well as prepreg, metal foil-clad laminate, resin composite sheet, printed wiring board, and semiconductor device.

Hereinafter, an embodiment for carrying out the present invention (hereinafter simply referred to as “this embodiment”) will be described in detail. In addition, the following embodiment is an example for explaining the present invention, and the present invention is not limited to this embodiment.

In addition, in this specification, “~” is used to mean that the numerical values described before and after it are included as the lower limit and the upper limit.

In this specification, various physical properties and characteristic values are assumed to be at 23°C, unless otherwise specified.

In the notation of a group (atomic group) in this specification, a notation that does not describe substitution or unsubstitution includes a group (atomic group) that has a substituent as well as a group (atomic group) that does not have a substituent. For example, “alkyl group” includes not only an alkyl group without a substituent (unsubstituted alkyl group) but also an alkyl group with a substituent (substituted alkyl group). In this specification, for notations that do not describe substitution or non-substitution, it is preferable to use unsubstituted.

In this specification, relative dielectric constant refers to the ratio of the dielectric constant of a material to the vacuum dielectric constant. In addition, in this specification, the relative dielectric constant is sometimes simply referred to as “dielectric constant.”

In this specification, “(meth)acrylic” represents both acrylic and methacryl, or either.

If the standards indicated in this specification differ depending on the year or the measurement method, etc., they shall be based on the standards as of January 1, 2021, unless otherwise stated.

In this specification, the resin solid content refers to components excluding fillers and solvents, and refers to thermoplastic elastomer (A), thermoplastic elastomer (B), and thermosetting resin compatible with both thermoplastic elastomer (A) and thermoplastic elastomer (B). (C), and other resins (D), silane coupling agents, and other resin additive components (additives such as flame retardants, etc.) mixed as necessary.

The resin composition of the present embodiment includes a thermoplastic elastomer (A), a thermoplastic elastomer (B), and a thermosetting resin (C) compatible with both the thermoplastic elastomer (A) and the thermoplastic elastomer (B), The thermoplastic elastomer (A) is a thermoplastic elastomer containing a styrene monomer unit and a conjugated diene monomer unit and having a number average molecular weight of 50,000 or more, wherein all of the conjugated diene bonds of the thermoplastic elastomer are hydrogenated, and the thermoplastic elastomer is The elastomer (B) is a thermoplastic elastomer that contains a styrene monomer unit and a conjugated diene monomer unit and has a number average molecular weight of 50,000 or more, in which some and/or all of the conjugated diene bonds of the thermoplastic elastomer are hydrogenated. It is characterized as a thermoplastic elastomer with an unsaturated bond. With such a structure, a resin composition excellent in moisture absorption and heat resistance can be obtained while maintaining an excellent low dielectric loss tangent.

In addition, in the present embodiment, it is presumed that by blending a thermoplastic elastomer, flexibility can be provided to the resin composition and the occurrence of cracks in the resulting cured product can be effectively suppressed. Additionally, it is presumed that thermal expansion of the cured product can be effectively suppressed by blending a thermoplastic elastomer. In particular, it is presumed that by using the thermoplastic elastomer (A), a resin composition with excellent dielectric properties can be obtained. This is presumed to be due to the effect of lowering the polarity of the elastomer by hydrogenating the conjugated diene bond. In addition, since the thermoplastic elastomer (B) is a resin with a large number average molecular weight of 50,000 or more and a high polarity, the resin component (thermoplastic elastomer (A) and a thermosetting resin compatible with the above (A) and (B) ( It is assumed that the compatibility with C)) is excellent, and the moisture absorption and heat resistance of the resin composition is improved.

＜Thermoplastic elastomer (A)＞

The resin composition of this embodiment contains a thermoplastic elastomer (A). The thermoplastic elastomer (A) is a thermoplastic elastomer containing a styrene monomer unit and a conjugated diene monomer unit and having a number average molecular weight of 50,000 or more, in which all of the conjugated diene bonds of the thermoplastic elastomer are hydrogenated (as described herein). (sometimes referred to as “hydrogenated styrene thermoplastic elastomer”). By including the thermoplastic elastomer (A), the effects of excellent low dielectric dissipation properties, crack resistance, and low thermal expansion properties are achieved.

The thermoplastic elastomer (A) in this embodiment contains a styrene monomer unit. By including a styrene monomer unit, compatibility with the thermosetting resin (C) tends to be excellent. Styrene monomers include styrene, α-methylstyrene, p-methylstyrene, divinylbenzene (vinylstyrene), N,N-dimethyl-p-aminoethylstyrene, N,N-diethyl-p-aminoethylstyrene, etc. These are examples, and among these, styrene, α-methylstyrene, and p-methylstyrene are preferable from the viewpoint of availability and productivity. Among these, styrene is particularly preferable.

The content of the styrene monomer unit is preferably in the range of 10 to 50 mass%, more preferably in the range of 13 to 45 mass%, and even more preferably in the range of 15 to 40 mass% of the total monomer units. 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. Moreover, if it is 10 mass% or more, it is preferable because the increase in adhesion can be suppressed, glue residue and stop marks are less likely to occur, and the ease of peeling between adhesive surfaces tends to improve.

The thermoplastic elastomer (A) 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.

For the method of measuring the content of the styrene monomer unit in the thermoplastic elastomer (A) of the present embodiment, the description in International Publication No. 2017/126469 can be taken into consideration, and this content is incorporated into this specification. The same applies to conjugated diene monomer units, etc., which will be described later.

The thermoplastic elastomer (A) in this embodiment contains a conjugated diene monomer unit. By containing a conjugated diene monomer unit, it tends to be excellent in low dielectric dissipation properties, crack resistance, and low thermal expansion properties. 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 -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 (A) may contain only one type or two or more types of conjugated diene monomer units.

In the thermoplastic elastomer (A) used in this embodiment, 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 40/60, It is more preferable that it is in the range of 7/93 to 37/63, and even more preferably it is in the range of 10/90 to 35/65. If the mass ratio of the styrene polymer unit and the conjugated diene monomer unit is in the range of 5/95 to 40/60, adhesion growth can be suppressed, adhesive force can be maintained high, and the ease of peeling between adhesive surfaces becomes good.

In the thermoplastic elastomer (A) used in this embodiment, all of the conjugated diene bonds of the thermoplastic elastomer have been hydrogenated. Here, fully hydrogenated means that the double bond based on the conjugated diene monomer unit in the thermoplastic elastomer (A) is substantially hydrogenated, and in addition to the hydrogenation rate (hydrogenation rate) being 100%, it is 80% or more. The purpose is to include The hydrogenation rate in the thermoplastic elastomer (A) used in this embodiment is preferably 85% or more, more preferably 90% or more, and still more preferably 95% or more.

The thermoplastic elastomer (A) used in this embodiment 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 monomer units derived from aromatic vinyl compounds other than styrene monomer.

In the thermoplastic elastomer (A) used in this embodiment, 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, and 97% by mass or more of the total monomer units. It is more desirable.

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

The number average molecular weight of the thermoplastic elastomer (A) used in this embodiment is 50,000 or more. When set to 50,000 or more, crack resistance tends to be excellent. The number average molecular weight is preferably 60,000 or more, more preferably 70,000 or more, more preferably 80,000 or more, more preferably 90,000 or more, still more preferably 100,000 or more, and even more preferably 150,000 or more. The upper limit of the number average molecular weight of the thermoplastic elastomer (A) is preferably 400,000 or less, more preferably 350,000 or less, and still more preferably 300,000 or less. By setting it below the above upper limit, compatibility with the thermoplastic elastomer (B) and thermosetting resin (C) tends to be further improved.

When the resin composition of the present embodiment contains two or more types of thermoplastic elastomers (A), it is preferable that the number average molecular weight of their mixture satisfies the above range.

The thermoplastic elastomer (A) used in this embodiment may be a block polymer or a random polymer.

Examples of the composition of the thermoplastic elastomer (A) used in this embodiment include SEBS (styrene-ethylene/butylene-styrene copolymer), SEPS (styrene-ethylene/propylene-styrene copolymer), and the like.

Commercially available thermoplastic elastomers (A) used in this embodiment include SEPTON (registered trademark) 2104 manufactured by Kuraray Co., Ltd., S.O.E. manufactured by Asahi Kasei Co., Ltd. (registered trademark) S1606, S1613, S1605, manufactured by JSR Corporation, DYNARON (registered trademark) 9901P, etc. are examples.

The content of the thermoplastic elastomer (A) in the resin composition of the present embodiment is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and still more preferably 2 parts by mass or more, based on 100 parts by mass of the resin solid content. It is more preferable that it is 3 parts by mass or more, and it is even more preferable that it is 4 parts by mass or more. By exceeding the above lower limit, the low dielectric loss tangent, crack resistance, and low thermal expansion tend to be further improved. Moreover, the upper limit of the content of the thermoplastic elastomer (A) is preferably 20 parts by mass or less, more preferably 18 parts by mass or less, even more preferably 15 parts by mass or less, based on 100 parts by mass of the resin solid content. It is more preferable that it is 10 parts by mass or less, and it is even more preferable that it is 10 parts by mass or less. By setting it below the above upper limit, moisture absorption and heat resistance tends to improve further.

The resin composition of this embodiment may contain only one type of thermoplastic elastomer (A), 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.

＜Thermoplastic elastomer (B)＞

The resin composition of this embodiment contains a thermoplastic elastomer (B). The thermoplastic elastomer (B) is a thermoplastic elastomer containing a styrene monomer unit and a conjugated diene monomer unit and having a number average molecular weight of 50,000 or more, in which some of the conjugated diene bonds of the thermoplastic elastomer are hydrogenated, and/or all of them are hydrogenated. It is a thermoplastic elastomer with an unsaturated bond. By including the thermoplastic elastomer (B), compatibility with the thermoplastic elastomer (A) is improved and moisture absorption and heat resistance are excellent.

The thermoplastic elastomer (B) in this embodiment contains a styrene monomer unit. By including a styrene monomer unit, compatibility with the thermosetting resin (C) tends to be excellent. Styrene monomers include styrene, α-methylstyrene, p-methylstyrene, divinylbenzene (vinylstyrene), N,N-dimethyl-p-aminoethylstyrene, N,N-diethyl-p-aminoethylstyrene, etc. These are examples, and among these, styrene, α-methylstyrene, and p-methylstyrene are preferable from the viewpoint of availability and productivity. Among these, styrene is particularly preferable.

The content of the styrene monomer unit is preferably in the range of 10 to 50 mass%, more preferably in the range of 13 to 45 mass%, and even more preferably in the range of 15 to 40 mass% of the total monomer units. 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. Moreover, if it is 10 mass% or more, it is preferable because the increase in adhesion can be suppressed, glue residue and stop marks are less likely to occur, and the ease of peeling between adhesive surfaces tends to improve.

The thermoplastic elastomer (B) 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.

For the method of measuring the content of the styrene monomer unit in the thermoplastic elastomer (B) of the present embodiment, the description in International Publication No. 2017/126469 can be taken into consideration, and this content is incorporated into this specification. The same applies to conjugated diene monomer units, etc., which will be described later.

The thermoplastic elastomer (B) in this embodiment contains a conjugated diene monomer unit. By containing a conjugated diene monomer unit, it tends to be excellent in low dielectric dissipation properties, crack resistance, and low thermal expansion properties. 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 -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 (B) may contain only one type or two or more types of conjugated diene monomer units.

In the thermoplastic elastomer (B) used in this embodiment, 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 40/60, It is more preferable that it is in the range of 7/93 to 37/63, and even more preferably it is in the range of 10/90 to 35/65. If the mass ratio of the styrene polymer unit and the conjugated diene monomer unit is in the range of 5/95 to 40/60, adhesion growth can be suppressed, adhesive force can be maintained high, and the ease of peeling between adhesive surfaces becomes good.

In the thermoplastic elastomer (B) used in this embodiment, the conjugated diene bond of the thermoplastic elastomer is not hydrogenated or only a portion of the conjugated diene bond is hydrogenated. Here, being only partially hydrogenated means that part of the double bond based on the conjugated diene monomer unit in the thermoplastic elastomer (B) is hydrogenated, and the hydrogenation rate (hydrogenation rate) is less than 80%. The hydrogenation rate of the thermoplastic elastomer (B) used in this embodiment is more preferably 60% or less, further preferably 40% or less, still more preferably 20% or less, even more preferably 10% or less, and 5 % or less is even more preferable.

The thermoplastic elastomer (B) used in this embodiment 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 monomer units derived from aromatic vinyl compounds other than styrene monomer.

In the thermoplastic elastomer (B) used in this embodiment, 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, and 97% by mass or more of the total monomer units. More preferably, it is even more preferable that it is 99% by mass or more.

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

The number average molecular weight of the thermoplastic elastomer (B) used in this embodiment is 50,000 or more. By setting it to 50,000 or more, crack resistance and compatibility with the thermoplastic elastomer (A) tend to be more excellent. The number average molecular weight is preferably 60,000 or more, more preferably 70,000 or more, more preferably 80,000 or more, more preferably 100,000 or more, more preferably 120,000 or more, and even more preferably 150,000 or more. The upper limit of the number average molecular weight of the thermoplastic elastomer (B) is preferably 400,000 or less, more preferably 350,000 or less, and still more preferably 300,000 or less. By setting it below the above upper limit, compatibility with the thermosetting resin (C) tends to be further improved.

When the resin composition of the present embodiment contains two or more types of thermoplastic elastomers (B), it is preferable that the number average molecular weight of their mixture satisfies the above range.

The thermoplastic elastomer (B) used in this embodiment may be a block polymer or a random polymer.

Examples of the composition of the thermoplastic elastomer (B) used in this embodiment include SBS (styrene-butadiene-styrene copolymer).

Commercially available thermoplastic elastomers (B) used in this embodiment include TR2250, manufactured by JSR Corporation, and S.O.E., manufactured by Asahi Kasei Corporation. (registered trademark) S1609, etc. are exemplified.

The content of the thermoplastic elastomer (B) in the resin composition of the present embodiment is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and still more preferably 2 parts by mass or more, based on 100 parts by mass of the resin solid content. It is more preferable that it is 3 parts by mass or more, and it is even more preferable that it is 4 parts by mass or more. By exceeding the above lower limit, the low dielectric loss tangent, crack resistance, and low thermal expansion tend to be further improved. Moreover, the upper limit of the content of the thermoplastic elastomer (B) is preferably 20 parts by mass or less, more preferably 18 parts by mass or less, even more preferably 15 parts by mass or less, based on 100 parts by mass of the resin solid content. It is more preferable that it is 10 parts by mass or less, and it is even more preferable that it is 10 parts by mass or less. By setting it below the above upper limit, moisture absorption and heat resistance tends to improve further.

The resin composition of this embodiment may contain only one type of thermoplastic elastomer (B), 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 the resin composition of the present embodiment, the mass ratio of the thermoplastic elastomer (A) and the thermoplastic elastomer (B) is preferably 1:1 to 10. When the thermoplastic elastomer (B) is used at 1 part by mass or more per 1 mass part of the thermoplastic elastomer (A), the moisture absorption and heat resistance tends to be further improved. Additionally, when the thermoplastic elastomer (B) is contained at 10 parts by mass or less per 1 part by mass of the thermoplastic elastomer (A), the low dielectric dissipation property and crack resistance tend to be further improved. The mass ratio of the thermoplastic elastomer (A) and the thermoplastic elastomer (B) is more preferably 1:1 to 9, more preferably 1:1 to 8, still more preferably 1:1 to 7, and 1:1 to 8. : 1 to 5 is more preferable.

The total content of the thermoplastic elastomer (A) and the thermoplastic elastomer (B) in the resin composition of the present embodiment is preferably 1 to 40 parts by mass based on 100 parts by mass of the resin solid content. By exceeding the above lower limit, the low dielectric loss tangent, crack resistance, and low thermal expansion tend to be further improved. Moreover, by setting it below the above upper limit, the moisture absorption and heat resistance tends to improve further.

The total amount is more preferably 3 parts by mass or more, more preferably 5 parts by mass or more, even more preferably 7 parts by mass or more, and even more preferably 10 parts by mass or more, based on 100 parts by mass of the resin solid content. Moreover, the total amount is more preferably 35 parts by mass or less, more preferably 30 parts by mass or less, even more preferably 25 parts by mass or less, and even more preferably 20 parts by mass or less, based on 100 parts by mass of the resin solid content. .

＜Commercially used thermosetting resin (C)＞

The resin composition of the present embodiment contains a thermosetting resin (C) that is compatible with both the thermoplastic elastomer (A) and the thermoplastic elastomer (B). By including a commercially available thermosetting resin (C) (hereinafter, in this specification, also referred to as “commercially available thermosetting resin (C)” or “thermosetting resin (C)”), the effect of improving low dielectric properties and moisture absorption and heat resistance is achieved. do.

Here, compatible means that after the thermoplastic elastomer (A), the thermoplastic elastomer (B), and the thermosetting resin (C) are sufficiently mixed and allowed to stand, coarse separation does not occur, and usually can be observed with the naked eye.

The commonly used thermosetting resin (C) is preferably a thermosetting resin containing an aromatic ring and a vinyl group. By using such a resin, it is easy to become compatible with the styrene monomer units contained in the thermoplastic elastomer (A) and the thermoplastic elastomer (B), and compatibility tends to be further improved.

The molecular weight of the commercially available thermosetting resin (C), in terms of number average molecular weight Mn, is preferably 300 or more, more preferably 500 or more, still more preferably 1,000 or more, and even more preferably 1,500 or more. The upper limit is preferably 130,000 or less, more preferably 120,000 or less, still more preferably 110,000 or less, and even more preferably 100,000 or less. When two or more types of thermosetting resins (C) are included, the number average molecular weight of the mixture is preferably within the above range.

In this embodiment, the commercially available thermosetting resin (C) is selected from the group consisting of a polymer having a structural unit represented by formula (V), and a polyphenylene ether compound having a carbon-carbon unsaturated double bond at the terminal. It is preferable to include more than one type. When such a resin is used, the effect of the present invention is exhibited more effectively.

[Formula 14]

(In formula (V), Ar represents an aromatic hydrocarbon linking group. * represents the bonding position.)

The commonly used thermosetting resin (C) may further contain a structural unit derived from maleic anhydride. For details of such resin, the description of International Publication No. 2017/209108 can be taken into consideration, and this content is incorporated into this specification.

Furthermore, the commonly used thermosetting resin (C) may contain a structural unit derived from a compound having an acid group and an acid anhydride group.

In the resin composition of the present embodiment, the content of the commonly used thermosetting resin (C) is preferably 10 to 90 parts by mass when the resin solid content in the resin composition is 100 parts by mass. The lower limit of the content of the commercially available thermosetting resin (C) is preferably 15 parts by mass or more, more preferably 20 parts by mass or more, and even more preferably 25 parts by mass or more, when the resin solid content in the resin composition is 100 parts by mass. do. By setting the content of the commonly used thermosetting resin (C) to the above lower limit or more, low dielectric properties, particularly low dielectric loss tangent, can be effectively achieved. On the other hand, the upper limit of the content of the commonly used thermosetting resin (C) is preferably 80 parts by mass or less, more preferably 60 parts by mass or less, and 50 parts by mass or less, when the resin solid content in the resin composition is 100 parts by mass. It is more preferable that it is 40 parts by mass or less. By setting it below the above upper limit, the peeling strength of the metal foil of the obtained cured product can be effectively increased.

The above-mentioned commonly used thermosetting resin (C) may be contained in the resin composition as one type, or may be contained as two or more types. When two or more types are contained, it is preferable that the total amount falls within the above range.

<<Polymer having a structural unit represented by formula (V)>>

The resin composition of the present embodiment preferably contains a polymer having a structural unit represented by formula (V). By containing a polymer having a structural unit represented by formula (V), a resin composition with more excellent low dielectric properties (low dielectric constant, low dielectric loss tangent) can be obtained.

[Formula 15]

(In formula (V), Ar represents an aromatic hydrocarbon linking group. * represents the bonding position.)

The aromatic hydrocarbon linking group may be a group consisting only of aromatic hydrocarbons which may have a substituent, or a group consisting of a combination of an aromatic hydrocarbon which may have a substituent and another linking group, and is preferably a group consisting only of aromatic hydrocarbons which may have a substituent. In addition, the substituent that the aromatic hydrocarbon may have is substituent Z (for example, an alkyl group with 1 to 6 carbon atoms, an alkenyl group with 2 to 6 carbon atoms, an alkynyl group with 2 to 6 carbon atoms, an alkoxy group with 1 to 6 carbon atoms, and hyde hydroxyl group, amino group, carboxyl group, halogen atom, etc.). Moreover, it is preferable that the aromatic hydrocarbon does not have a substituent.

The aromatic hydrocarbon linking group is usually a divalent linking group.

The aromatic hydrocarbon linking group specifically includes a phenylene group, naphthalenediyl group, anthracenediyl group, phenanthrenediyl group, biphenyldiyl group, and fluorenediyl group, which may have a substituent. A phenylene group is preferred. Examples of the substituent include the above-mentioned substituent Z, but it is preferable that groups such as the above-mentioned phenylene group do not have a substituent.

The structural unit represented by formula (V) more preferably includes at least one of a structural unit represented by the following formula (V1), a structural unit represented by the following formula (V2), and a structural unit represented by the following formula (V3). do. In addition, * in the following formula represents a binding position. In addition, hereinafter, the structural units represented by formulas (V1) to (V3) may be collectively referred to as "structural unit (a)."

[Formula 16]

In formulas (V1) to (V3), L ¹ is an aromatic hydrocarbon linking group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10 carbon atoms). Specifically, examples include phenylene group, naphthalenediyl group, anthracenediyl group, phenanthrenediyl group, biphenyldiyl group, and fluorenediyl group, which may have a substituent. Among them, phenylene group which may have a substituent is preferable. do. Examples of the substituent include the above-mentioned substituent Z, but it is preferable that groups such as the above-mentioned phenylene group do not have a substituent.

The compound forming the structural unit (a) is preferably a divinyl aromatic compound, for example, divinylbenzene, bis(1-methylvinyl)benzene, divinylnaphthalene, divinylanthracene, and divinylbiphenyl. , divinylphenanthrene, etc. Among them, divinylbenzene is particularly preferable. These divinyl aromatic compounds may be used one type, or two or more types may be used as needed.

As described above, the polymer having the structural unit represented by formula (V) may be a homopolymer of the structural unit (a), or may be a copolymer with a structural unit derived from another monomer.

When the polymer having the structural unit represented by the formula (V) is a copolymer, the copolymerization ratio of the structural unit (a) is preferably 5 mol% or more, more preferably 10 mol% or more, and the copolymerization ratio is 15 mol% or more. It is more desirable. The upper limit is preferably 90 mol% or less, more preferably 85 mol% or less, further preferably 80 mol% or less, even more preferably 70 mol% or less, more preferably 60 mol% or less, and 50 mol% or less. It is more preferable that it is % or less, it is even more preferable that it is 40 mol% or less, it is especially preferable that it is 30 mol% or less, and it may be 25 mol% or less.

Examples of structural units derived from other monomers include structural unit (b) derived from an aromatic compound having one vinyl group (monovinyl aromatic compound).

The structural unit (b) derived from a monovinyl aromatic compound is preferably a structural unit represented by the following formula (V4).

[Formula 17]

In formula (V4), L ² is an aromatic hydrocarbon linking group, and specific examples of preferable ones include the above L ¹ .

R ^V1 is a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms (preferably an alkyl group). When R ^V1 is a hydrocarbon group, the number of carbon atoms is preferably 1 to 6, and more preferably 1 to 3. R ^V1 and L ² may have the substituent Z described above.

When the polymer having the structural unit represented by formula (V) is a copolymer containing structural unit (b) derived from a monovinyl aromatic compound, examples of the monovinyl aromatic compound include styrene, vinylnaphthalene, vinylbiphenyl, etc. vinyl aromatic compounds; o-methylstyrene, m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, o-ethylvinylbenzene, m-ethylvinylbenzene, p-ethylvinylbenzene, methylvinylbiphenyl, ethylvinylbiphenyl, etc. and nuclear alkyl-substituted vinyl aromatic compounds. The monovinyl aromatic compound exemplified here may have the substituent Z described above as appropriate. Moreover, these monovinyl aromatic compounds may be used one type or two or more types may be used.

When the polymer having the structural unit represented by formula (V) is a copolymer containing the structural unit (b), the copolymerization ratio of the structural unit (b) is preferably 10 mol% or more, and more preferably 15 mol% or more. Furthermore, it may be 20 mol% or more, 30 mol% or more, 40 mol% or more, 50 mol% or more, 60 mol% or more, 70 mol% or more, and 75 mol% or more. The upper limit is preferably 98 mol% or less, more preferably 90 mol% or less, and even more preferably 85 mol% or less.

The polymer having the structural unit represented by formula (V) may have structural units other than the structural unit (a) and structural unit (b). Other structural units include, for example, structural unit (c) derived from a cycloolefin compound. Cycloolefin compounds include hydrocarbons having a double bond in the ring structure. Specifically, in addition to monocyclic olefins such as cyclobutene, cyclopentene, cyclohexene, and cyclooctene, compounds having a norbornene ring structure such as norbornene and dicyclopentadiene, and aromatics such as indene and acenaphthylene. Cycloolefin compounds in which rings are condensed, etc. can be mentioned. Examples of norbornene compounds include those described in paragraphs 0037 to 0043 of Japanese Patent Application Laid-Open No. 2018-39995, the contents of which are incorporated into this specification. In addition, the cycloolefin compound exemplified here may further have the substituent Z described above.

When the polymer having the structural unit represented by formula (V) is a copolymer containing the structural unit (c), the copolymerization ratio of the structural unit (c) is preferably 10 mol% or more, and more preferably 20 mol% or more. And, it is more preferable that it is 30 mol% or more. The upper limit is preferably 90 mol% or less, more preferably 80 mol% or less, further preferably 70 mol% or less, may be 50 mol% or less, and may be 30 mol% or less.

The polymer having the structural unit represented by formula (V) may further incorporate a structural unit (d) derived from a different polymerizable compound (hereinafter also referred to as another polymerizable compound). Other polymerizable compounds (monomers) include, for example, compounds containing three vinyl groups. Specifically, 1,3,5-trivinylbenzene, 1,3,5-trivinylnaphthalene, and 1,2,4-trivinylcyclohexane can be mentioned. Alternatively, ethylene glycol diacrylate, butadiene, etc. may be mentioned. The copolymerization ratio of the structural unit (d) derived from another polymerizable compound is preferably 30 mol% or less, more preferably 20 mol% or less, and still more preferably 10 mol% or less.

As one embodiment of the polymer having the structural unit represented by the formula (V), a polymer essentially containing the structural unit (a) and containing at least one type of structural units (b) to (d) is exemplified. Furthermore, an embodiment is exemplified in which the total of structural units (a) to (d) accounts for 95 mol% or more, and even 98 mol% or more, of the total structural units.

Another embodiment of a polymer having a structural unit represented by formula (V), wherein the structural unit (a) is essential and the structural unit containing an aromatic ring is 90 mol% or more among all structural units excluding the terminals. It is preferable, it is more preferable that it is 95 mol% or more, and it may be 100 mol%.

In addition, in calculating the mole percent per total structural unit, one structural unit refers to a monomer (e.g., divinyl aromatic compound, monovinyl Aromatic compounds, etc.) shall be derived from one molecule.

The method for producing the polymer having the structural unit represented by formula (V) is not particularly limited and can be carried out by conventional methods. For example, raw materials containing a divinyl aromatic compound (if necessary, a monovinyl aromatic compound, a cyclo Examples include coexistence of olefin compounds, etc.) and polymerization in the presence of a Lewis acid catalyst. As the Lewis acid catalyst, a metal fluoride such as boron trifluoride or a complex thereof can be used.

The structure of the chain terminal of the polymer having the structural unit represented by formula (V) is not particularly limited, but speaking of groups derived from the above divinyl aromatic compound, those having the structure of the following formula (E1) can be mentioned. In addition, L ¹ in formula (E1) is the same as defined in formula (V1) above. * indicates binding position.

*-CH=CH-L ¹ -CH=CH ₂ (E1)

When a group derived from a monovinyl aromatic compound becomes a chain terminal, it may have a structure of the following formula (E2). In the formula, L ² and R ^V1 each have the same meaning as defined in the above formula (V4). * indicates binding position.

*-CH=CH-L ² -R ^V1 (E2)

The molecular weight of the polymer having the structural unit represented by formula (V), in terms of number average molecular weight Mn, is preferably 300 or more, more preferably 500 or more, still more preferably 1,000 or more, and even more preferably 1,500 or more. The upper limit of the number average molecular weight Mn is preferably 130,000 or less, more preferably 120,000 or less, further preferably 110,000 or less, and still more preferably 100,000 or less.

The molecular weight of the polymer having the structural unit represented by the formula (V), in terms of weight average molecular weight Mw, is preferably 1,000 or more, more preferably 2,000 or more, and still more preferably 3,000 or more. By exceeding the above lower limit, the excellent low dielectric properties of the polymer having the structural unit represented by formula (V), especially Df and dielectric properties after moisture absorption, can be effectively exhibited in the cured product of the resin composition. The upper limit of the weight average molecular weight Mw is preferably 160,000 or less, more preferably 150,000 or less, further preferably 140,000 or less, and even more preferably 130,000 or less. By setting the value below the above upper limit, embedding defects tend to be less likely to occur when prepreg or resin sheets are laminated on a circuit forming board.

The monodispersity (Mw/Mn) expressed as the ratio of the weight average molecular weight Mw and the number average molecular weight Mn is preferably 100 or less, more preferably 50 or less, and even more preferably 20 or less. As a lower limit of monodispersity, it is realistic that it is 1.1 or more, and even if it is 10 or more, the required performance is satisfied.

The Mw and Mn are measured according to the description of the Examples described later.

When the resin composition of the present embodiment contains two or more types of polymers having structural units represented by formula (V), it is preferable that Mw, Mn, and Mw/Mn of the mixture satisfy the above range.

The equivalent weight of the vinyl group of the polymer having the structural unit represented by formula (V) is 200 g/eq. It is preferable that it is more than 230 g/eq. It is more preferable that it is 250 g/eq. It is more desirable to have more than this. Additionally, the equivalent weight of the vinyl group is 1200 g/eq. It is preferably less than or equal to 1000 g/eq. It is more preferable that it is less than or equal to 800 g/eq. or less, 600 g/eq. or less, 400 g/eq. or less, 300 g/eq. The following may be acceptable. By exceeding the above lower limit, the storage stability of the resin composition tends to improve and the fluidity of the resin composition tends to improve. Therefore, formability is improved, voids are less likely to occur during formation of prepreg, etc., and a printed wiring board with higher reliability tends to be obtained. On the other hand, by setting it below the above upper limit, the moisture absorption and heat resistance of the resulting cured product tends to improve.

In addition, it is preferable that the cured product of the polymer having a structural unit represented by formula (V) used in this embodiment has excellent dielectric properties. For example, the cured product of the polymer having the structural unit represented by the formula (V) used in this embodiment preferably has a relative dielectric constant (Dk) at 10 GHz measured according to the cavity resonator perturbation method of 2.80 or less. , it is more preferable that it is 2.60 or less, it is still more preferable that it is 2.50 or less, and it is still more preferable that it is 2.40 or less. In addition, the practical lower limit of the relative dielectric constant is, for example, 1.80 or more. In addition, the cured product of the polymer having the structural unit represented by the formula (V) used in this embodiment preferably has a dielectric loss tangent (Df) of 0.0030 or less at 10 GHz, as measured according to the cavity resonator perturbation method, and 0.0020. It is more preferable that it is 0.0010 or less, and it is still more preferable that it is 0.0010 or less. Additionally, the practical lower limit of the dielectric loss tangent is, for example, 0.0001 or more.

Dielectric loss tangent (Df) is measured according to the method described in the Examples described later. The relative dielectric constant (Dk) is also measured according to the Df measurement method in the examples.

Regarding the polymer having the structural unit represented by formula (V) in this specification, the compounds described in paragraphs 0029 to 0058 of International Publication No. 2017/115813 and their synthesis reaction conditions, etc., paragraphs 0013 to 0013 of Japanese Patent Application Publication No. 2018-039995. Compounds described in 0058 and their synthesis reaction conditions, etc., compounds described in paragraphs 0008 to 0043 of Japanese Patent Application Laid-Open No. 2018-168347, and their synthesis reaction conditions, etc., compounds described in paragraphs 0014 to 0042 of Japanese Patent Application Laid-Open No. 2006-070136, and the like. Synthesis reaction conditions, etc., refer to the compounds described in paragraphs 0014 to 0061 of Japanese Patent Application Laid-Open No. 2006-089683 and their synthesis reaction conditions, etc., and the compounds described in paragraphs 0008 to 0036 of Japanese Patent Application Laid-Open No. 2008-248001 and their synthesis reaction conditions. It can be done and is incorporated into this specification.

When the resin composition of the present embodiment contains a polymer having a structural unit represented by formula (V), when the resin solid content in the resin composition is 100 parts by mass, the content of the polymer having a structural unit represented by formula (V) is It is preferably 5 to 50 parts by mass. The lower limit of the content of the polymer having the structural unit represented by formula (V) is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and 20 parts by mass or more when the resin solid content in the resin composition is 100 parts by mass. It may be 25 parts by mass or more. By setting the content of the polymer having the structural unit represented by formula (V) to the above lower limit or more, low dielectric properties, especially low dielectric loss tangent, can be effectively achieved. On the other hand, the upper limit of the content of the polymer having the structural unit represented by formula (V) is preferably 45 parts by mass or less, more preferably 40 parts by mass or less, and 35 parts by mass, when the resin solid content in the resin composition is 100 parts by mass. It is more preferable that it is less than 100%. Moreover, by setting it below the above upper limit, the peeling strength of the metal foil of the obtained cured product can be effectively increased.

The polymer having the structural unit represented by the formula (V) may be contained in the resin composition as one type, or may be contained in two or more types. When two or more types are contained, it is preferable that the total amount falls within the above range.

<<Polyphenylene ether compound having a carbon-carbon unsaturated double bond at the terminal>>

The resin composition of this embodiment may contain a polyphenylene ether compound having a carbon-carbon unsaturated double bond at the terminal.

The polyphenylene ether compound having a carbon-carbon unsaturated double bond at the terminal is preferably a polyphenylene ether compound having a group selected from the group consisting of a (meth)acrylic group, maleimide group, and vinylbenzyl group at the terminal. Moreover, the polyphenylene ether compound having a carbon-carbon unsaturated double bond at the terminal is preferably a polyphenylene ether compound having two or more carbon-carbon unsaturated double bonds at the terminal. There is a tendency to more effectively improve the low dielectric properties of printed wiring boards by using these polyphenylene ether compounds.

Hereinafter, these details will be explained.

Examples of the polyphenylene ether compound having a carbon-carbon unsaturated double bond at the terminal include a compound having a phenylene ether skeleton represented by the following formula (X1).

[Formula 18]

(In formula (X1), R ²⁴ , R ²⁵ , R ²⁶ , and R ²⁷ may be the same or different, and represent an alkyl group with 6 or less carbon atoms, an aryl group, a halogen atom, or a hydrogen atom.)

A polyphenylene ether compound having a carbon-carbon unsaturated double bond at the terminal has the formula (X2):

[Formula 19]

(In formula (X2), R ²⁸ , R ²⁹ , R ³⁰ , R ³⁴ , and R ³⁵ may be the same or different and represent an alkyl group or phenyl group having 6 or less carbon atoms. R ³¹ , R ³² , and R ³³ are , may be the same or different, and are a hydrogen atom, an alkyl group with 6 or less carbon atoms, or a phenyl group.)

A repeating unit, and/or, represented by Equation (X3):

[Formula 20]

(In formula (X3), R ³⁶ , R ³⁷ , R ³⁸ , R ³⁹ , R ⁴⁰ , R ⁴¹ , R ⁴² , and R ⁴³ may be the same or different, and are a hydrogen atom, an alkyl group with 6 or less carbon atoms, or a phenyl group. -A- is a straight-chain, branched, or cyclic divalent hydrocarbon group having 20 or less carbon atoms.) may further include a repeating unit represented by .

The polyphenylene ether compound having a carbon-carbon unsaturated double bond at the terminal is a modified polyphenylene ether compound in which part or all of the terminal is functionalized with an ethylenically unsaturated group (hereinafter referred to as “modified polyphenylene ether compound (g)). It is preferable that it is a modified polyphenylene ether compound having two or more groups selected from the group consisting of (meth)acrylic group, maleimide group, and vinylbenzyl group at the terminal. By employing such a modified polyphenylene ether compound (g), it becomes possible to further reduce the dielectric loss tangent (Df) of the cured product of the resin composition. These may be used 1 type or in combination of 2 or more types.

Examples of the modified polyphenylene ether compound (g) include a compound represented by the formula (OP-1).

[Formula 21]

⁽ In ^formula (OP ^- 1 ₎ , , represents an alkenyl group or an alkynyl group, n ₁ represents an integer from 1 to 6, n ₂ represents an integer from 1 to 100, and n ₃ represents an integer from 1 to 4.)

When n ₂ and/or n ₃ are an integer of 2 or more, n ₂ structural units (YO) and/or n ₃ structural units may be the same or different, respectively. n ₃ is preferably 2 or more, and more preferably 2.

The modified polyphenylene ether compound (g) in the present embodiment is preferably a compound represented by the formula (OP-2).

[Formula 22]

where -(O-X-O)- is the formula (OP-3):

[Formula 23]

(In formula (OP-3), R ⁴ , R ⁵ , R ⁶ , R ¹⁰ , and R ¹¹ may be the same or different, and are an alkyl group or phenyl group having 6 or less carbon atoms. R ⁷ , R ⁸ , and R ⁹ may be the same or different, and is a hydrogen atom, an alkyl group with 6 or less carbon atoms, or a phenyl group.)

and/or formula (OP-4):

[Formula 24]

(In formula (OP-4), R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , and R ¹⁹ may be the same or different, and may be a hydrogen atom, an alkyl group with 6 or less carbon atoms, or It is a phenyl group. -A- is a straight-chain, branched, or cyclic divalent hydrocarbon group having 20 or less carbon atoms.

Also, -(Y-O)- is in the formula (OP-5):

[Formula 25]

(In formula (OP-5), R ²⁰ and R ²¹ may be the same or different, and are an alkyl group or phenyl group having 6 or less carbon atoms. R ²² and R ²³ may be the same or different, and may be a hydrogen atom or a carbon number of 6 or less. It is an alkyl group or a phenyl group.) is preferably represented by .

In the formula (OP-2), at least one of a and b represents an integer of 0 to 100 other than 0, and is preferably an integer of 0 to 50, and more preferably an integer of 1 to 30. When a and/or b are an integer of 2 or more, the 2 or more -(Y-O)- may each independently be an arrangement of one type of structure, or two or more types of structures may be arranged in blocks or randomly.

Examples of -A- in formula (OP-4) include methylene group, ethylidene group, 1-methylethylidene group, 1,1-propylidene group, and 1,4-phenylenebis(1- divalent organic groups such as methylethylidene) group, 1,3-phenylenebis(1-methylethylidene) group, cyclohexylidene group, phenylmethylene group, naphthylmethylene group, and 1-phenylethylidene group. However, it is not limited to these.

In the modified polyphenylene ether compound (g), R ⁴ , R ⁵ , R ⁶ , R ¹⁰ , R ¹¹ , R ²⁰ , and R ²¹ are alkyl groups having 3 or less carbon atoms, and R ⁷ , R ⁸ , and R ⁹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²² , and R ²³ are preferably a hydrogen atom or an alkyl group having 3 or less carbon atoms, In particular, -(OXO)- represented by formula (OP-3) or formula (OP-4) is formula (OP-9), formula (OP-10), and/or formula (OP-11), and formula ( It is preferable that -(YO)- represented by OP-5) is the formula (OP-12) or (OP-13). When a and/or b are integers of 2 or more, 2 or more -(YO)- are each independently a structure in which 2 or more formulas (OP-12) and/or (OP-13) are arranged, or the formula ( OP-12) and equation (OP-13) may have a block or randomly arranged structure.

[Formula 26]

[Formula 27]

(In formula (OP-10), R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , and R ⁴⁷ may be the same or different, and are a hydrogen atom or a methyl group. -B- is a straight chain, branch, or ring having 20 or less carbon atoms. It is a divalent hydrocarbon group.)

Specific examples of -B- include the same as specific examples of -A- in the formula (OP-4).

[Formula 28]

(In formula (OP-11), -B- is a straight-chain, branched, or cyclic divalent hydrocarbon group having 20 or less carbon atoms.)

Specific examples of -B- include the same as specific examples of -A- in the formula (OP-4).

[Formula 29]

[Formula 30]

The polyphenylene ether compound having a carbon-carbon unsaturated double bond at the terminal may be produced by a known method, or a commercial product may be used. Commercially available products include, for example, "SA9000" manufactured by SABIC Innovative Plastics, which is a modified polyphenylene ether compound having a methacryl group at the terminal. Also, examples of modified polyphenylene ether compounds having a vinylbenzyl group at the terminal include “OPE-2St1200” and “OPE-2st2200” manufactured by Mitsubishi Gas Chemical. In addition, as a modified polyphenylene ether compound whose terminal is a vinylbenzyl group, a polyphenylene ether compound whose terminal is a hydroxyl group, such as "SA90" manufactured by SABIC Innovative Plastics, is modified into a vinylbenzyl group using vinylbenzyl chloride, etc. You can also use what you ordered.

In addition, details of polyphenylene ether compounds having a carbon-carbon unsaturated double bond at the terminal are described in Japanese Patent Application Laid-open No. 2006-028111, Japanese Patent Application Laid-Open No. 2018-016709, International Publication No. 2019-138992, International Publication No. The description of No. 2022-054303 may be taken into consideration, and these contents are incorporated into this specification.

Number average molecular weight of polyphenylene ether compound having a carbon-carbon unsaturated double bond at the terminal (preferably, modified polyphenylene ether compound (g)) converted to polystyrene by GPC (gel permeation chromatography) method (details) (according to the method described in the examples described later) is preferably 500 or more and 3,000 or less. When the number average molecular weight is 500 or more, stickiness tends to be further suppressed when the resin composition of this embodiment is formed into a coating film. When the number average molecular weight is 3,000 or less, solubility in solvents tends to be further improved.

In addition, the weight average molecular weight of the polyphenylene ether compound (preferably the modified polyphenylene ether compound (g)) having a carbon-carbon unsaturated double bond at the terminal as converted to polystyrene by GPC (details are given in the Examples described later). (according to the described method) is preferably 800 or more and 10,000 or less, and more preferably 800 or more and 5,000 or less. By setting it above the lower limit, the relative dielectric constant (Dk) and dielectric loss tangent (Df) of the cured product of the resin composition tend to become lower, and by setting it below the above upper limit, the resin composition is resistant to solvents when producing varnishes, etc., which will be described later. The solubility, low viscosity, and moldability tend to be improved.

In addition, in the case of the modified polyphenylene ether compound (g), the equivalent weight of the carbon-carbon unsaturated double bond at the terminal is preferably 400 to 5000 g per carbon-carbon unsaturated double bond, and is more preferably 400 to 2500 g. desirable. By exceeding the above lower limit, the relative dielectric constant (Dk) and dielectric loss tangent (Df) of the cured product of the resin composition tend to become lower. By setting it below the above upper limit, the solubility, low viscosity, and moldability of the resin composition in solvents tend to be further improved.

When the resin composition of the present embodiment contains a polyphenylene ether compound having a carbon-carbon unsaturated double bond at the terminal, the lower limit of the content of the polyphenylene ether compound having a carbon-carbon unsaturated double bond at the terminal is the resin It is preferably 1 part by mass or more, more preferably 3 parts by mass or more, even more preferably 5 parts by mass or more, and even more preferably 7 parts by mass or more, relative to 100 parts by mass of the resin solid content in the composition. By exceeding the above lower limit, the low water absorption and low dielectric properties (Dk and/or Df) of the obtained cured product tend to be further improved. In addition, the upper limit of the content of the polyphenylene ether compound having a carbon-carbon unsaturated double bond at the terminal is preferably 70 parts by mass or less, and more preferably 60 parts by mass or less, with respect to 100 parts by mass of the resin solid content in the resin composition. , it is more preferable that it is 50 parts by mass or less, it is still more preferable that it is 40 parts by mass or less, and it may be 30 parts by mass or less and 25 parts by mass or less. By setting it below the said upper limit, the copper foil peeling strength of the obtained hardened|cured material tends to improve more.

The resin composition in this embodiment may contain only one type or two or more types of polyphenylene ether compounds having a carbon-carbon unsaturated double bond at the terminal. When two or more types are included, it is preferable that the total amount falls within the above range.

＜Other resin (D)＞

The resin composition of this embodiment may further contain another resin (D). The other resin (D) includes at least one selected from the group consisting of maleimide compounds, cyanate ester compounds, epoxy compounds, phenol compounds, alkenyl substituted nadimide compounds, oxetane resins, and benzoxazine compounds. is preferable, and it is more preferable that it contains at least one type of other resin (D) selected from the group consisting of cyanate ester compounds, maleimide compounds, and epoxy compounds. These other resins (D) are not necessarily essential components for achieving the effects of the present invention, but by mixing these components, various physical properties are imparted to the resin composition or cured product, or the dielectric properties of the resin composition or cured product are improved. Moisture absorption and heat resistance can be further improved. These other resins (D) may be used individually or in combination of two or more types.

＜＜Cyanate ester compound＞＞

The resin composition of this embodiment may contain a cyanate ester compound.

The cyanate ester compound contains at least one cyanate group (cyanato group) in one molecule (preferably 2 to 12, more preferably 2 to 6, further preferably 2 to 4, even more preferably 2 or 3, more preferably 2) There is no particular limitation as long as it is a compound included, and compounds commonly used in the field of printed wiring boards can be widely used. Moreover, the cyanate ester compound is preferably a compound in which the cyanate group is directly bonded to the aromatic skeleton (aromatic ring).

Cyanate ester compounds include, for example, phenol novolak-type cyanate ester compounds, naphthol aralkyl-type cyanate ester compounds (naphthol aralkyl-type cyanate), naphthylene ether-type cyanate ester compounds, and biphenyl aralkyl. type cyanate ester compound, xylene resin type cyanate ester compound, trisphenolmethane type cyanate ester compound, adamantane skeleton type cyanate ester compound, bisphenol M type cyanate ester compound, bisphenol A type cyanate ester compound, and at least one member selected from the group consisting of diallyl bisphenol A type cyanate compounds. Among these, from the viewpoint of further improving the low water absorption of the obtained cured product, phenol novolak-type cyanate ester compounds, naphthol aralkyl-type cyanate ester compounds, naphthylene ether-type cyanate ester compounds, and xylene resin-type cyanate esters. The compound is preferably at least one selected from the group consisting of a bisphenol M-type cyanate ester compound, a bisphenol A-type cyanate compound, and a diallylbisphenol A-type cyanate ester compound, and is a naphthol aralkyl-type cyanate ester compound. It is more preferable. These cyanate ester compounds may be prepared by known methods, or commercial products may be used. Additionally, cyanate compounds having a naphthol aralkyl skeleton, naphthylene ether skeleton, xylene skeleton, trisphenolmethane skeleton, or adamantane skeleton have a relatively large functional group equivalent number and a small number of unreacted cyanate ester groups. Therefore, the cured product of the resin composition using these tends to be much more excellent in low water absorption. Additionally, plating adhesion tends to be further improved, mainly due to having an aromatic skeleton or an adamantane skeleton.

The resin composition of this embodiment preferably contains a cyanate ester compound in a range that does not impair the effect of the present invention. When the resin composition of the present embodiment contains a cyanate ester compound, the lower limit of the content is preferably 0.1 parts by mass or more, more preferably 2 parts by mass or more, with respect to 100 parts by mass of the resin solid content in the resin composition. It may be 5 parts by mass or more. When the content of the cyanate ester compound is 0.1 part by mass or more, the heat resistance, combustion resistance, chemical resistance, low relative dielectric constant, low dielectric loss tangent, and insulation properties of the obtained cured product tend to be improved. When the resin composition of the present embodiment contains a cyanate ester compound, the upper limit of the content of the cyanate ester compound is preferably 70 parts by mass or less, and 50 parts by mass or less, with respect to 100 parts by mass of the resin solid content in the resin composition. It is more preferable that it is 40 parts by mass or less, even more preferably 30 parts by mass or less, and even more preferably 20 parts by mass or less.

The resin composition in this embodiment may contain only one type of cyanate ester compound, 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.

＜＜maleimide compound＞＞

The resin composition of this embodiment may contain a maleimide compound. The resin composition of the present embodiment contains at least 1 per 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 it is a compound having a maleimide group, and compounds commonly used in the field of printed wiring boards can be widely used.

In this embodiment, the maleimide compound is a compound represented by the formula (M0), a compound represented by the formula (M1), a compound represented by the formula (M2), a compound represented by the formula (M3), and a compound represented by the formula (M4) , and compounds represented by the formula (M5), preferably a compound represented by the formula (M0), a compound represented by the formula (M1), a compound represented by the formula (M3), a compound represented by the formula It is more preferable to include at least one selected from the group consisting of a compound represented by (M4) and a compound represented by the formula (M5), a compound represented by the formula (M1), a compound represented by the formula (M3), and a compound represented by the formula It is more preferable that it contains at least one type selected from the group consisting of the compound represented by (M5), and it is even more preferable that it contains the compound represented by the formula (M1) and/or the compound represented by the formula (M3). When these maleimide compounds are used as materials for printed wiring boards (for example, metal foil-clad laminates), excellent heat resistance can be imparted.

[Formula 31]

(In the formula (M0), R ⁵¹ each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group, R ⁵² each independently represents a hydrogen atom or a methyl group, and n ₁ is an integer of 1 or more. represents.)

R ⁵¹ is each independently selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, and phenyl group. It is preferable that it is one type, it is more preferable that it is a hydrogen atom and/or a methyl group, and it is still more preferable that it is a hydrogen atom.

R ⁵² is preferably a methyl group.

n ₁ is preferably an integer of 1 to 10, more preferably 1 to 5, further preferably 1 to 3, still more preferably 1 or 2, and even more preferably 1.

Specifically, the following compounds can be cited as preferred examples of formula (M0).

[Formula 32]

In the above formula, R ⁸ each independently represents a hydrogen atom, a methyl group, or an ethyl group, and a methyl group is preferable.

The compound represented by the formula (M0) may be one type or a mixture of two or more types. Examples of mixtures include mixtures of compounds with different n ₁ , mixtures of compounds with different types of substituents of R ⁵¹ and/or R ⁵² , bonding positions of the maleimide group and the oxygen atom to the benzene ring (meta position, para position, ortho position) A mixture of compounds with different positions) and a mixture of compounds with a combination of two or more of the above-mentioned different points can be mentioned. Hereinafter, the same applies to formulas (M1) to (M5).

[Formula 33]

(In formula (M1), 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, R ^M7 and R ^M8 are each independently an alkyl group, and lx is 0 or 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. Alkyl group with 1 to 10 carbon atoms, alkyloxy group with 1 to 10 carbon atoms, alkylthio group with 1 to 10 carbon atoms, aryl group with 6 to 10 carbon atoms, aryloxy group with 1 to 10 carbon atoms, arylthio group with 1 to 10 carbon atoms , px represents an integer of 0 to 3, and nx represents an integer of 1 to 20.

R ^M1 , R ^M2 , R ^M3 , and R ^M4 in the formula each independently represent a hydrogen atom or an organic group. Here, the organic group 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 these, 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 a hydrogen atom.

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 having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, ethyl group, propyl group, or butyl group, and among these, 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, ethyl group, propyl group, or butyl group. preferred, and a methyl group is particularly preferred. However, Ar ^M is preferably unsubstituted.

A is an alicyclic group with a 4- to 6-membered ring, and an alicyclic group with a 5-membered ring (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 more preferable. 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, ethyl group, propyl group, or butyl group, and among these, 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. Here, the organic group 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 these, 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.

R ^M15 each independently represents an alkyl group with 1 to 10 carbon atoms, an alkyloxy group with 1 to 10 carbon atoms, an alkylthio group with 1 to 10 carbon atoms, an aryl group with 6 to 10 carbon atoms, an aryloxy group with 1 to 10 carbon atoms, It represents an arylthio group with 1 to 10 carbon atoms, a halogen atom, a hydroxyl group or a mercapto group, and is preferably an alkyl group with 1 to 4 carbon atoms, a cycloalkyl group with 3 to 6 carbon atoms, or an aryl group with 6 to 10 carbon atoms.

px represents an integer of 0 to 3, an integer of 0 to 2 is preferable, 0 or 1 is more preferable, and 0 is still more preferable.

nx represents an integer from 1 to 20. nx may be an integer of 10 or less.

In addition, the resin composition of the present embodiment may contain only one type or two or more types of compounds having different values of nx as a compound represented by the formula (M1). When two or more types are included, the average value (average number of repeating units) of nx in the compound represented by formula (M1) in the resin composition, n, has a low melting point (low softening point), low melt viscosity, and excellent handling properties. In order to achieve this, it is preferable that it is 0.92 or more, more preferably 0.95 or more, more preferably 1.0 or more, and even more preferably 1.1 or more. Moreover, n is preferably 10.0 or less, more preferably 8.0 or less, further preferably 7.0 or less, even more preferably 6.0 or less, and may be 5.0 or less. The same applies to equation (M1-1), etc., which will be described later.

The compound represented by formula (M1) is preferably a compound represented by the following formula (M1-1).

[Formula 34]

(In formula (M1-1), 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 ^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. represents.)

R ^M21 , R ^M22 , R ^M23 , and R ^M24 in the formula 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. . 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 having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, ethyl group, propyl group, or butyl group, and among these, 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. .

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 having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, ethyl group, propyl group, or butyl group, and among these, 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. .

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

nx represents an integer between 1 and 20. nx may be an integer of 10 or less.

The compound represented by formula (M1-1) is preferably a compound represented by the following formula (M1-2).

[Formula 35]

(In formula (M1-2), 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 ^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. represents.)

In formula (M1-2), R ^M21 , R ^M22 , R ^M23 , R ^M24 , R ^M25 , R ^M26 , R ^M27 , R M28, R ^M29 , R ^M30 , R ^M31 , ^{R M32 ,} R ^M33 , R ^M34 , R ^M35 , R ^M36 , R ^M37 , R M38 ^{, R M39 ,} and nx are R ^M21 , R ^M22 , R ^M23 , R ^M24 , R ^M25 , R ^M26 , R ^M27 in formula (M1-1), respectively. R ^M28 , R ^M29 , R ^M30 , R ^M31 , R ^M32 , R ^M33 , R ^M34 , R ^M35 , R ^M36 , R ^M37 , R ^M38 , R ^M39 , and nx have the same meaning, and the preferred range is also the same.

The compound represented by formula (M1-1) is preferably a compound represented by the following formula (M1-3), and is more preferably a compound represented by the following formula (M1-4).

[Formula 36]

(In formula (M1-3), nx represents an integer between 1 and 20.)

nx may be an integer of 10 or less.

[Formula 37]

(In formula (M1-4), nx represents an integer between 1 and 20.)

nx may be an integer of 10 or less.

The molecular weight of the compound represented by formula (M1) is preferably 500 or more, more preferably 600 or more, and still more preferably 700 or more. By exceeding the above lower limit, the low dielectric properties and low water absorption of the obtained cured product tend to be further improved. Moreover, the molecular weight of the compound represented by formula (M1) is preferably 10,000 or less, more preferably 9,000 or less, further preferably 7,000 or less, still more preferably 5,000 or less, and even more preferably 4,000 or less. By setting it below the above upper limit, the heat resistance and handleability of the resulting cured product tend to be further improved.

[Formula 38]

(In formula (M2), R ⁵⁴ each independently represents a hydrogen atom or a methyl group, and n ₄ represents an integer of 1 or more.)

n ₄ is preferably an integer of 1 to 10, more preferably 1 to 5, further preferably 1 to 3, still more preferably 1 or 2, and may be 1.

The compound represented by formula (M2) may be a mixture of compounds having different n ₄ values, and is preferably a mixture. Moreover, as described in the part of the compound represented by the formula (M0), the other parts may be a mixture of different compounds.

[Formula 39]

(In formula (M3), R ⁵⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group, and n ₅ represents an integer from 1 to 10.)

R ⁵⁵ is each independently selected from the group consisting of a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, and phenyl group. It is preferable that it is one type, it is more preferable that it is a hydrogen atom and/or a methyl group, and it is still more preferable that it is a hydrogen atom.

n ₅ is preferably an integer of 1 to 5, more preferably 1 to 3, and even more preferably 1 or 2.

The compound represented by formula (M3) may be a mixture of compounds having different n ₅ values, and is preferably a mixture. Moreover, as described in the part of the compound represented by the formula (M0), the other parts may be a mixture of different compounds.

[Formula 40]

(In formula (M4), R ⁵⁶ each independently represents a hydrogen atom, a methyl group, or an ethyl group, and R ⁵⁷ each independently represents a hydrogen atom or a methyl group.)

R ⁵⁶ is each independently preferably a methyl group or an ethyl group, more preferably a methyl group or an ethyl group in each of the two benzene rings, and R ⁵⁷ is preferably a methyl group.

[Formula 41]

(In formula (M5), R ⁵⁸ each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group, R ⁵⁹ each independently represents a hydrogen atom or a methyl group, and n ₆ is an integer of 1 or more. represents.)

R ⁵⁸ is each independently selected from the group consisting of a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, and phenyl group. It is preferable that it is one type, it is more preferable that it is a hydrogen atom and/or a methyl group, and it is still more preferable that it is a hydrogen atom.

R ⁵⁹ is preferably a methyl group.

_n6 is preferably an integer of 1 to 10, more preferably 1 to 5, further preferably 1 to 3, still more preferably 1 or 2, and may be 1.

The compound represented by formula (M5) may be a mixture of compounds with different n ₆ , and is preferably a mixture. Moreover, as described in the part of the compound represented by the formula (M0), the other parts may be a mixture of different compounds.

The maleimide compound may be manufactured by a known method, or a commercial item may be used. Commercially available products include, for example, “BMI-80” manufactured by K-I Chemical Company as a compound represented by formula (M0), and “NE-X-9470S” manufactured by DIC Corporation as a compound represented by formula (M1). , "BMI-2300" manufactured by Daiwa Chemical Industry Co., Ltd. as a compound represented by the formula (M2), a compound represented by the formula (M3), and "MIR-3000-70MT" manufactured by Nippon Chemical Co., Ltd., as a compound represented by the formula (M4). Examples of the compound represented by formula (M5) include "BMI-70" manufactured by K.I Chemical Co., Ltd. and "MIR-5000" manufactured by Nippon Chemical Co., Ltd.

In addition, maleimide compounds other than the above include, for example, N-phenylmaleimide, oligomers of phenylmethane maleimide, m-phenylenebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, 4,4'-diphenyletherbismaleimide, 4,4'-diphenylsulfonebismaleimide, 1,3-bis(3 -maleimidephenoxy)benzene, 1,3-bis(4-maleimidephenoxy)benzene, prepolymers thereof, and prepolymers of these maleimides and amines.

When the resin composition of the present embodiment contains a maleimide compound, the lower limit of the content 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 in the resin composition. It is more preferable that it is more than 20 parts by mass, and it may be 20 parts by mass or more. When the content of the maleimide compound is 1 part by mass or more, the low dielectric properties and flame resistance of the obtained cured product tend to improve. Moreover, the upper limit of the content of the maleimide compound is preferably 70 parts by mass or less, more preferably 60 parts by mass or less, even more preferably 50 parts by mass or less, based on 100 parts by mass of the resin solid content in the resin composition. It may be less than 20%. When the content of the maleimide compound is 70 parts by mass or less, the metal foil peel strength and low water absorption tend to improve.

The resin composition in this embodiment may contain only one type of maleimide compound, and 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.

＜＜Epoxy compound＞＞

The resin composition of this embodiment may contain an epoxy compound.

The epoxy compound has one or more (preferably 2 to 12, more preferably 2 to 6, further preferably 2 to 4, further preferably 2 or 3, even more preferably 2) epoxy groups per molecule. There is no particular limitation as long as it is a compound or resin having , and compounds commonly used in the field of printed wiring boards can be widely used.

Epoxy compounds include, for example, 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, bisphenol A novolak-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. 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 resin, phosphorus Examples include epoxy resins, compounds obtained by epoxidizing double bonds of glycidylamine, glycidyl ester, and butadiene, and compounds obtained by the reaction of hydroxyl group-containing silicone resins with epichlorohydrin. By using these, the moldability and adhesion of the resin composition are improved. 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, and biphenyl aralkyl type epoxy resin is preferred. It is more preferable that it is an epoxy resin.

The resin composition of this embodiment preferably contains an epoxy compound in a range that does not impair the effect of the present invention. When the resin composition of the present embodiment contains an epoxy compound, the content is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, and 2 parts by mass or more, based on 100 parts by mass of the resin solid content in the resin composition. It is more desirable. When the content of the epoxy compound is 0.1 part by mass or more, the metal foil peeling strength and toughness tend to improve. When the resin composition of the present embodiment contains an epoxy compound, the upper limit of the content of the epoxy compound is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, with respect to 100 parts by mass of the resin solid content in the resin composition. It is more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, even more preferably 8 parts by mass or less, and even more preferably 5 parts by mass or less. When the content of the epoxy compound is 50 parts by mass or less, the electrical properties of the obtained cured product tend to improve.

The resin composition in this embodiment may contain only one type of epoxy compound, 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.

Moreover, the resin composition in this embodiment can also be configured to substantially not contain an epoxy compound. Substantially not included means that the content of the epoxy compound is less than 1 part by mass based on 100 parts by mass of the resin solid content in the resin composition, preferably less than 0.1 part by mass, and more preferably less than 0.01 part by mass.

In addition to the above, regarding other resins (D), the descriptions of paragraphs 0037 to 0123 and 0133 to 0145 of Japanese Patent Application Laid-Open No. 2020-117714 can be taken into consideration, and these contents are incorporated into this specification.

As for the total amount of the other resin (D), when the other resin (D) is included, the total content is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, based on 100 parts by mass of the resin solid content, It is more preferable that it is 20 parts by mass or more, and it is even more preferable that it is 30 parts by mass or more. By exceeding the above lower limit, the glass transition temperature and heat resistance tend to improve further. Moreover, the upper limit of the total content of the other resins (D) is preferably 70 parts by mass or less, more preferably 60 parts by mass or less, even more preferably 50 parts by mass or less, based on 100 parts by mass of the resin solid content. It may be less than the mass part. By setting it below the above upper limit, the low dielectric loss tangent tends to improve further.

＜Flame retardant (E)＞

The resin composition of this embodiment may contain a flame retardant (E). Examples of the flame retardant (E) include phosphorus-based flame retardants, halogen-based flame retardants, inorganic flame retardants, and silicone-based flame retardants, with phosphorus-based flame retardants being preferred.

As the flame retardant (E), known ones can be used, for example, brominated epoxy resin, brominated polycarbonate, brominated polystyrene, brominated styrene, brominated phthalimide, tetrabromobisphenol A, pentabromobenzyl (meth)acryl. Halogen-based flame retardants such as latex, pentabromotoluene, tribromophenol, hexabromobenzene, decabromodiphenyl ether, bis-1,2-pentabromophenylethane, chlorinated polystyrene, chlorinated paraffin, red phosphorus, and tricre. Syl phosphate, triphenyl phosphate, cresyl diphenyl phosphate, trixylenyl phosphate, trialkyl phosphate, dialkyl phosphate, tris(chloroethyl) phosphate, phosphazene, 1,3-phenylenebis(2,6-dixylene) phosphorus-based flame retardants such as (nyl phosphate), 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, aluminum hydroxide, magnesium hydroxide, partial boehmite, boehmite , inorganic flame retardants such as zinc borate and antimony trioxide, and silicone-based flame retardants such as silicone rubber and silicone resin.

In the present embodiment, among these, 1,3-phenylenebis(2,6-dixylenyl phosphate) is preferable because it does not impair low dielectric properties.

When the resin composition of the present embodiment contains a flame retardant (E), the content 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 the content of the flame retardant is preferably 25 parts by mass or less, and more preferably 20 parts by mass or less.

Flame retardant (E) can be used individually or in combination of two or more types. When two or more types are used, the total amount is within the above range.

＜Filler (F)＞

It is preferable that the resin composition of this embodiment contains a filler (F). By including the filler (F), physical properties such as dielectric properties (low dielectric constant, low dielectric loss tangent, etc.), flame resistance, and low thermal expansion of the resin composition and its cured product can be further improved.

Additionally, the filler (F) used in this embodiment preferably has excellent low dielectric properties. For example, the filler (F) used in this embodiment preferably has a relative dielectric constant (Dk) measured according to the cavity resonator perturbation method of 8.0 or less, more preferably 6.0 or less, and still more preferably 4.0 or less. Moreover, the practical lower limit of the relative dielectric constant is, for example, 2.0 or more. Additionally, the filler (F) used in this embodiment preferably has a dielectric loss tangent (Df) of 0.05 or less, more preferably 0.01 or less, as measured by the cavity resonator perturbation method. Additionally, the practical lower limit of the dielectric loss tangent is, for example, 0.0001 or more.

The type of filler (F) used in this embodiment is not particularly limited, and those generally used in the industry can be preferably used. Specifically, silica such as natural silica, fused silica, synthetic silica, amorphous silica, aerosil, hollow silica, alumina, white carbon, titanium white, titanium oxide, zinc oxide, magnesium oxide, zirconium oxide, etc. Metal oxides, zinc borate, zinc stannate, forsterite, complex oxides such as barium titanate, strontium titanate, and calcium titanate, nitrides such as boron nitride, aggregated boron nitride, silicon nitride, and aluminum nitride, aluminum hydroxide, heat-treated aluminum hydroxide products ( Aluminum hydroxide is heat-treated to reduce a portion of the water of crystallization), metal hydroxides (including hydrates) such as boehmite and magnesium hydroxide, molybdenum compounds such as molybdenum oxide and zinc molybdate, barium sulfate, 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 fiber ( In addition to inorganic fillers such as E glass, T glass, D glass, S glass, and Q glass), hollow glass, and spherical glass, rubber powders such as styrene type, butadiene type, and acrylic type, and core shell type Organic fillers such as rubber powder, silicone resin powder, silicone rubber powder, and silicone composite powder can be mentioned.

In this embodiment, the filler (F) preferably contains an inorganic filler and is composed of silica, aluminum hydroxide, aluminum nitride, boron nitride, forsterite, titanium oxide, barium titanate, strontium titanate, and calcium titanate. It is more preferable that it contains at least one type selected from the group, and from the viewpoint of low dielectric properties, it is more preferable that it contains at least one type selected from the group consisting of silica and aluminum hydroxide, and it is even more preferred that it contains silica. desirable. By using these fillers, properties such as heat resistance, dielectric properties, thermal expansion properties, dimensional stability, and flame retardancy of the cured resin composition are further improved.

The content of the filler (F) in the resin composition of the present embodiment can be appropriately set depending on the desired characteristics and is not particularly limited, but is preferably 10 parts by mass or more with respect to 100 parts by mass of the resin solid content in the resin composition. It is more preferably 20 parts by mass or more, more preferably 40 parts by mass or more, even more preferably 60 parts by mass or more, and even more preferably 80 parts by mass or more. By exceeding the above lower limit, low thermal expansion property and low dielectric loss tangent tend to be further improved. In addition, the upper limit of the content of the filler is preferably 300 parts by mass or less, more preferably 250 parts by mass or less, further preferably 200 parts by mass or less, and even more preferably 150 parts by mass or less, based on 100 parts by mass of the resin solid content. It is preferable, and it is even more preferable that it is 120 parts by mass or less. By setting it below the above upper limit, moldability tends to improve further.

In the resin composition of the present embodiment, an example of a preferred embodiment is exemplified by an embodiment in which the content of the filler (F) is 30% by mass to 80% by mass of the components excluding the solvent.

The resin composition of this embodiment may contain only one type of filler (F), 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 the resin composition of this embodiment, when using a filler (F), especially an inorganic filler, a silane coupling agent may be further included. By including a silane coupling agent, the dispersibility of the filler (F) and the adhesive strength between the resin component and the filler (F) and the substrate described later tend to be further improved.

The silane coupling agent is not particularly limited and includes silane coupling agents generally used for surface treatment of inorganic materials, and aminosilane-based compounds (e.g., γ-aminopropyltriethoxysilane, N-β-( aminoethyl)-γ-aminopropyltrimethoxysilane, etc.), epoxysilane-based compounds (e.g., γ-glycidoxypropyltrimethoxysilane, etc.), vinylsilane-based compounds (e.g., vinyltrimethoxysilane, etc.) silanes, etc.), styrylsilane-based compounds (e.g., styryltrimethoxysilane, etc.), acrylic silane-based compounds (e.g., γ-acryloxypropyltrimethoxysilane, etc.), cationic silane-based compounds (e.g., For example, N-β-(N-vinylbenzyl aminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride, etc.), phenylsilane-based compounds, etc. can be mentioned. Silane coupling agents are used individually or in combination of two or more types.

In particular, as the silane coupling agent, at least one selected from the group consisting of vinyl silane-based compounds, acrylic silane-based compounds, and styryl silane-based compounds is used, and as the commonly used thermosetting resin (C), an aromatic ring and a vinyl silane-based compound are used. By using a thermosetting resin containing a group (in particular, a polymer having a structural unit represented by the formula (V)), a resin composition excellent in moisture absorption and heat resistance is obtained while maintaining excellent dielectric properties.

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

<Monomer or oligomer having an ethylenically unsaturated group>

In the resin composition of this embodiment, it is also possible to use together a monomer or oligomer having an ethylenically unsaturated group in order to increase thermosetting properties and curability by active energy rays (for example, photocurability by ultraviolet rays, etc.). The oligomer or monomer having an ethylenically unsaturated group used in the present embodiment is not particularly limited as long as it is an oligomer or monomer having one or more ethylenically unsaturated groups in one molecule, but examples include (meth)acryloyl group and vinyl group. and monomers or oligomers having these.

In addition, in this specification, compounds corresponding to monomers or oligomers having an ethylenically unsaturated group, which also correspond to polyphenylene ether compounds having a carbon-carbon unsaturated double bond at the terminal, have a carbon-carbon unsaturated double bond at the terminal. It is a polyphenylene ether compound having.

More specifically, the monomer having an ethylenically unsaturated group includes Compound (F1) (Compound (F1)), which has a molecular weight of less than 1000 and contains one organic group containing an ethylenically unsaturated bond in the molecule. . It is presumed that by using compound (F1), the ethylenically unsaturated bond of compound (F1) reacts with the commonly used thermosetting resin (C), thereby improving the moisture absorption and heat resistance of the resulting cured product.

The ethylenically unsaturated bond constituting the organic group containing the ethylenically unsaturated bond is not included as a part of the aromatic ring. On the other hand, the intention is to include ethylenically unsaturated bonds included as part of the non-directional ring. Examples of ethylenically unsaturated bonds contained as part of a non-directional ring include a cyclohexenyl group in the molecule. In addition, the meaning includes ethylenically unsaturated bonds contained in parts other than the terminal of the organic group of the straight or branched chain, that is, in the straight or branched chain.

The organic group containing the ethylenically unsaturated bond is more preferably one selected from the group consisting of a vinyl group, an allyl group, an acrylic group, and a methacryl group, and is even more preferably a vinyl group.

In addition, in this specification, a compound corresponding to a monomer or oligomer having an ethylenically unsaturated group and also a silane coupling agent is referred to as a silane coupling agent.

Compound (F1) used in this embodiment is preferably composed only of atoms selected from carbon atoms, hydrogen atoms, oxygen atoms, and silicon atoms, and contains atoms selected from carbon atoms, hydrogen atoms, and oxygen atoms. It is more preferable that it consists only of.

Compound (F1) used in this embodiment may or may not have a polar group. Compound (F1) used in this embodiment preferably does not have a polar group. Examples of polar groups include amino groups, carboxyl groups, hydroxy groups, and nitro groups.

In this embodiment, the molecular weight of compound (F1) is preferably 70 or more, more preferably 80 or more, and still more preferably 90 or more. By exceeding the above lower limit, volatilization of compound (F1) from the resin composition of the present embodiment, its cured product, etc. tends to be suppressed. The upper limit of the molecular weight of the compound (F1) is preferably 500 or less, more preferably 400 or less, further preferably 300 or less, still more preferably 200 or less, and may be 150 or less. By setting it below the upper limit, the effect of increasing reactivity with the commonly used thermosetting resin (C) tends to be further improved.

When the resin composition of the present embodiment contains two or more types of compound (F1), the average molecular weight value of compound (F1) is preferably within the above range, and the molecular weight of each compound is preferably within the above preferred range. It is more desirable.

In this embodiment, compound (F1) preferably has a boiling point of 110°C or higher, more preferably 115°C or higher, and even more preferably 120°C or higher. By exceeding the above lower limit, volatilization of compound (F1) when thermosetting the resin composition is suppressed, and thermosetting resin (C) and compound (F1) can be reacted. The boiling point of the compound (F1) is preferably 300°C or lower, more preferably 250°C or lower, and still more preferably 200°C or lower. By setting it below the above upper limit, it is possible to make it difficult for it to remain as a residual solvent in the cured product.

When the resin composition of the present embodiment contains two or more types of compounds (F1), the average boiling point may fall within the above range, but it is preferable that the boiling point of each compound falls within the above preferred range.

Compound (F1) includes (meth)acrylic acid ester compound, aromatic vinyl compound (preferably styrene-based compound), saturated fatty acid vinyl compound, vinyl cyanide compound, ethylenically unsaturated carboxylic acid, ethylenically unsaturated carboxylic acid anhydride, and ethylene. Examples include polyunsaturated dicarboxylic acid monoalkyl esters and ethylenically unsaturated carboxylic acid amides, and at least one selected from the group consisting of (meth)acrylic acid ester compounds, aromatic vinyl compounds, and saturated fatty acid vinyl compounds is preferred, Aromatic vinyl compounds are more preferred.

Specific examples of compound (F1) include methylstyrene and ethylvinylbenzene.

On the other hand, the resin composition according to the present embodiment also preferably contains styrene oligomer (F2) in order to improve low dielectric constant and low dielectric loss tangent. The styrene oligomer (F2) according to the present embodiment is obtained by polymerizing at least one member selected from the group consisting of styrene, the above-mentioned styrene derivative, and vinyltoluene, and its number average molecular weight is 178 to 1600 and the average number of aromatic rings is 2. It is a compound without a branched structure with a total amount of 2 to 14 aromatic rings of 50% by mass or more and a boiling point of 300°C or more.

Examples of the styrene oligomer (F2) used in this embodiment include styrene polymer, vinyltoluene polymer, α-methylstyrene polymer, vinyltoluene-α-methylstyrene polymer, and styrene-α-styrene polymer. . As the styrene polymer, commercially available products may be used, for example, Picolastic A5 (manufactured by Eastman Chemical), Picolastic A-75 (manufactured by Eastman Chemical), Picotex 75 (manufactured by Eastman Chemical), FTR-8100 ( Examples include FTR-8120 (manufactured by Mitsui Chemicals Co., Ltd.) and FTR-8120 (manufactured by Mitsui Chemicals Co., Ltd.). Moreover, examples of the vinyltoluene-α-methylstyrene polymer include Picotex LC (manufactured by Eastman Chemical Company). In addition, α-methylstyrene polymers include Crystallex 3070 (manufactured by Eastman Chemical), Crystalex 3085 (manufactured by Eastman Chemical), Crystalex (3100), Crystalex 5140 (manufactured by Eastman Chemical), and FMR-0100 (Mitsui). Examples include FMR-0150 (manufactured by Mitsui Chemicals Co., Ltd.). Additionally, examples of the 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 together.

In the resin composition of the present embodiment, α-methylstyrene oligomer is preferred because it is heat-cured well and has excellent fine wiring embedding properties, solder heat resistance, low relative dielectric constant, and low dielectric loss tangent.

In addition, for details of the monomer or oligomer having an ethylenically unsaturated group, the description in paragraphs 0069 to 0087 of International Publication No. 2017/135168 and paragraphs 0065 to 0067 of International Publication No. 2019/230945 can be referred to, the contents of which are Incorporated herein.

In particular, a monomer or oligomer having an ethylenically unsaturated group is used, and as the commonly used thermosetting resin (C), a thermosetting resin containing an aromatic ring and a vinyl group (in particular, a polymer having a structural unit represented by formula (V)) By using , a resin composition with excellent moisture absorption and heat resistance is obtained while maintaining excellent dielectric properties.

When the resin composition of the present embodiment contains a monomer or oligomer having an ethylenically unsaturated group, the content is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, based on 100 parts by mass of the resin solid content, and 2 It is more preferable that it is 3 parts by mass or more, and even more preferably 5 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 monomer or oligomer having an ethylenically unsaturated group is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and even more preferably 20 parts by mass or less, based on 100 parts by mass of the resin solid content. , it is more preferable that it is 15 parts by mass or less, and it is even more preferable that it is 10 parts by mass or less. By setting it below the above upper limit, heat resistance tends to improve further. In addition, low dielectric constant, low dielectric loss tangent, and chemical resistance tend to be further improved.

The resin composition of this embodiment may contain only one type, or may contain two or more types of monomers or oligomers having an ethylenically unsaturated group. When two or more types are included, it is preferable that the total amount falls within the above range.

＜Active ester compound＞

The resin composition of this embodiment may contain an active ester compound.

The active ester compound is not particularly limited, and for example, 2 or more per molecule (preferably 2 to 12, more preferably 2 to 6, further preferably 2 to 4, even more preferably 2 or 3, more preferably compounds having an active ester group of 2).

The active ester compound may be a straight-chain, branched, or cyclic compound. Among these, an active ester compound obtained by reacting a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxy compound and/or a thiol compound is preferred in terms of further improving the heat resistance of the resulting cured product, and the carboxylic acid An active ester compound obtained by reacting a compound with at least one compound selected from the group consisting of a phenol compound, a naphthol compound, and a thiol compound is more preferable, and is obtained by reacting a carboxylic acid compound with an aromatic compound having a phenolic hydroxyl group. More preferably, an aromatic compound having two or more active ester groups in one molecule is obtained by reacting a compound having two or more carboxylic acids in one molecule with an aromatic compound having a phenolic hydroxyl group, and has two or more active compounds in one molecule. Aromatic compounds having an ester group are particularly preferred.

Examples of the carboxylic acid compound include one or more selected from the group consisting of benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid, and among these, the resulting cured From the viewpoint of further improving the heat resistance of water, at least one selected from the group consisting of succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, and terephthalic acid is preferred, and one type selected from the group consisting of isophthalic acid and terephthalic acid. The above is more preferable.

Examples of the thiocarboxylic acid compound include at least one selected from thioacetic acid and thiobenzoic acid.

The phenol compounds or naphthol compounds include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydride At least one selected from the group consisting of hydroxybenzophenone, tetrahydroxybenzophenone, phloroglucine, benzenetriol, dicyclopentadienyldiphenol, and phenol novolac, and the heat resistance and solvent resistance of the resulting cured product. From the viewpoint of further improving solubility, bisphenol A, bisphenol F, bisphenol S, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucine, benzenetriol, dicyclopentadienyldi Phenol and phenol novolak are preferred, and catechol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, and trihydroxybenzophenone. , tetrahydroxybenzophenone, phloroglucine, benzenetriol, dicyclopentadienyldiphenol, and phenol novolak, more preferably at least one selected from the group consisting of 1,5-dihydroxynaphthalene, A group consisting of 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyldiphenol, and phenol novolak. More preferably, at least one selected from the group consisting of dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyldiphenol, and phenol novolak ( Preferably, at least one selected from the group consisting of dicyclopentadienyldiphenol and phenol novolac, more preferably dicyclopentadienyldiphenol).

Examples of the thiol compound include one or more selected from the group consisting of benzenedithiol and triazinedithiol.

In addition, the active ester compound is preferably a compound that has two or more carboxylic acids in one molecule and also contains an aliphatic chain from the viewpoint of further improving compatibility with the epoxy compound, and from the viewpoint of further improving heat resistance. , it is preferable that it is a compound having an aromatic ring. More specific active ester compounds include those described in Japanese Patent Application Laid-Open No. 2004-277460.

The active ester compound may be a commercially available product or may be prepared by a known method. Commercially available products include compounds containing a dicyclopentadienyldiphenol structure (e.g., EXB9451, EXB9460, EXB9460S, HPC-8000-65T (all manufactured by DIC), etc.), acetylated compounds of phenol novolak (e.g. , DC808 (manufactured by Mitsubishi Chemical Corporation)), and benzoylates of phenol novolacs (e.g., YLH1026, YLH1030, YLH1048 (all manufactured by Mitsubishi Chemical Corporation)), which provide stability in storage of the varnish and curing of the resin composition. From the viewpoint of further improving the low thermal expansion property of the hardened product, EXB9460S is preferable.

The active ester compound can be prepared by a known method, and can be obtained, for example, by a condensation reaction of a carboxylic acid compound and a hydroxy compound. Specific examples include (a) a carboxylic acid compound or its halide, (b) a hydroxy compound, and (c) an aromatic monohydroxy compound, relative to 1 mole of the carboxy group or acid halide group of (a), (b) A method of reacting at a ratio of 0.05 to 0.75 mol of phenolic hydroxyl group and (c) 0.25 to 0.95 mol of phenolic hydroxyl group can be mentioned.

The active ester compound is preferably included in a range that does not impair the effect of the present invention. When the resin composition of the present embodiment contains an active ester compound, it is preferably 1 part by mass or more, and preferably 90 parts by mass or less, based on 100 parts by mass of the resin solid content in the resin composition.

The resin composition in this embodiment may contain only one type of active ester compound, 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.

Moreover, the resin composition in this embodiment can also be configured to substantially not contain an active ester compound. Substantially not included means that the content of the active ester compound is less than 1 part by mass based on 100 parts by mass of the resin solid content in the resin composition, preferably less than 0.1 part by mass, and more preferably less than 0.01 part by mass.

＜Dispersant＞

The resin composition of this embodiment may contain a dispersant. As the dispersant, those generally used for paints can be preferably used, and the type is not particularly limited. The dispersant is preferably a copolymer-based wetting dispersant, and specific examples thereof include DISPERBYK (registered trademark) -110, 111, 161, 180, 2009, 2152, 2155 manufactured by Big Chemi Japan Co., Ltd. , BYK (registered trademark) - W996, W9010, W903, W940, etc.

When the resin composition of the present embodiment contains a dispersant, the lower limit of the content is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and 0.3 parts by mass, based on 100 parts by mass of the resin solid content in the resin composition. It can be more than that. Moreover, the upper limit of the content of the dispersant is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 3 parts by mass or less, based on 100 parts by mass of the resin solid content in the resin composition.

Dispersants can be used individually or in combination of two or more types. When two or more types are used, the total amount is within the above range.

＜Curing accelerator＞

The resin composition of this embodiment may further contain a curing accelerator. The curing accelerator is not particularly limited, but examples include imidazoles such as 2-ethyl-4-methylimidazole and triphenylimidazole; Benzoyl peroxide, lauroyl peroxide, acetyl peroxide, parachlorobenzoyl peroxide, di-tert-butyl-di-perphthalate, α,α'-di(t-butylperoxy)diisopropylbenzene, 2,5 -Organic peroxides such as dimethyl-2,5-di(t-butylperoxy)hexane and 2,5-dimethyl-2,5-bis(t-butylperoxy)hexene-3; azo compounds such as azobisnitrile (for example, azobisisobutyronitrile); N,N-dimethylbenzylamine, N,N-dimethylaniline, N,N-dimethyltoluidine, 2-N-ethylanilinoethanol, tri-n-butylamine, pyridine, quinoline, N-methylmorpholine, triethanolamine , tertiary amines such as triethylenediamine, tetramethylbutanediamine, and N-methylpiperidine; Phenols such as phenol, xylenol, cresol, resorcin, and catechol; High-temperature decomposition type radical generators such as 2,3-dimethyl-2,3-diphenylbutane; Organic metal salts such as lead naphthenate, lead stearate, zinc naphthenate, zinc octylate, manganese octylate, tin oleate, dibutyltin maleate, manganese naphthenate, cobalt naphthenate, and iron acetylacetone; Those obtained by dissolving these organometallic salts in hydroxyl group-containing compounds such as phenol and bisphenol; Inorganic metal salts such as tin chloride, zinc chloride, and aluminum chloride; and organic tin compounds such as dioctyl tin oxide, other alkyl tin oxides, and alkyl tin oxides.

Preferred curing accelerators are imidazoles and organometallic salts, and it is more preferable to use a combination of both imidazoles and organometallic salts.

Additionally, in the present embodiment, a configuration that substantially does not contain polymerization initiators such as organic peroxides and azo compounds can also be used. Substantially not included means that the content of the polymerization initiator is less than 0.1 parts by mass based on 100 parts by mass of the resin solid content in the resin composition.

When the resin composition of the present embodiment contains a curing accelerator, the lower limit of the content is preferably 0.005 parts by mass or more, more preferably 0.01 parts by mass or more, based on 100 parts by mass of the resin solid content in the resin composition. It is more desirable to have more than wealth. Moreover, the upper limit of the content of the curing accelerator is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 2 parts by mass or less, based on 100 parts by mass of the resin solid content in the resin composition.

The curing accelerator can be used individually or in combination of two or more types. When two or more types are used, the total amount is within the above range.

＜Solvent＞

The resin composition of this embodiment may contain a solvent, and it is preferable that it contains an organic solvent. When containing a solvent, the resin composition of the present embodiment is in a form (solution or varnish) in which at least part, preferably all, of the various resin solid contents described above are dissolved or dissolved in the solvent. The solvent is not particularly limited as long as it is a polar organic solvent or a non-polar organic solvent that can dissolve or be compatible with at least part, preferably all, of the various resin solids described above. Examples of the polar organic solvent include ketones (e.g. For example, 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, etc.) , ethyl acetate, butyl acetate, isoamyl acetate, methyl methoxypropionate, methyl hydroxyisobutyrate, etc.), amides (e.g., dimethoxyacetamide, dimethylformamide, etc.), and non-polar organic Examples of solvents include aromatic hydrocarbons (eg, toluene, xylene, etc.).

Solvents can be used individually or in combination of two or more types. When two or more types are used, the total amount is within the above range.

＜Other ingredients＞

The resin composition of the present embodiment may contain, in addition to the above components, various polymer compounds such as thermoplastic resins and oligomers thereof, and various additives. Additives include ultraviolet absorbers, antioxidants, photopolymerization initiators, optical whitening agents, photosensitizers, dyes, pigments, thickeners, flow regulators, lubricants, antifoaming agents, leveling agents, brighteners, polymerization inhibitors, etc. These additives can be used individually or in combination of two or more types.

＜Use＞

The resin composition of this embodiment is used as a cured product. Specifically, the resin composition of this embodiment can be suitably used as a low relative dielectric constant material and/or a low dielectric loss tangent material, and as a resin composition for electronic materials such as the insulating layer of a printed wiring board and a material for a semiconductor package. The resin composition of this embodiment can be suitably used as a material for prepreg, metal foil-clad laminate using prepreg, resin composite sheet, and printed wiring board.

The resin composition of the present embodiment is used as a layered material (including film-like, sheet-like, etc.) such as prepreg and resin composite sheet that becomes the insulating layer of a printed wiring board. In this case, the thickness is preferably 5 μm or more, and more preferably 10 μm or more. The upper limit of the thickness is preferably 200 μm or less, and more preferably 180 μm or less. In addition, the thickness of the layered material means the thickness including the glass cloth, for example, when the resin composition of the present embodiment is impregnated into a glass cloth or the like.

The material formed from the resin composition of this embodiment may be used for applications in which a pattern is formed by exposure and development, or may be used for applications without exposure and development. In particular, it is suitable for applications without exposure and development.

＜＜Prepreg＞＞

The prepreg of this embodiment is formed from a base material (prepreg base material) and the resin composition of this embodiment. The prepreg of this embodiment is, for example, applied (e.g., impregnated and/or applied) to a substrate with the resin composition of this embodiment, and then heated (e.g., 2 to 15 degrees Celsius at 120 to 220°C). It is obtained by semi-hardening by a method such as minute drying. In this case, the adhesion amount of the resin composition to the substrate, that is, the amount of the resin composition (including the filler (F)) relative to the total amount of prepreg after semi-curing, is preferably in the range of 20 to 99% by mass, and is 20 to 80% by mass. It is more preferable that it is in the range of mass%.

The base material is not particularly limited as long as it is a base material used for various printed wiring board materials. Materials of the substrate include, for example, glass fiber (e.g., E-glass, D-glass, L-glass, S-glass, T-glass, Q-glass, UN-glass, NE-glass, spherical glass) glass, etc.), inorganic fibers other than glass (e.g., quartz, etc.), and organic fibers (e.g., polyimide, polyamide, polyester, liquid crystalline polyester, polytetrafluoroethylene, etc.). The form of the base material is not particularly limited and includes woven fabric, non-woven fabric, roving, chopped strand mat, and surfacing mat. These base materials may be used individually, or two or more types may be used together. Among these substrates, from the viewpoint of dimensional stability, woven fabrics that have been treated with super-opening or weather stripping are preferable, and from the viewpoints of strength and low water absorption, the substrate has a thickness of 200 ㎛ or less and a mass of 250 g/m2. The following glass woven fabrics are preferable, and from the viewpoint of moisture absorption and heat resistance, glass woven fabrics surface-treated with a silane coupling agent such as epoxysilane or aminosilane are preferable. From the viewpoint of electrical properties, low-dielectric glass cloth made of glass fibers showing a low relative dielectric constant and low dielectric loss tangent, such as L-glass, NE-glass, or Q-glass, is more preferable.

Examples of a low relative dielectric constant include those with a relative dielectric constant of 5.0 or less (preferably 3.0 to 4.9). Examples of a base material having a low dielectric loss tangent include a base material having a dielectric loss tangent of 0.006 or less (preferably 0.001 to 0.005). The relative permittivity and dielectric loss tangent are values measured at 10 GHz using a perturbation method cavity resonator.

＜＜Metal foil clad laminate＞＞

The metal foil-clad laminate of the present embodiment includes at least one layer formed from the prepreg of the present embodiment, and metal foil disposed on one side or both sides of the layer formed from the prepreg. As a method of manufacturing the metal foil-clad laminate of the present embodiment, for example, at least one prepreg of the present embodiment is disposed (preferably two or more sheets are overlapped), and metal foil is disposed on one or both sides of the prepreg and laminated. A molding method may be mentioned. More specifically, it can be manufactured by placing metal foil such as copper or aluminum on one or both sides of the prepreg and laminating it. The number of prepregs is preferably 1 to 10 sheets, more preferably 2 to 10 sheets, and even more preferably 2 to 9 sheets. The metal foil is not particularly limited as long as it is used for printed wiring board materials, and examples include copper foil such as rolled copper foil and electrolytic copper foil. The thickness of the metal foil (preferably copper foil) is not particularly limited and may be about 1.5 to 70 μm. The molding method includes methods commonly used when molding laminated boards and multilayer boards for printed wiring boards, and more specifically, using a multi-stage press machine, a multi-stage vacuum press machine, a continuous molding machine, an autoclave molding machine, etc., at a temperature of 180 degrees Celsius. A method of laminate molding at about ∼350°C, heating time of about 100 to 300 minutes, and surface pressure of about 20 to 100 kg/cm2 can be mentioned. In addition, a multilayer board can also be obtained by laminate molding by combining the prepreg of this embodiment and a separately manufactured wiring board for the inner layer. As a method of manufacturing a multilayer board, for example, copper foil of about 35 μm is placed on both sides of one sheet of prepreg of the present embodiment, laminated by the above molding method, then an inner layer circuit is formed, and this circuit is blackened. Processing is performed to form an inner layer circuit board, and then the inner layer circuit board and the prepreg of the present embodiment are alternately arranged one at a time, and copper foil is further arranged on the outermost layer, and laminated under the above conditions, preferably under vacuum. By molding, a multilayer plate can be manufactured. The metal foil-clad laminate of this embodiment can be suitably used as a printed wiring board.

In addition, the metal foil-clad laminate of the present embodiment preferably has a low dielectric loss tangent (Df) measured using a laminate from which the metal foil has been removed by etching. Specifically, the dielectric loss tangent (Df) at 10 GHz measured according to the cavity resonator perturbation method is preferably 0.0040 or less, more preferably 0.0030 or less, even more preferably 0.0025 or less, and even more preferably less than 0.0025. . The lower limit of the dielectric loss tangent (Df) is not specifically determined, but for example, 0.0001 or more is practical.

The measurement of dielectric loss tangent follows the description of the examples described later.

In addition, the metal foil-clad laminate of the present embodiment preferably has a low coefficient of thermal expansion (CTE) measured using a laminate from which the metal foil has been removed by etching. Specifically, it is preferable that the CTE is 10 ppm/°C or less. For the lower limit, 0 is ideal, but 0.001 ppm/°C or higher is practical.

Measurement of CTE follows the description in the Examples described later.

As described above, the resin composition for electronic materials obtained by using the resin composition of the present embodiment (a resin composition consisting of a combination of specific components) has a cured product that has crack resistance in addition to dielectric properties (low dielectric loss tangent) and moisture absorption and heat resistance. It can be made to have excellent properties such as durability, appearance of the cured product, and low thermal expansion.

＜＜Printed wiring board＞＞

The printed wiring board of this embodiment is a printed wiring board including an insulating layer and a conductor layer disposed on the surface of the insulating layer, wherein the insulating layer is a layer formed of the resin composition of this embodiment and the prepreg of this embodiment. It includes at least one of the layers formed by. Such a printed wiring board can be manufactured according to a conventional method, and the manufacturing method is not particularly limited. Below, an example of a method for manufacturing a printed wiring board is shown. First, prepare a metal foil-clad laminate such as the copper foil-clad laminate described above. Next, an etching process is performed on the surface of the metal foil-clad laminate to form an inner layer circuit, and an inner layer substrate is manufactured. The inner layer circuit surface of this inner layer substrate is subjected to surface treatment to increase the adhesive strength as necessary, and then the required number of prepregs described above are overlapped on the inner layer circuit surface, and additionally, a metal foil for the outer layer circuit is placed on the outside. are stacked, heated and pressed, and integrally formed. In this way, a multilayer laminate is manufactured in which an insulating layer made of a base material and a cured resin composition is formed between the metal foil for the inner layer circuit and the outer layer circuit. Next, after drilling through holes and via holes in this multi-layer laminate, a plated metal film is formed on the wall of this hole to connect the metal foil for the inner layer circuit and the outer layer circuit, and is further applied to the metal foil for the outer layer circuit. A printed wiring board is manufactured by performing an etching process to form an outer layer circuit.

The printed wiring board obtained in the above production example has an insulating layer and a conductor layer formed on the surface of the insulating layer, and the insulating layer contains the resin composition of the present embodiment described above and/or its cured product. That is, the prepreg of the present embodiment described above (e.g., the prepreg formed of the base material and the resin composition of the present embodiment impregnated or applied thereto), the resin composition of the metal foil-clad laminate of the present embodiment described above. The formed layer becomes the insulating layer of this embodiment.

Additionally, this embodiment also relates to a semiconductor device including the printed wiring board. For details of the semiconductor device, the description in paragraphs 0200 to 0202 of Japanese Patent Application Publication No. 2021-021027 can be taken into consideration, and these contents are incorporated into this specification.

＜＜Resin composite sheet＞＞

The resin composite sheet of this embodiment includes a support and a layer formed of the resin composition of this embodiment disposed on the surface of the support. The resin composite sheet can be used as a build-up film or dry film solder resist. The method for producing the resin composite sheet is not particularly limited, but includes, for example, a method of obtaining a resin composite sheet by applying (coating) a solution obtained by dissolving the resin composition of the present embodiment in a solvent to a support and drying it. there is.

Examples of the support used here include polyethylene film, polypropylene film, polycarbonate film, polyethylene terephthalate film, ethylene tetrafluoroethylene copolymer film, and a release film obtained by applying a release agent to the surface of these films, Organic film substrates such as polyimide films, conductor foils such as copper foil and aluminum foil, plate-shaped materials such as glass plates, SUS (Steel Use Stainless) plates, and FRP (Fiber-Reinforced Plastics) include, but are not particularly limited. .

Examples of the application method (coating method) include a method of applying a solution obtained by dissolving the resin composition of the present embodiment in a solvent onto a support using a bar coater, die coater, doctor blade, baker applicator, etc. . In addition, after drying, a single-layer sheet can be formed by peeling or etching the support from the resin composite sheet in which the support and the resin composition are laminated. In addition, a single-layer sheet can be obtained without using a support by supplying a solution obtained by dissolving the resin composition of the present embodiment in a solvent into a mold having a sheet-shaped cavity, drying it, or molding it into a sheet.

In addition, in the production of the single-layer sheet or resin composite sheet of the present embodiment, the drying conditions for removing the solvent are not particularly limited, but if the temperature is low, the solvent tends to remain in the resin composition, and if the temperature is high, the curing of the resin composition progresses. From this point, 1 to 90 minutes is preferable at a temperature of 20°C to 200°C. In addition, the single-layer sheet or resin composite sheet can be used in an uncured state by simply drying the solvent, or, if necessary, in a semi-cured (B-staged) state. In addition, the thickness of the resin layer in the single-layer sheet or resin composite sheet of this embodiment can be adjusted by the concentration and application thickness of the solution of the resin composition of this embodiment used for application (coating), and is not particularly limited. However, in general, the thicker the coating thickness, the easier it is for the solvent to remain during drying, so 0.1 to 500 µm is preferable.

Example

The present invention will be described in more detail below with reference to examples. Materials, usage amount, ratio, processing content, processing sequence, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the spirit of the present invention. Accordingly, the scope of the present invention is not limited to the specific examples shown below.

If the measuring device used in the examples is difficult to obtain due to discontinuation of production, etc., measurement can be performed using another device with equivalent performance.

<Synthesis Example 1 Synthesis of modified polyphenylene ether compound>

＜＜Synthesis of bifunctional phenylene ether oligomer＞＞

In a 12 L vertically long reactor equipped with a stirring device, thermometer, air inlet pipe, and baffle plate, 9.36 g (42.1 mmol) of CuBr ₂ , 1.81 g (10.5 mmol) of N,N'-di-t-butylethylenediamine, n - 67.77 g (671.0 mmol) of butyldimethylamine and 2,600 g of toluene were added, stirred at a reaction temperature of 40°C, and 2,2', 3,3', 5,5' dissolved in 2,300 g of methanol in advance. -Hexamethyl-(1,1'-biphenol)-4,4'-diol 129.32 g (0.48 mol), 2,6-dimethylphenol 878.4 g (7.2 mol), N,N'-di-t-butyl A mixed solution of 1.22 g (7.2 mmol) of ethylenediamine and 26.35 g (260.9 mmol) of n-butyldimethylamine was mixed with nitrogen and air to adjust the oxygen concentration to 8% by volume. The mixed gas was bubbled at a flow rate of 5.2 L/min. It was added dropwise over 230 minutes while ringing and stirred. After completion of the dropwise addition, 1,500 g of water in which 48.06 g (126.4 mmol) of tetrasodium ethylenediamine tetraacetate was dissolved was added to stop the reaction. The aqueous layer and the organic layer were separated, and the organic layer was washed with a 1 N aqueous hydrochloric acid solution and then with pure water. The obtained solution was concentrated to 50% by mass using an evaporator to obtain 1981 g of a toluene solution of the bifunctional phenylene ether oligomer (resin "A"). The number average molecular weight of resin "A" as calculated by GPC in terms of polystyrene was 1975, the weight average molecular weight in terms of polystyrene as determined by GPC was 3514, and the hydroxyl equivalent weight was 990.

＜＜Synthesis of modified polyphenylene ether compound＞＞

In a reactor equipped with a stirring device, a thermometer, and a reflux tube, 833.4 g of a toluene solution of resin “A”, 76.7 g of vinylbenzyl chloride (“CMS-P” manufactured by AGC Semi Chemicals), 1,600 g of methylene chloride, and benzyldimethyl. 6.2 g of amine, 199.5 g of pure water, and 83.6 g of a 30.5 mass% NaOH aqueous solution were charged, and stirring was performed at a reaction temperature of 40°C. After stirring for 24 hours, the organic layer was washed with a 1 N aqueous hydrochloric acid solution and then with pure water. The obtained solution was concentrated with an evaporator, solidified by dropping it into methanol, and the solid was recovered by filtration and dried under vacuum to obtain 450.1 g of a modified polyphenylene ether compound. The number average molecular weight of the modified polyphenylene ether compound in terms of polystyrene according to GPC was 2250, the weight average molecular weight in terms of polystyrene by GPC was 3920, and the vinyl equivalent was 1189 g/vinyl group.

<Synthesis Example 2 Synthesis of naphthol aralkyl type cyanate compound (SNCN)>

α-Naphthol aralkyl resin (SN495V, OH group equivalent: 236 g/eq., manufactured by Nippon Chemical Co., Ltd.: naphthol aralkyl has a repeating unit number of 1 to 5) 0.47 mol (in terms of OH group) was dissolved in 500 mL of chloroform, and 0.7 mol of triethylamine was added to this solution to prepare Solution 1. While maintaining the temperature at -10°C, Solution 1 was added dropwise to 300 g of a 0.93 mole cyanogen chloride chloroform solution injected into the reactor over 1.5 hours, and the mixture was stirred for 30 minutes after completion of the dropwise addition. After that, a mixed solution of 0.1 mol of triethylamine and 30 g of chloroform was added dropwise into the reactor and stirred for 30 minutes to complete the reaction. After the by-produced triethylamine hydrochloride was separated by filtration from the reaction solution, the obtained filtrate was washed with 500 mL of 0.1 N hydrochloric acid, and then washing with 500 mL of water was repeated four times. After drying this with sodium sulfate, evaporating at 75°C and further degassing under reduced pressure at 90°C, an α-naphthol aralkyl type cyanate compound represented by formula (S1) (R ^C1 in the formula) is obtained as a brown solid. R ^C4 is all hydrogen atoms, and n ^c is a mixture of 1 to 5) was obtained. As a result of analyzing the obtained α-naphthol aralkyl type cyanate compound using an infrared absorption spectrum, absorption of the cyanate ester group was confirmed around 2264 cm ^-1 .

[Formula 42]

＜Synthesis Example 3 Synthesis of polymer (va) having structural units represented by formula (V)>

2.25 moles (292.9 g) of divinylbenzene, 1.32 moles (172.0 g) of ethylvinylbenzene, 11.43 moles (1190.3 g) of styrene, and 15.0 moles (1532.0 g) of n-propyl acetate were introduced into the reactor, and 600 mmol of ethylvinylbenzene was added to the reactor at 70°C. Diethyl ether complex of boron trifluoride was added, and reaction was performed for 4 hours. After the polymerization reaction was stopped with an aqueous sodium bicarbonate solution, the oil layer was washed three times with pure water, devolatilized under reduced pressure at 60°C, and polymer (va) having a structural unit represented by formula (V) was recovered. The obtained polymer (va) having a structural unit represented by formula (V) was weighed, and it was confirmed that 860.8 g of polymer (va) having a structural unit represented by formula (V) was obtained.

The obtained polymer (va) having the structural unit represented by formula (V) had a number average molecular weight Mn of 2,060, a weight average molecular weight Mw of 30,700, and a monodispersity Mw/Mn of 14.9. By performing ¹³ C-NMR and ¹ H-NMR analysis, resonance lines derived from each monomer unit used as a raw material were observed in the polymer (va) having the structural unit represented by formula (V). Based on the NMR measurement results and the GC analysis results, the ratio of each monomer unit (structural unit derived from each raw material) in the polymer (va) having the structural unit represented by formula (V) was calculated as follows.

Constituent unit derived from divinylbenzene: 20.9 mol% (24.3 mass%)

Constituent unit derived from ethylvinylbenzene: 9.1 mol% (10.7 mass%)

Constituent unit derived from styrene: 70.0 mol% (65.0 mass%)

Moreover, the structural unit having a residual vinyl group derived from divinylbenzene was 16.7 mol% (18.5 mass%).

＜Measurement of weight average molecular weight and number average molecular weight＞

The weight average molecular weight (Mw) and number average molecular weight (Mn) were measured by gel permeation chromatography (GPC). Use a liquid delivery pump (LC-20AD, manufactured by Shimadzu Corporation), differential refractive index detector (RID-10A, manufactured by Shimadzu Corporation), and GPC column (GPC KF-801, 802, 803, 804, manufactured by Showa Denko). , was carried out using tetrahydrofuran as the solvent, flow rate of 1.0 mL/min, column temperature of 40°C, and a calibration curve based on monodisperse polystyrene.

Example 1

30 parts by mass of the modified polyphenylene ether compound obtained in Synthesis Example 1, 30 parts by mass of maleimide compound (MIR-3000-70MT, manufactured by Nippon Kayaku Co., Ltd., equivalent to the compound represented by formula (M3)), in Synthesis Example 2 above 5 parts by mass of the obtained naphthol aralkyl type cyanate compound (SNCN), α-methylstyrene oligomer (KA3085 (brand name), weight average molecular weight: 664, manufactured by Eastman Chemical Co., Ltd.) 5 parts by mass, phosphorus-based flame retardant (PX-200, die Hachi Chemical Co., Ltd.) 15 parts by mass, hydrogenated styrene-based thermoplastic elastomer (SEBS, SEPTON2104, Mn 83000, manufactured by Kuraray Co., Ltd.) 7.5 parts by mass, non-hydrogenated styrene-based thermoplastic elastomer (SBS, TR2250, Mn 115000, manufactured by JSR Co., Ltd.) 7.5 100 parts by mass of silica (manufactured by Admatex Co., Ltd., SC2050-MNU) were mixed and diluted to 65% by mass in terms of solid content using methyl ethyl ketone to obtain a varnish. In addition, the compounding amount of each component represents the solid content.

This varnish was impregnated and coated on NE glass woven fabric with a thickness of 0.1 mm (2013 S101S, manufactured by Nitto Textile Co., Ltd.) and dried by heating at 165°C for 5 minutes to obtain a prepreg (thickness 0.1 mm) with a resin composition content of 60% by mass. . In addition, the characteristics of the NE glass woven fabric used are as follows.

IPC applicable varieties : 2013

Density (piece/25 mm) vertical : 46

Density (piece/25 ㎜) horizontal : 44.1

Thickness (㎜) : 0.070

Mass (g/㎡) : 80.7

One or eight sheets of the obtained prepreg were overlapped, a 12 μm thick electrolytic copper foil (3EC-M3-VLP, manufactured by Mitsui Metal Mining Co., Ltd.) was placed on both sides, and the pressure was 30 kgf/cm2 and the temperature was 220°C to 120°C. Vacuum pressing was performed for a minute to obtain a copper foil-clad laminate with an insulating layer thickness of 0.1 mm or 0.8 mm as a metal foil-clad laminate.

The obtained copper foil-clad laminate was evaluated for physical properties (dielectric loss tangent (Df), moisture absorption heat resistance, crack resistance, appearance after curing, coefficient of thermal expansion (CTE)) according to the method described later.

＜Dielectric loss tangent＞

For the obtained copper foil-clad laminate, a test piece (30 mm × 150 mm × 0.8 mm) was prepared from which the copper foil was removed by etching, and the dielectric loss tangent (Df) at 10 GHz was measured using a perturbation method cavity resonator. The measurement temperature was 23°C.

The perturbation method cavity resonator used was Agilent8722ES, manufactured by Agilent Technologies.

The evaluation was as follows.

A: less than 0.0025

B: 0.0025 or more

＜Moisture absorption and heat resistance＞

For the obtained copper foil-clad laminate, all of the copper foil on one side was removed by etching, and on the other side, half of the copper foil on the side was removed by etching to prepare a test piece (50 mm × 50 mm × 0.8 mm). . This test piece was left standing for 3 hours in the presence of saturated water vapor at 121°C and 2 atm using a pressure cooker tester, and then immersed in a solder tank at 260°C for 30 seconds to observe the presence or absence of peeling. The pressure cooker tester used was the PC-3 type manufactured by Hirayama Seisakusho.

A: No problem

B: There is peeling

＜Crack resistance (MIT test)＞

For the obtained copper foil-clad laminate, in accordance with JIS C5016:1994, a test piece (15 mm Install the wire, fix the upper part of the test specimen to the plunger, install a load of 1 kgf on the lower part, and start bending in both directions at an angle of 135° and a speed of 175 cpm while energized, when a disconnection is reached. The number of reciprocating bends up to was measured.

The evaluation was as follows.

S: 81 or more times

A: More than 71 times and less than 80 times

B: More than 40 times and less than 70 times

C: 39 times or less

＜Appearance after curing＞

The copper foil of the obtained copper foil-clad laminate was removed by etching, and a test piece (330 mm × 330 mm × 0.1 mm) for external appearance observation after curing was obtained. The surface was observed to confirm the separation state of the thermoplastic elastomer (A) and/or the thermoplastic elastomer (B) and the thermosetting resin (C), and the presence or absence of external appearance abnormalities was evaluated according to the following evaluation criteria.

The evaluation was as follows. The evaluation was conducted by five experts and was decided by majority vote.

A: No problem

B: Appearance is defective

＜Coefficient of linear thermal expansion (CTE)＞

Thermal expansion of the test piece (4.5 mm The coefficient was measured and its value was obtained. Specifically, after removing and downsizing the copper foil on both sides of the copper foil-clad laminate obtained above by etching, the temperature was raised from 30°C to 340°C at 10°C per minute using a thermomechanical analysis device (manufactured by TA Instruments), and the temperature was raised to 30°C. The coefficient of linear thermal expansion (CTE (X)) (unit: ppm/°C) in the plane direction at 300°C was measured. The measurement direction was the longitudinal direction (Warp) of the glass cloth of the laminated board. ppm is the volume ratio. For other details, follow JIS C 6481 5.19 above.

The evaluation was as follows.

A: 10 ppm/℃ or less

B: exceeding 10 ppm/℃

Example 2

In Example 1, the hydrogenated styrene-based thermoplastic elastomer (SEPTON2104) was replaced with the same amount of hydrogenated styrene-based thermoplastic elastomer (SEBS, S.O.E. (registered trademark) S1605, Mn 250000, manufactured by Asahi Kasei Co., Ltd.), and everything else was carried out in the same manner. .

Example 3

In Example 2, instead of the non-hydrogenated styrene-based thermoplastic elastomer (SBS, TR2250, Mn 115000, manufactured by Asahi Chemical Co., Ltd.), an equal amount of partially hydrogenated styrene-based thermoplastic elastomer (SBBS, S.O.E. (registered trademark) S1609, Mn 228000, Asahi) was used. (manufactured by Hwaseong Co., Ltd.) was mixed, and other operations were performed in the same manner.

Example 4

In Example 3, the blending amount of the modified polyphenylene ether compound obtained in Synthesis Example 1 was changed to 15 parts by mass, and additionally, 15 parts by mass of the polymer (va) obtained in Synthesis Example 3 was blended, other things remaining the same. It was carried out.

Example 5

In Example 4, the blending amount of hydrogenated styrene-based thermoplastic elastomer (SEBS, S.O.E. (registered trademark) S1605, Mn 250000, manufactured by Asahi Chemical Co., Ltd.) was changed to 2 parts by mass, and in addition, some hydrogenated styrene-based thermoplastic elastomer (SBBS, The mixing amount of S.O.E. (registered trademark) S1609, Mn 228000, manufactured by Asahi Kasei Co., Ltd. was changed to 13 parts by mass, and everything else was performed in the same manner.

Comparative Example 1

In Example 1, the hydrogenated styrene thermoplastic elastomer (SEPTON2104) and the non-hydrogenated styrene thermoplastic elastomer (TR2250) were not blended, and the blending amount of the maleimide compound (MIR-3000-70MT) was changed to 45 parts by mass, and the other The same was carried out.

Comparative Example 2

In Example 1, the hydrogenated styrene-based thermoplastic elastomer (SEPTON2104) and the non-hydrogenated styrene-based thermoplastic elastomer (TR2250) were not blended, but 15 parts by mass of hydrogenated styrene-based thermoplastic elastomer (S1605) was blended, and other operations were performed in the same manner. did.

Comparative Example 3

In Example 1, instead of the non-hydrogenated styrene-based thermoplastic elastomer (TR2250), the same amount of hydrogenated styrene-based thermoplastic elastomer (S1605) was blended, and other operations were performed in the same manner.

Comparative Example 4

In Example 1, the modified polyphenylene ether compound obtained in Synthesis Example 1 was not blended, the blending amount of the maleimide compound (MIR-3000-70MT) was changed to 60 parts by mass, and other operations were performed in the same manner.

Comparative Example 5

In Comparative Example 4, instead of the hydrogenated styrene-based thermoplastic elastomer (SEPTON2104), the same amount of hydrogenated styrene-based thermoplastic elastomer (S1605) was blended, and other operations were performed in the same manner.

Claims (21)

A thermoplastic elastomer (A), a thermoplastic elastomer (B), and a thermosetting resin (C) compatible with both the thermoplastic elastomer (A) and the thermoplastic elastomer (B),
The thermoplastic elastomer (A) is a thermoplastic elastomer containing a styrene monomer unit and a conjugated diene monomer unit and having a number average molecular weight of 50,000 or more, wherein all of the conjugated diene bonds of the thermoplastic elastomer are hydrogenated,
The thermoplastic elastomer (B) is a thermoplastic elastomer containing a styrene monomer unit and a conjugated diene monomer unit and having a number average molecular weight of 50,000 or more, wherein a portion of the conjugated diene bond of the thermoplastic elastomer is hydrogenated, and/or, A resin composition that is a thermoplastic elastomer with all unsaturated bonds. According to claim 1,
A resin composition wherein the total content of the thermoplastic elastomer (A) and the thermoplastic elastomer (B) in the resin composition is 1 to 40 parts by mass based on 100 parts by mass of the resin solid content. The method of claim 1 or 2,
A resin composition wherein the mass ratio of the thermoplastic elastomer (A) to the thermoplastic elastomer (B) in the resin composition is 1:1 to 10. The method of claim 1 or 2,
A resin composition wherein the commonly used thermosetting resin (C) is a thermosetting resin containing an aromatic ring and a vinyl group. The method of claim 1 or 2,
The commercially available thermosetting resin (C) contains at least one member selected from the group consisting of a polymer having a structural unit represented by formula (V), and a polyphenylene ether compound having a carbon-carbon unsaturated double bond at the terminal. , resin composition.

(In formula (V), Ar represents an aromatic hydrocarbon linking group. * represents the bonding position.) The method of claim 1 or 2,
A resin composition wherein the content of the commonly used thermosetting resin (C) is 10 to 90 parts by mass based on 100 parts by mass of the resin solid content. The method of claim 1 or 2,
Additionally, a resin composition containing at least one other resin (D) selected from the group consisting of cyanate ester compounds, maleimide compounds, and epoxy compounds. According to claim 7,
The maleimide compound is a compound represented by the formula (M0), a compound represented by the formula (M1), a compound represented by the formula (M2), a compound represented by the formula (M3), a compound represented by the formula (M4), and a compound represented by the formula (M5) ) A resin composition containing at least one member selected from the group consisting of compounds represented by .

(In the formula (M0), R ⁵¹ each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group, R ⁵² each independently represents a hydrogen atom or a methyl group, and n ₁ is an integer of 1 or more. represents.)

(In formula (M1), 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, R ^M7 and R ^M8 are each independently an alkyl group, and lx is 0 or 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. Alkyl group with 1 to 10 carbon atoms, alkyloxy group with 1 to 10 carbon atoms, alkylthio group with 1 to 10 carbon atoms, aryl group with 6 to 10 carbon atoms, aryloxy group with 1 to 10 carbon atoms, arylthio group with 1 to 10 carbon atoms , px represents an integer of 0 to 3, and nx represents an integer of 1 to 20.

(In formula (M2), R ⁵⁴ each independently represents a hydrogen atom or a methyl group, and n ₄ represents an integer of 1 or more.)

(In formula (M3), R ⁵⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group, and n ₅ represents an integer from 1 to 10.)

(In formula (M4), R ⁵⁶ each independently represents a hydrogen atom, a methyl group, or an ethyl group, and R ⁵⁷ each independently represents a hydrogen atom or a methyl group.)

(In formula (M5), R ⁵⁸ each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group, R ⁵⁹ each independently represents a hydrogen atom or a methyl group, and n ₆ is an integer of 1 or more. represents.) According to claim 7,
A resin composition in which the maleimide compound contains a compound represented by formula (M1) and/or a compound represented by formula (M3).

(In formula (M1), 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, R ^M7 and R ^M8 are each independently an alkyl group, and lx is 0 or 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. Alkyl group with 1 to 10 carbon atoms, alkyloxy group with 1 to 10 carbon atoms, alkylthio group with 1 to 10 carbon atoms, aryl group with 6 to 10 carbon atoms, aryloxy group with 1 to 10 carbon atoms, arylthio group with 1 to 10 carbon atoms , px represents an integer of 0 to 3, and nx represents an integer of 1 to 20.

(In formula (M3), R ⁵⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group, and n ₅ represents an integer from 1 to 10.) The method of claim 1 or 2,
A resin composition further comprising a flame retardant (E). According to claim 10,
A resin composition in which the flame retardant (E) contains a phosphorus-based flame retardant. The method of claim 1 or 2,
A resin composition further comprising a filler (F). According to claim 12,
A resin composition wherein the filler (F) contains at least one member selected from the group consisting of silica, aluminum hydroxide, aluminum nitride, boron nitride, forsterite, titanium oxide, barium titanate, strontium titanate, and calcium titanate. According to claim 12,
A resin composition in which the content of the filler (F) is 10 to 300 parts by mass based on 100 parts by mass of the resin solid content. The method of claim 1 or 2,
Additionally, a resin composition containing 0.5 to 30 parts by mass of a monomer or oligomer having an ethylenically unsaturated group based on 100 parts by mass of the resin solid content. According to claim 1,
The total content of the thermoplastic elastomer (A) and the thermoplastic elastomer (B) in the resin composition is 1 to 40 parts by mass based on 100 parts by mass of the resin solid content,
In the resin composition, the mass ratio of the thermoplastic elastomer (A) to the thermoplastic elastomer (B) is 1:1 to 10,
The commercially available thermosetting resin (C) is a thermosetting resin containing an aromatic ring and a vinyl group,
The commercially available thermosetting resin (C) contains at least one member selected from the group consisting of a polymer having a structural unit represented by formula (V), and a polyphenylene ether compound having a carbon-carbon unsaturated double bond at the terminal, ,

(In formula (V), Ar represents an aromatic hydrocarbon linking group. * represents the bonding position.)
The content of the commonly used thermosetting resin (C) is 10 to 90 parts by mass based on 100 parts by mass of the resin solid content,
Additionally, it contains at least one other resin (D) selected from the group consisting of cyanate ester compounds, maleimide compounds, and epoxy compounds,
The maleimide compound contains at least one member selected from the group consisting of a compound represented by formula (M1), a compound represented by formula (M3), and a compound represented by formula (M5),
Additionally, it contains a flame retardant (E),
The flame retardant (E) includes a phosphorus-based flame retardant,
Additionally, it comprises a filler (F),
The filler (F) contains at least one member selected from the group consisting of silica, aluminum hydroxide, aluminum nitride, boron nitride, forsterite, titanium oxide, barium titanate, strontium titanate, and calcium titanate,
The content of the filler (F) is 10 to 300 parts by mass based on 100 parts by mass of the resin solid content,
Additionally, a resin composition containing 0.5 to 30 parts by mass of a monomer or oligomer having an ethylenically unsaturated group based on 100 parts by mass of the resin solid content.

(In formula (M1), 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, R ^M7 and R ^M8 are each independently an alkyl group, and lx is 0 or 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. Alkyl group with 1 to 10 carbon atoms, alkyloxy group with 1 to 10 carbon atoms, alkylthio group with 1 to 10 carbon atoms, aryl group with 6 to 10 carbon atoms, aryloxy group with 1 to 10 carbon atoms, arylthio group with 1 to 10 carbon atoms , px represents an integer of 0 to 3, and nx represents an integer of 1 to 20.

(In formula (M3), R ⁵⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group, and n ₅ represents an integer from 1 to 10.)

(In formula (M5), R ⁵⁸ each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group, R ⁵⁹ each independently represents a hydrogen atom or a methyl group, and n ₆ is an integer of 1 or more. represents.) A prepreg formed from a base material and the resin composition according to claim 1, 2 or 16. A metal foil-clad laminate comprising at least one layer formed from the prepreg according to claim 17 and metal foil disposed on one side or both sides of the layer formed from the prepreg. A resin composite sheet comprising a support and a layer formed of the resin composition according to claim 1, 2 or 16 disposed on the surface of the support. A printed wiring board comprising an insulating layer and a conductor layer disposed on a surface of the insulating layer, wherein the insulating layer includes a layer formed of the resin composition according to claim 1, 2, or 16. . A semiconductor device comprising the printed wiring board according to claim 20.