JP2024054955A - Resin composition for adhesives, crosslinked body, thermosetting adhesive film or sheet, laminate, circuit board and electronic apparatus - Google Patents

Abstract

To provide a resin composition for adhesives that improves low dielectric properties and transparency within high-frequency regions.SOLUTION: A resin composition for adhesives comprises a thermosetting cyclic olefinic copolymer (m), a crosslinker (X), and an antioxidant (Y), the thermosetting cyclic olefinic copolymer (m) comprising (A) at least one olefin-derived repeating unit, (B) at least one cyclic nonconjugated diene-derived repeating unit, and (C) at least one cyclic olefin-derived repeating unit.SELECTED DRAWING: None

Description

The present invention relates to an adhesive resin composition, a crosslinked body, a thermosetting adhesive film or sheet, a laminate, a circuit board, and an electronic device.

In recent years, in addition to an increase in wireless communication devices that use high-frequency bands, the increasing speed of communication has inevitably led to more frequent use of higher frequency bands. Accordingly, in order to minimize transmission loss at high frequencies, there is a demand for materials that make up circuit boards (such as base materials, adhesives, glass cloth, and fillers) to have small dielectric tangents.

Patent Document 1 and Patent Document 2 disclose that a sheet obtained by crosslinking a cyclic olefin copolymer copolymerized with a specific diene compound with an organic peroxide or the like exhibits excellent dielectric properties.

Patent Document 3 also discloses that by using polyphenylene ether resin in the adhesive layer of a high-frequency substrate, an adhesive layer with a small dielectric tangent can be obtained.

JP 2010-100843 A International Publication No. 2012/046443 JP 2021-147621 A

According to the investigations of the present inventors, in the cured product of the adhesive composition described in Patent Document 3, there was room for further improvement in the low dielectric properties in the high frequency range in order to accommodate the even higher frequencies of electrical signals that are expected in the future.
Furthermore, the adhesive composition described in Patent Document 3 has a cured product with a brown color, and is therefore not suitable for applications requiring transparency, so there is room for further improvement in terms of transparency.

The present invention was made in consideration of the above circumstances, and provides an adhesive resin composition that has low dielectric properties and improved transparency in the high frequency range.

As a result of intensive research aimed at solving the above problems, the inventors discovered that by using a specific cyclic olefin copolymer, it is possible to obtain an adhesive resin composition that has low dielectric properties and transparency in the high frequency range, and thus completed the present invention.

〔上記一般式（Ｉ）において、Ｒ^３００は水素原子または炭素原子数１～２９の直鎖状または分岐状の炭化水素基を示す。〕

〔上記一般式（ＩＩＩ）中、ｕは０または１であり、ｖは０または正の整数であり、ｗは０または１であり、Ｒ^６１～Ｒ^７６ならびにＲ^ａ１およびＲ^ｂ１は互いに同一でも異なっていてもよく、水素原子、ハロゲン原子、炭素原子数１～２０のアルキル基、炭素原子数１～２０のハロゲン化アルキル基、炭素原子数３～１５のシクロアルキル基または炭素原子数６～２０の芳香族炭化水素基であり、Ｒ^１０４は水素原子または炭素原子数１～１０のアルキル基であり、tは０～１０の正の整数であり、Ｒ^７５およびＲ^７６は互いに結合して単環または多環を形成していてもよい。〕

〔上記一般式（Ｖ）中、ｕは０または１であり、ｖは０または正の整数であり、ｗは０または１であり、Ｒ^６１～Ｒ^７８ならびにＲ^ａ１およびＲ^ｂ１は互いに同一でも異なっていてもよく、水素原子、ハロゲン原子、炭素原子数１～２０のアルキル基、炭素原子数１～２０のハロゲン化アルキル基、炭素原子数３～１５のシクロアルキル基または炭素原子数６～２０の芳香族炭化水素基であり、Ｒ^７５～Ｒ^７８は互いに結合して単環または多環を形成していてもよい。〕
［２］
前記熱硬化型環状オレフィン系共重合体（ｍ）とは異なる環状オレフィン系（共）重合体（ｎ）をさらに含み、
前記環状オレフィン系（共）重合体（ｎ）は、エチレンまたはα－オレフィンと環状オレフィンとの共重合体（ｎ１）（ただし、前記共重合体（ｎ１）は前記一般式（ＩＩＩ）で表される環状非共役ジエン由来の繰り返し単位を含まない）および環状オレフィンの開環重合体（ｎ２）から選択される少なくとも一種を含み、
前記熱硬化型環状オレフィン系共重合体（ｍ）と前記環状オレフィン系（共）重合体（ｎ）との合計量を１００質量％としたとき、
前記熱硬化型環状オレフィン系共重合体（ｍ）の含有量が５質量％以上９５質量％以下であり、
前記環状オレフィン系（共）重合体（ｎ）の含有量が５質量％以上９５質量％以下である、［１］に記載の接着性樹脂組成物。
［３］
バインダー樹脂をさらに含有する、［１］または［２］に記載の接着性樹脂組成物。
［４］
前記バインダー樹脂は変性ポリオレフィンを含む、［３］に記載の接着性樹脂組成物。
［５］
前記熱硬化型環状オレフィン系共重合体（ｍ）中の繰り返し単位の合計モル数を１００モル％とした場合に、
前記オレフィン由来の繰り返し単位（Ａ）の含有量が１０モル％以上９０モル％以下、
前記環状非共役ジエン由来の繰り返し単位（Ｂ）の含有量が１モル％以上４０モル％以下、および
前記環状オレフィン由来の繰り返し単位（Ｃ）の含有量が１モル％以上５０モル％以下である、［１］～［４］のいずれかに記載の接着性樹脂組成物。
［６］
前記環状非共役ジエン由来の繰り返し単位（Ｂ）を構成する環状非共役ジエンが、５－ビニル－２－ノルボルネンを含む、［１］～［５］のいずれかに記載の接着性樹脂組成物。
［７］
前記環状オレフィン由来の繰り返し単位（Ｃ）を構成する環状オレフィンが、テトラシクロ［４．４．０．１^２，５．１^７，１０］－３－ドデセンおよびビシクロ［２．２．１］－２－ヘプテンからなる群から選択される少なくとも一種を含む、［１］～［６］のいずれかに記載の接着性樹脂組成物。
［８］
［１］～［７］のいずれかに記載の接着性樹脂組成物の架橋体。
［９］
［１］～［７］のいずれかに記載の接着性樹脂組成物または［８］に記載の架橋体を含む熱硬化性接着フィルムまたはシート。
［１０］
［９］に記載の熱硬化性接着フィルムまたはシートを基材に積層した積層体。
［１１］
［１］～［７］のいずれかに記載の接着性樹脂組成物または［８］に記載の架橋体を含む電気絶縁層と、前記電気絶縁層上に設けられた導体層とを含む回路基板。
［１２］
電気絶縁層と、導体層と、前記電気絶縁層と前記導体層とを接着するための接着層と、を含み、前記接着層が［１］～［７］のいずれかに記載の接着性樹脂組成物または［８］に記載の架橋体を含む回路基板。
［１３］
［１１］または［１２］に記載の回路基板を備えた電子機器。 [1]
A thermosetting cyclic olefin copolymer (m);
A crosslinking agent (X);
An antioxidant (Y);
An adhesive resin composition comprising:
The thermosetting cyclic olefin copolymer (m) is
(A) one or more olefin-derived repeating units represented by the following general formula (I),
(B) one or more repeating units derived from a cyclic non-conjugated diene represented by the following general formula (III),
(C) one or more repeating units derived from a cyclic olefin represented by the following general formula (V):

[In the above general formula (I), R ³⁰⁰ represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms.]

[In the above general formula (III), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, R ⁶¹ to R ⁷⁶ as well as R ^a1 and R ^b1 may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, R ¹⁰⁴ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, t is a positive integer of 0 to 10, and R ⁷⁵ and R ⁷⁶ may be bonded to each other to form a monocycle or polycycle.]

[In the above general formula (V), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, R ⁶¹ to R ⁷⁸ as well as R ^a1 and R ^b1 may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and R ⁷⁵ to R ⁷⁸ may be bonded to each other to form a monocycle or multiple rings.]
[2]
The thermosetting cyclic olefin copolymer (m) further comprises a cyclic olefin (co)polymer (n) different from the thermosetting cyclic olefin copolymer (m),
The cyclic olefin (co)polymer (n) comprises at least one selected from a copolymer (n1) of ethylene or an α-olefin with a cyclic olefin (provided that the copolymer (n1) does not contain a repeating unit derived from a cyclic non-conjugated diene represented by the general formula (III)) and a ring-opening polymer (n2) of a cyclic olefin,
When the total amount of the thermosetting cyclic olefin copolymer (m) and the cyclic olefin (co)polymer (n) is taken as 100 mass%,
The content of the thermosetting cyclic olefin copolymer (m) is 5% by mass or more and 95% by mass or less,
The adhesive resin composition according to [1], wherein the content of the cyclic olefin (co)polymer (n) is 5% by mass or more and 95% by mass or less.
[3]
The adhesive resin composition according to [1] or [2], further comprising a binder resin.
[4]
The adhesive resin composition according to [3], wherein the binder resin contains a modified polyolefin.
[5]
When the total mole number of repeating units in the thermosetting cyclic olefin copolymer (m) is taken as 100 mol %,
The content of the repeating unit (A) derived from the olefin is 10 mol % or more and 90 mol % or less,
The adhesive resin composition according to any one of [1] to [4], wherein the content of the repeating unit (B) derived from the cyclic non-conjugated diene is 1 mol % or more and 40 mol % or less, and the content of the repeating unit (C) derived from the cyclic olefin is 1 mol % or more and 50 mol % or less.
[6]
The adhesive resin composition according to any one of [1] to [5], wherein the cyclic non-conjugated diene constituting the repeating unit (B) derived from the cyclic non-conjugated diene includes 5-vinyl-2-norbornene.
[7]
The adhesive resin composition according to any one of [1] to [6], wherein the cyclic olefin constituting the cyclic olefin-derived repeating unit (C) includes at least one selected from the group consisting of tetracyclo[ ^{4.4.0.12,5.17,10} ]-3- ^dodecene and bicyclo[2.2.1]-2-heptene.
[8]
A crosslinked product of the adhesive resin composition according to any one of [1] to [7].
[9]
A thermosetting adhesive film or sheet comprising the adhesive resin composition according to any one of [1] to [7] or the crosslinked product according to [8].
[10]
A laminate obtained by laminating the thermosetting adhesive film or sheet according to [9] on a substrate.
[11]
A circuit board comprising an electrical insulating layer containing the adhesive resin composition according to any one of [1] to [7] or the crosslinked body according to [8], and a conductor layer provided on the electrical insulating layer.
[12]
A circuit board comprising an electrical insulating layer, a conductor layer, and an adhesive layer for bonding the electrical insulating layer and the conductor layer, wherein the adhesive layer comprises the adhesive resin composition according to any one of [1] to [7] or the crosslinked body according to [8].
[13]
An electronic device comprising the circuit board according to [11] or [12].

The present invention provides an adhesive resin composition that has low dielectric properties and improved transparency in the high frequency range.

Hereinafter, the present invention will be described based on an embodiment. In the embodiment, "A to B" indicating a numerical range means A or more and B or less unless otherwise specified.
In addition, in this specification, the term "cyclic olefin (co)polymer" means at least one polymer selected from the group consisting of homopolymers of cyclic olefins and copolymers of cyclic olefins and monomer components other than cyclic olefins.

[Adhesive resin composition]
The adhesive resin composition of the present embodiment contains a thermosetting cyclic olefin copolymer (m), a crosslinking agent (X), and an antioxidant (Y).

Each ingredient is explained in detail below.

[Thermosetting cyclic olefin copolymer (m)]
The thermosetting cyclic olefin copolymer (m) of the present embodiment contains (A) one or more olefin-derived repeating units represented by the following general formula (I), (B) one or more cyclic non-conjugated diene-derived repeating units represented by the following general formula (III), and (C) one or more cyclic olefin-derived repeating units represented by the following general formula (V).

In the above general formula (I), R ³⁰⁰ represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms.

In the above general formula (III), u is 0 or 1, v is 0 or a positive integer, preferably an integer of 0 to 2, more preferably 0 or 1, w is 0 or 1, R ⁶¹ to R ⁷⁶ as well as R ^a1 and R ^b1 may be the same or different from one another and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, R ¹⁰⁴ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, t is a positive integer of 0 to 10, and R ⁷⁵ and R ⁷⁶ may be bonded to each other to form a monocycle or polycycle.

In the above general formula (V), u is 0 or 1, v is 0 or a positive integer, preferably an integer of 0 to 2, more preferably 0 or 1, w is 0 or 1, R ⁶¹ to R ⁷⁸ as well as R ^a1 and R ^b1 may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and R ⁷⁵ to R ⁷⁸ may be bonded to each other to form a monocycle or polycycle.

In the thermosetting cyclic olefin copolymer (m), when the total number of moles of repeating units in the thermosetting cyclic olefin copolymer (m) is taken as 100 mol%,
The content of the repeating unit (A) derived from an olefin is preferably 10 mol% or more and 90 mol% or less, more preferably 20 mol% or more and 85 mol% or less, even more preferably 30 mol% or more and 80 mol% or less, even more preferably 40 mol% or more and 70 mol% or less, even more preferably 50 mol% or more and 70 mol% or less, and even more preferably 55 mol% or more and 65 mol% or less,
The content of the repeating unit (B) derived from a cyclic non-conjugated diene is preferably 1 mol% or more and 40 mol% or less, more preferably 5 mol% or more and 40 mol% or less, even more preferably 5 mol% or more and 35 mol% or less, and still more preferably 7 mol% or more and 30 mol% or less,
The content of the repeating unit (C) derived from a cyclic olefin is preferably from 1 mol % to 50 mol %, more preferably from 3 mol % to 40 mol %, and further preferably from 10 mol % to 35 mol %.
When the content of each repeating unit in the thermosetting cyclic olefin copolymer (m) is within the above range, the crosslinked body obtained from the adhesive resin composition has improved dielectric properties and is also excellent in adhesion and heat resistance. Furthermore, a crosslinked body (Q) having excellent mechanical properties, dielectric properties, transparency and gas barrier properties can be obtained. In other words, a crosslinked body (Q) having a good balance of these physical properties can be obtained.

The olefin monomer, which is one of the copolymerization raw materials for the thermosetting cyclic olefin copolymer (m), is a monomer that undergoes addition copolymerization to give the skeleton represented by the above formula (I), and is an olefin represented by the following general formula (Ia).

In the above general formula (Ia), R ³⁰⁰ represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms. Examples of the olefin represented by general formula (Ia) include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. From the viewpoint of obtaining a crosslinked product (Q) having better heat resistance, mechanical properties, dielectric properties, transparency and gas barrier properties, among these, one or two types selected from the group consisting of ethylene and propylene are preferred, and ethylene is more preferred. Two or more types of olefin monomers represented by the above formula (Ia) may be used.

The cyclic non-conjugated diene monomer, which is one of the copolymerization raw materials for the thermosetting cyclic olefin copolymer (m), undergoes addition copolymerization to form the structural unit represented by the above formula (III). Specifically, a cyclic non-conjugated diene represented by the following general formula (IIIa), which corresponds to the above general formula (III), is used.

In the above general formula (IIIa), u is 0 or 1, v is 0 or a positive integer, preferably an integer of 0 to 2, more preferably 0 or 1, w is 0 or 1, R ⁶¹ to R ⁷⁶ as well as R ^a1 and R ^b1 may be the same or different from each other and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, R ¹⁰⁴ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, t is a positive integer of 0 to 10, and R ⁷⁵ and R ⁷⁶ may be bonded to each other to form a monocycle or polycycle.

The cyclic non-conjugated diene represented by the above general formula (IIIa) is not limited, but examples thereof include cyclic non-conjugated dienes represented by the following chemical formulas: Of these, one selected from the group consisting of 5-vinyl-2-norbornene and 8-vinyl-9-methyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]-3-dodecene is preferred, and 5-vinyl-2-norbornene is more preferred.

The cyclic non-conjugated diene represented by the above general formula (IIIa) can also be specifically represented by the following general formula (IIIb):

In the general formula (IIIb), n is an integer of 0 to 10, R ₁ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ₂ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

The thermosetting cyclic olefin copolymer (m) of this embodiment is characterized in that it contains a structural unit derived from a cyclic non-conjugated diene represented by general formula (III) and thus has a double bond in the side chain portion, i.e., in the portion other than the main chain of the copolymer.

The cyclic olefin monomer, which is one of the copolymerization raw materials for the thermosetting cyclic olefin copolymer (m), undergoes addition copolymerization to form the structural unit represented by the above formula (V). Specifically, a cyclic olefin monomer represented by the following general formula (Va) corresponding to the above general formula (V) is used.

In the above general formula (Va), u is 0 or 1, v is 0 or a positive integer, preferably an integer of 0 to 2, more preferably 0 or 1, w is 0 or 1, R ⁶¹ to R ⁷⁸ as well as R ^a1 and R ^b1 may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and R ⁷⁵ to R ⁷⁸ may be bonded to each other to form a monocycle or polycycle.

As specific examples of the cyclic olefin represented by the above general formula (Va), the compounds described in WO 2006/118261 can be used.
As the cyclic olefin represented by the above general formula (Va), at least one selected from the group consisting of bicyclo[2.2.1]-2-heptene (also called ^norbornene ) and tetracyclo[ ^{4.4.0.12,5.17,10} ]-3-dodecene (also called tetracyclododecene) is preferred. These cyclic olefins have a rigid ring structure, so that the elastic modulus of the crosslinked body consisting of the thermosetting cyclic olefin copolymer (m) and the adhesive resin composition is easily maintained, and they have the advantage of being easy to control the crosslinking because they do not contain a heterogeneous double bond structure.

By using the olefin monomer represented by the general formula (Ia) and the cyclic olefin represented by the general formula (Va) as the copolymerization components, the solubility of the thermosetting cyclic olefin copolymer (m) in a solvent is improved, resulting in good moldability and improved product yield.

The thermosetting cyclic olefin copolymer (m) may be composed of (A) one or more olefin-derived repeating units represented by general formula (I), (B) one or more cyclic olefin-derived repeating units represented by general formula (III), and (C) one or more cyclic olefin-derived repeating units represented by general formula (V), as well as repeating units derived from a cyclic olefin other than the cyclic non-conjugated diene represented by general formula (III) and the cyclic olefin represented by general formula (V), and/or a chain polyene.
In this case, as the copolymerization raw materials for the thermosetting cyclic olefin copolymer (m), in addition to the olefin monomer represented by the general formula (Ia), the cyclic non-conjugated diene monomer represented by the general formula (IIIa), and the cyclic olefin monomer represented by the general formula (Va), a cyclic olefin monomer other than the cyclic non-conjugated diene monomer represented by the general formula (IIIa) and the cyclic olefin monomer represented by the general formula (Va), and/or a chain polyene monomer can be used.
As such a cyclic olefin monomer and a chain polyene monomer, a cyclic olefin represented by the following general formula (VIa) or (VIIa) or a chain polyene represented by the following general formula (VIIIa) can be used. Two or more different types of these cyclic olefins and chain polyenes can be used.

In general formula (VIa), x and d each represent 0 or an integer of 1 or more, preferably an integer of 0 or more and 2 or less, more preferably 0 or 1; y and z each represent 0, 1, or 2; R ⁸¹ to R ⁹⁹ may be the same or different from one another and represent a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group which is an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or an alkoxy group; the carbon atom to which R ⁸⁹ and R ⁹⁰ are bonded may be bonded directly to the carbon atom to which R ⁹³ is bonded or the carbon atom to which R ⁹¹ is bonded may be bonded via an alkylene group having 1 to 3 carbon atoms; and when y=z=0, R ⁹⁵ and R ⁹² , or R ⁹⁵ and R ⁹⁹ may be bonded to each other to form a monocyclic or polycyclic aromatic ring.

In formula (VIIa), R ¹⁰⁰ and R ¹⁰¹ may be the same or different and each represent a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and f is in the range of 1≦f≦18.

In general formula (VIIIa), R ²⁰¹ to R ²⁰⁶ may be the same or different and each represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and P represents a linear or branched hydrocarbon group having 1 to 20 carbon atoms, which may contain a double bond and/or a triple bond.

Specific examples of the cyclic olefins represented by general formula (VIa) and general formula (VIIa) include the compounds described in paragraphs 0037 to 0063 of WO 2006/118261.

Specific examples of the chain polyene represented by the general formula (VIIIa) include 1,4-hexadiene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4,5-dimethyl-1,4-hexadiene, 7-methyl-1,6-octadiene, DMDT, 1,3-butadiene, and 1,5-hexadiene. Cyclizable polyenes cyclized from polyenes such as 1,3-butadiene and 1,5-hexadiene may also be used.

When the thermosetting cyclic olefin copolymer (m) contains a structural unit derived from a chain polyene represented by the above general formula (VIIIa), or a structural unit derived from a cyclic non-conjugated diene represented by the general formula (III) and a cyclic olefin other than the cyclic olefin represented by the general formula (V) [e.g., general formula (VIa), general formula (VIIa)], the content of the structural unit is preferably 0.1 to 100 mol%, more preferably 0.1 to 50 mol%, based on the total molar number of repeating units derived from one or more olefins represented by the above general formula (I), repeating units derived from one or more cyclic non-conjugated dienes represented by the above general formula (III), and repeating units derived from one or more cyclic olefins represented by the above general formula (V).

By using the olefin monomer represented by the general formula (I), the cyclic olefin represented by the general formula (VIa) or (VIIa), and the linear polyene represented by the general formula (VIIIa) as the copolymerization components, the solubility of the thermosetting cyclic olefin copolymer (m) in a solvent is further improved, resulting in good moldability and improved product yield. Among these, the cyclic olefin represented by the general formula (VIa) or (VIIa) is preferred. These cyclic olefins have a rigid ring structure, so that the elastic modulus of the crosslinked body consisting of the thermosetting cyclic olefin copolymer (m) and the adhesive resin composition is easily maintained, and since they do not contain a heterogeneous double bond structure, they have the advantage of being easy to control the crosslinking.

The comonomer content and glass transition point (Tg) of the thermosetting cyclic olefin copolymer (m) can be controlled by adjusting the monomer charging ratio according to the intended application. The Tg of the thermosetting cyclic olefin copolymer (m) is, for example, 300°C or less, preferably 250°C or less, more preferably 200°C or less, even more preferably 170°C or less, and even more preferably 150°C or less. When the Tg is equal to or less than the above upper limit, the melt moldability of the thermosetting cyclic olefin copolymer (m) and its solubility in a solvent when it is made into a varnish are improved.

The intrinsic viscosity [η] of the thermosetting cyclic olefin copolymer (m) measured in decahydronaphthalene at 135°C is preferably in the range of 0.10 to 15 dl/g, more preferably 0.10 to 5 dl/g, and even more preferably 0.15 to 3 dl/g. When the intrinsic viscosity [η] is equal to or less than the upper limit, the moldability is improved. When the intrinsic viscosity [η] is equal to or more than the lower limit, the heat resistance and mechanical properties of the crosslinked body (Q) obtained by crosslinking the adhesive resin composition are improved.
The intrinsic viscosity [η] of the thermosetting cyclic olefin copolymer (m) can be controlled by the polymerization conditions such as the polymerization catalyst, co-catalyst, amount of _H2 added, and polymerization temperature.

[Method for producing thermosetting cyclic olefin copolymer (m)]
The thermosetting cyclic olefin copolymer (m) according to this embodiment can be produced, for example, according to the method for producing a cyclic olefin copolymer described in paragraphs 0075 to 0219 of WO 2012/046443. Details are omitted here.

The adhesive resin composition of the present embodiment contains a crosslinking agent (X). The adhesive resin composition can form a crosslinked body (Q) described later by crosslinking the thermosetting cyclic olefin copolymer (m) in the adhesive resin composition with the crosslinking agent (X).
The content of the crosslinking agent (X) in the adhesive resin composition of this embodiment is, from the viewpoint of further improving the performance balance of the adhesiveness, heat resistance and mechanical properties of the crosslinked body (Q), preferably 0.02 parts by mass or more, more preferably 0.05 parts by mass or more, even more preferably 0.1 parts by mass or more, even more preferably 0.5 parts by mass or more, even more preferably 1.0 parts by mass or more, and even more preferably 1.5 parts by mass or more, relative to 100 parts by mass of the thermosetting cyclic olefin copolymer (m); from the viewpoint of further improving the dielectric properties of the crosslinked body (Q), it is preferably 20.0 parts by mass or less, more preferably 10.0 parts by mass or less, even more preferably 5.0 parts by mass or less, and even more preferably 3.5 parts by mass or less.
The crosslinking agent (X) may be one or two selected from the group consisting of radical initiators, sulfur, and hydrosilyl group-containing compounds. A method of crosslinking using electron beams or other radiation may also be used. From the viewpoint of improving the handling when crosslinking the adhesive resin composition, it is preferable that the crosslinking agent (X) contains a radical initiator.

The crosslinking with a radical initiator can be carried out in the same manner as in the case of polyolefins, that is, by blending a radical initiator with the adhesive resin composition and heating the composition to crosslink the composition.
The content of the radical initiator in the adhesive resin composition of this embodiment is, from the viewpoint of further improving the performance balance of the adhesiveness, heat resistance and mechanical properties of the crosslinked body (Q), preferably 0.02 parts by mass or more, more preferably 0.05 parts by mass or more, even more preferably 0.1 parts by mass or more, even more preferably 0.5 parts by mass or more, even more preferably 1.0 parts by mass or more, and even more preferably 1.5 parts by mass or more, relative to 100 parts by mass of the thermosetting cyclic olefin copolymer (m); from the viewpoint of further improving the dielectric properties of the crosslinked body (Q), it is preferably 20.0 parts by mass or less, more preferably 10.0 parts by mass or less, even more preferably 5.0 parts by mass or less, and even more preferably 3.5 parts by mass or less.

As the radical initiator, known thermal radical initiators, photoradical initiators, and combinations of these can be used. When using a thermal radical initiator among these radical initiators, from the viewpoint of storage stability, the 10-hour half-life temperature is, for example, 80°C or higher, preferably 120°C or higher. Examples of such initiators include dialkyl peroxides such as dicumyl peroxide, t-butylcumyl peroxide, 2,5-bis(t-butylperoxy)2,5-dimethylhexane, 2,5-bis(t-butylperoxy)2,5-dimethylhexyne-3, di-t-butyl peroxide, isopropylcumyl-t-butyl peroxide, and bis(α-t-butylperoxyisopropyl)benzene; 1,1-bis(t-butylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclododecane, n-butyl-4,4-bis(t-butylperoxy)valerate, and ethyl-3,3-bis(t-butylperoxy). ) butyrate, 3,3,6,6,9,9-hexamethyl-1,2,4,5-tetraoxycyclononane and other peroxyketals; bis(t-butylperoxy)isophthalate, t-butylperoxybenzoate, t-butylperoxyacetate and other peroxyesters; t-butyl hydroperoxide, t-hexyl hydroperoxide, cumin hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide and other hydroperoxides; 2,3-dimethyl-2,3-diphenylbutane and other bibenzyl compounds; 3,3,5,7,7-pentamethyl-1,2,4-trioxepane and other compounds.

Specific examples of the photoradical initiator among the radical initiators include benzoin alkyl ether, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzophenone, methylbenzoyl formate, isopropyl thioxanthone, and mixtures of two or more of these. In addition, a sensitizer can be used together with these photoradical initiators. Examples of sensitizers include carbonyl compounds such as anthraquinone, 1,2-naphthoquinone, 1,4-naphthoquinone, benzanthrone, p,p'-tetramethyldiaminobenzophenone, and chloranil, nitro compounds such as nitrobenzene, p-dinitrobenzene, and 2-nitrofluorene, aromatic hydrocarbons such as anthracene and chrysene, sulfur compounds such as diphenyl disulfide, and nitrogen compounds such as nitroaniline, 2-chloro-4-nitroaniline, 5-nitro-2-aminotoluene, and tetracyanoethylene.

When crosslinking is performed using sulfur or the like, a sulfur-based compound, and if necessary, a vulcanization accelerator and a vulcanization acceleration aid are blended into the adhesive resin composition, and the mixture is heated to carry out a crosslinking reaction. The blending amount of the sulfur-based compound is not particularly limited, but is preferably used in the range of 0.1 to 10 parts by mass, more preferably 0.3 to 5 parts by mass, per 100 parts by mass of the cyclic olefin copolymer (m) in order to efficiently proceed with the crosslinking reaction, improve the physical properties of the crosslinked product obtained, and from the standpoint of economy, etc. When a vulcanization accelerator or a vulcanization acceleration aid is used in combination, it is preferably used in the range of 0.1 to 20 parts by mass, more preferably 0.2 to 10 parts by mass.
Various known sulfur-based compounds can be used to cause the crosslinking reaction, and examples thereof include sulfur, sulfur monochloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, and selenium dimethyldithiocarbamate. Various vulcanization accelerators can also be used, including thiazole-based accelerators such as N-cyclohexyl-2-benzothiazole-sulfenamide, N-oxydiethylene-2-benzothiazole-sulfenamide, N,N-diisopropyl-2-benzothiazole-sulfenamide, 2-mercaptobenzothiazole, 2-(2,4-dinitrophenyl)mercaptobenzothiazole, 2-(2,6-diethyl-4-morpholinothio)benzothiazole, and benzothiazyl-disulfide; guanidine-based accelerators such as diphenylguanidine, triphenylguanidine, di-ortho-tolylguanidine, ortho-tolyl biguanide, and diphenylguanidine phthalate; acetaldehyde-aniline reactants; butyraldehyde-aniline condensates; aldehyde amines such as hexamethylenetetramine and acetaldehyde ammonia; and aldehyde-a ammonium-based compounds; imidazoline-based compounds such as 2-mercaptoimidazoline; thiourea-based compounds such as thiocarbanilide, diethylthiourea, dibutylthiourea, trimethylthiourea, and diortho thylthiourea; thiuram-based compounds such as tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, and dipentamethylenethiuram tetrasulfide; dithioacid salt-based compounds such as zinc dimethyldithiocarbamate, zinc diethylthiocarbamate, zinc di-n-butyldithiocarbamate, zinc ethylphenyldithiocarbamate, zinc butylphenyldithiocarbamate, sodium dimethyldithiocarbamate, selenium dimethyldithiocarbamate, and tellurium diethyldithiocarbamate; and xanthate-based compounds such as zinc dibutylxanthogenate. Examples of the vulcanization accelerator aid include metal oxide-based agents such as zinc oxide, active zinc white, zinc carbonate, complex zinc white, magnesium oxide, litharge, red lead, and basic lead carbonate; fatty acid-based agents such as stearic acid, oleic acid, lauric acid, and lead stearate; and organic amine/glycol-based agents such as triethanolamine and diethylene glycol.

The crosslinking agent (X) preferably contains a thermal radical initiator, and more preferably contains dicumyl peroxide. This improves storage stability and can further improve adhesion, dielectric properties, heat resistance, and mechanical properties.

When the adhesive resin composition is crosslinked with a radical initiator or sulfur, the crosslinking temperature is, for example, 100 to 300°C, preferably 120 to 250°C, and more preferably 120 to 220°C, and the temperature may be changed stepwise to perform crosslinking. If the temperature is equal to or higher than the lower limit, crosslinking can proceed sufficiently. If the temperature is equal to or lower than the upper limit, coloring of the crosslinked product obtained can be suppressed and the process can be simplified. For reference, polybutadiene, a typical double bond-containing polymer, generally cannot be crosslinked under the above conditions and requires crosslinking conditions at a high temperature such as 300°C.

When crosslinking is carried out using a radical initiator, crosslinking can be carried out in the presence of a crosslinking assistant.
The crosslinking aid is not limited, and examples thereof include oximes such as p-quinone dioxime and p,p'-dibenzoylquinone dioxime; acrylates or methacrylates such as ethylene dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, cyclohexyl methacrylate, acrylic acid/zinc oxide mixture, and allyl methacrylate; vinyl monomers such as divinylbenzene, vinyl toluene, and vinyl pyridine; allyl compounds such as hexamethylene diallyl nadimide, diaryl itaconate, diallyl phthalate, diallyl isophthalate, diallyl monoglycidyl isocyanurate, triallyl cyanurate, and triallyl isocyanurate; maleimide compounds such as N,N'-m-phenylene bismaleimide and N,N'-(4,4'-methylene diphenylene) dimaleimide; and cyclic non-conjugated dienes such as vinyl norbornene, ethylidene norbornene, and dicyclopentadiene.
Among these, allyl compounds such as hexamethylenediallylnadimide, diaryl itaconate, diallyl phthalate, diallyl isophthalate, diallyl monoglycidyl isocyanurate, triallyl cyanurate, and triallyl isocyanurate are preferred, and one or more selected from the group consisting of diallyl monoglycidyl isocyanurate, triallyl cyanurate, and triallyl isocyanurate are more preferred, and one or two selected from the group consisting of triallyl cyanurate and triallyl isocyanurate are even more preferred.
These crosslinking aids may be used alone or in combination.
When a crosslinking auxiliary is used, the content of the crosslinking auxiliary in the adhesive resin composition of this embodiment is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, and even more preferably 1.0 part by mass or more, relative to 100 parts by mass of the thermosetting cyclic olefin copolymer (m), and is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, and even more preferably 30 parts by mass or less.

The crosslinking reaction can be carried out by melting the mixture of the adhesive resin composition and the radical initiator, or by dissolving or dispersing the mixture in a solvent, or by volatilizing the solvent from the solution and forming the mixture into any shape, such as a film or coating, and then allowing the crosslinking reaction to proceed further.

When the reaction is carried out in a molten state, the mixture of raw materials is melt-kneaded and reacted using a kneading device such as a mixing roll, Banbury mixer, extruder, kneader, or continuous mixer. The crosslinking reaction can also be allowed to proceed further after molding using any method.

The adhesive resin composition of the present embodiment contains an antioxidant (Y).
The antioxidant (Y) preferably contains, for example, one or more selected from the group consisting of phenol-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, and thioether-based antioxidants, which can further improve the storage stability of the adhesive resin composition during storage and after it is made into a film.

Examples of phenol-based antioxidants include acrylate-based phenol compounds described in JP-A-63-179953 and JP-A-1-168643, such as 2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate and 2,4-di-t-amyl-6-(1-(3,5-di-t-amyl-2-hydroxyphenyl)ethyl)phenyl acrylate; 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, and octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate. , 2,2'-methylene-bis(4-methyl-6-t-butylphenol), 4,4'-butylidene-bis(6-t-butyl-m-cresol), 4,4'-thiobis(3-methyl-6-t-butylphenol), bis(3-cyclohexyl-2-hydroxy-5-methylphenyl)methane, 3,9-bis(2-(3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy)-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-trimethyl-2-phenylprop ... tyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, tetrakis(methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenylpropionate)methane [i.e., pentaerythritol tetrakis(3-(3,5-di-t-butyl-4-hydroxyphenylpropionate)], pentaerythritol tetrakis[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, triethylene glycol bis(3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate), tocopherol, etc. At least one selected from the group consisting of alkyl-substituted phenolic compounds; triazine group-containing phenolic compounds such as 6-(4-hydroxy-3,5-di-t-butylanilino)-2,4-bisoctylthio-1,3,5-triazine, 6-(4-hydroxy-3,5-dimethylanilino)-2,4-bisoctylthio-1,3,5-triazine, 6-(4-hydroxy-3-methyl-5-t-butylanilino)-2,4-bisoctylthio-1,3,5-triazine, and 2-octylthio-4,6-bis-(3,5-di-t-butyl-4-oxyanilino)-1,3,5-triazine; etc. Among these, at least one selected from the group consisting of acrylate-based phenolic compounds and alkyl-substituted phenolic compounds is preferred, and alkyl-substituted phenolic compounds are more preferred.

Examples of phosphorus-based antioxidants include triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, tris(nonylphenyl) phosphite, tris(dinonylphenyl) phosphite, tris(2,4-di-t-butylphenyl) phosphite, tris(2-t-butyl-4-methylphenyl) phosphite, tris(cyclohexylphenyl) phosphite, 2,2-methylenebis(4,6-di-t-butylphenyl) phosphite, Monophosphite compounds such as octyl phosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(3,5-di-t-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene; 4,4'-butylidene-bis(3-methyl-6-t-butylphenyl-di-tridecyl) 4,4'-isopropylidene-bis(phenyl-di-alkyl(C12-C15)phosphite), 4,4'-isopropylidene-bis(diphenyl monoalkyl(C12-C15)phosphite), 1,1,3-tris(2-methyl-4-di-tridecylphosphite-5-t-butylphenyl)butane, tetrakis(2,4-di-t-butylphenyl)-4,4'-biphenylene diphosphite, cyclic neopentane tetrayl bis(isodecyl phosphite), cyclic neopentane tetrayl bis(nonylphenyl phosphite), cyclic neopentane tetrayl bis(2,4-di-t-butylphenyl phosphite), cyclic neopentane tetrayl bis(2,4-dimethylphenyl phosphite), cyclic neopentane tetrayl bis(2,6-di-t-butylphenyl phosphite), and other diphosphite compounds. Among these, monophosphite compounds are preferred, and at least one selected from the group consisting of tris(nonylphenyl)phosphite, tris(dinonylphenyl)phosphite, tris(2,4-di-t-butylphenyl)phosphite, etc. is more preferred.

Examples of the sulfur-based antioxidant include at least one selected from the group consisting of dilauryl 3,3-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3-thiodipropionate, laurylstearyl 3,3-thiodipropionate, pentaerythritol-tetrakis-(β-lauryl-thio-propionate), and 3,9-bis(2-dodecylthioethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane.
Examples of the thioether-based antioxidant include at least one selected from the group consisting of tetrakis{methylene-3-(laurylthio)propionate}methane, bis[methyl-4-{3-n-alkyl(C12 or C14)thiopropioniodyl}-5-t-butylphenyl]sulfide, and ditridecyl-3,3′-thiodipropionate.

From the viewpoint of further improving storage stability, the content of the antioxidant (Y) in the adhesive resin composition of this embodiment is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, even more preferably 0.01% by mass or more, even more preferably 0.02% by mass or more, and is preferably 1.0% by mass or less, more preferably 0.50% by mass or less, even more preferably 0.30% by mass or less, even more preferably 0.20% by mass or less, even more preferably 0.10% by mass or less, based on the entire adhesive resin composition excluding the solvent.

[Cyclic olefin (co)polymer (n)]
The adhesive resin composition of the present embodiment may further contain a cyclic olefin (co)polymer (n) different from the thermosetting cyclic olefin copolymer (m).
Specifically, the cyclic olefin (co)polymer (n) contains at least one selected from a copolymer (n1) of ethylene or an α-olefin with a cyclic olefin and a ring-opening polymer (n2) of a cyclic olefin. By containing the thermosetting cyclic olefin copolymer (m) and the cyclic olefin (co)polymer (n), the adhesive resin composition of the present embodiment can further improve the adhesiveness and dielectric properties of the crosslinked body obtained by crosslinking the adhesive resin composition.
Here, the copolymer (n1) does not contain a repeating unit derived from the cyclic non-conjugated diene represented by the general formula (III). In this embodiment, the fact that the copolymer (n1) does not contain a repeating unit derived from the cyclic non-conjugated diene represented by the general formula (III) means that the content of the repeating unit derived from the cyclic non-conjugated diene represented by the general formula (III) is 0.05 mol% or less, when the total mole number of the repeating units in the copolymer (n1) is 100 mol%.
The cyclic olefin (co)polymer (n) is preferably a copolymer (n1) of ethylene or an α-olefin and a cyclic olefin, since it can further improve the dielectric properties of the crosslinked body obtained by crosslinking the adhesive resin composition.

In the adhesive resin composition of the present embodiment, the content of the thermosetting cyclic olefin copolymer (m) is, when the total amount of the thermosetting cyclic olefin copolymer (m) and the cyclic olefin (co)polymer (n) is taken as 100 mass%, from the viewpoint of improving the dielectric properties of the crosslinked body obtained by crosslinking the adhesive resin composition, preferably 5 mass% or more, more preferably 10 mass% or more, even more preferably 20 mass% or more, even more preferably 30 mass% or more, even more preferably 50 mass% or more, even more preferably 60 mass% or more, and preferably 95 mass% or less, more preferably 90 mass% or less, even more preferably 85 mass% or less, even more preferably 80 mass% or less, even more preferably 75 mass% or less.
When the total amount of the thermosetting cyclic olefin copolymer (m) and the cyclic olefin (co)polymer (n) is taken as 100 mass%, from the viewpoint of improving the dielectric properties of the crosslinked body obtained by crosslinking the adhesive resin composition, the content of the cyclic olefin (co)polymer (n) is preferably 5 mass% or more, more preferably 10 mass% or more, even more preferably 15 mass% or more, even more preferably 20 mass% or more, even more preferably 25 mass% or more, and is preferably 95 mass% or less, more preferably 90 mass% or less, even more preferably 80 mass% or less, even more preferably 70 mass% or less, even more preferably 50 mass% or less, and even more preferably 40 mass% or less.

The copolymer (n1) of ethylene or α-olefin and cyclic olefin can include, for example, the polymers described in paragraphs 0030 to 0123 of WO 2008/047468.

For example, it is a polymer having an alicyclic structure in at least a portion of the repeating structural units (hereinafter, simply referred to as a "polymer having an alicyclic structure"), and it is sufficient that at least a portion of the repeating units of the polymer has an alicyclic structure. Specifically, it is preferable to include a polymer having one or more structures represented by the following general formula (3).

(In formula (3), x and y represent copolymerization ratios and are real numbers satisfying 0/100≦y/x≦95/5. x and y are on a molar basis.
n represents the number of substituents Q and is a real number satisfying 0≦n≦2.
R ^a is a (2+n) valent group selected from the group consisting of hydrocarbon groups having 2 to 20 carbon atoms.
R ^b is a hydrogen atom or a monovalent group selected from the group consisting of hydrocarbon groups having 1 to 10 carbon atoms.
R ^c is a tetravalent group selected from the group consisting of hydrocarbon groups having 2 to 10 carbon atoms.
Q is COOR ^d (R ^d is a hydrogen atom or a monovalent group selected from the group consisting of hydrocarbon groups having 1 to 10 carbon atoms).
Each of R ^a , R ^b , R ^c and Q may be one type or two or more types in any ratio.

In the above general formula (3), R ^a is preferably one or more divalent groups selected from hydrocarbon groups having 2 to 12 carbon atoms, more preferably a divalent group represented by the following general formula (7) when n = 0, and most preferably a divalent group in the following general formula (7) where p is 0 or 1. The structure of R ^a may be used alone or in combination of two or more types.

In formula (7), p is an integer from 0 to 2.

The copolymer (n1) of ethylene or an α-olefin and a cyclic olefin is a cyclic olefin-based copolymer represented by the following general formula (4). For example, it is composed of a structural unit (A) derived from ethylene or a linear or branched α-olefin having 3 to 30 carbon atoms, and a structural unit (B) derived from a cyclic olefin.

In formula (4), R ^a is a divalent group selected from the group consisting of hydrocarbon groups having 2 to 20 carbon atoms.
R ^b is a hydrogen atom or a monovalent group selected from the group consisting of hydrocarbon groups having 1 to 10 carbon atoms.
Each of R ^a and R ^b may be one type, or two or more types in any ratio.
x and y each represent a copolymerization ratio and are real numbers satisfying 5/95≦y/x≦95/5, preferably 50/50≦y/x≦95/5, and more preferably 55/45≦y/x≦80/20. x and y are on a molar basis.

The copolymer (n1) of ethylene or α-olefin and cyclic olefin is preferably a copolymer of ethylene and cyclic olefin, and the cyclic olefin is preferably one or more selected from the group consisting of bicyclo[2.2.1]-2-heptene, tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene, 1,4-methano-1,4,4a,9a-tetrahydrofluorene, cyclopentadiene-benzyne adduct and cyclopentadiene-acenaphthylene adduct, and more preferably at least one selected from bicyclo[2.2.1]-2-heptene and tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene.
The copolymer (n1) of ethylene or α-olefin and cyclic olefin may be a polymer having one or more structures represented by the above general formula (3) or a polymer obtained by subjecting a cyclic olefin copolymer represented by the above general formula (4) to a hydrogenation treatment.

The copolymer (n1) of ethylene or α-olefin and cyclic olefin is also preferably a copolymer of an α-olefin and a cyclic olefin having 4 to 12 carbon atoms. The copolymer of an α-olefin and a cyclic olefin having 4 to 12 carbon atoms can include, for example, the polymers described in paragraphs 0056 to 0070 of WO 2015/178145.
Examples of the cyclic olefin constituting the copolymer of an α-olefin having 4 to 12 carbon atoms and a cyclic olefin include norbornene and substituted norbornene, and norbornene is preferred. The above cyclic olefins can be used alone or in combination of two or more.

The above-mentioned substituted norbornene is not limited, and examples of the substituents of the substituted norbornene include halogen atoms and monovalent or divalent hydrocarbon groups. Specific examples of the substituted norbornene include those represented by the following general formula (A).

（式中、Ｒ^１～Ｒ^１２は、それぞれ同一でも異なっていてもよく、水素原子、ハロゲン原子、及び、炭化水素基からなる群より選ばれるものであり、Ｒ^９とＲ^１０、Ｒ^１１とＲ^１２は、一体化して２価の炭化水素基を形成してもよく、Ｒ^９又はＲ^１０と、Ｒ^１１又はＲ^１２とは、互いに環を形成していてもよい。また、ｎは、０又は正の整数を示し、ｎが２以上の場合には、Ｒ^５～Ｒ^８は、それぞれの繰り返し単位の中で、それぞれ同一でも異なっていてもよい。ただし、ｎ＝０の場合、Ｒ^１～Ｒ^４及びＲ^９～Ｒ^１２の少なくとも１個は、水素原子ではない。）

(In the formula, R ¹ to R ¹² may be the same or different and are selected from the group consisting of hydrogen atoms, halogen atoms, and hydrocarbon groups; R ⁹ and R ¹⁰ , and R ¹¹ and R ¹² may be united to form a divalent hydrocarbon group; R ⁹ or R ¹⁰ and R ¹¹ or R ¹² may form a ring together; n represents 0 or a positive integer; when n is 2 or greater, R ⁵ to R ⁸ may be the same or different in each repeating unit; however, when n=0, at least one of R ¹ to R ⁴ and R ⁹ to R ¹² is not a hydrogen atom.)

The substituted norbornene represented by the general formula (A) will be described below. R ¹ to R ¹² in the general formula (A) may be the same or different and are each selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group.

Specific examples of R ¹ to R ⁸ include a hydrogen atom; a halogen atom such as fluorine, chlorine, or bromine; and an alkyl group having 1 to 20 carbon atoms, and these may be different from each other, may be partially different, or may all be the same.

Specific examples of R ⁹ to R ¹² include a hydrogen atom; a halogen atom such as fluorine, chlorine, or bromine; an alkyl group having from 1 to 20 carbon atoms; a cycloalkyl group such as a cyclohexyl group; a substituted or unsubstituted aromatic hydrocarbon group such as a phenyl group, a tolyl group, an ethylphenyl group, an isopropylphenyl group, a naphthyl group, or an anthryl group; a benzyl group, a phenethyl group, or another aralkyl group in which an aryl group is substituted on an alkyl group; and the like, which may be different from each other, may be partially different, or may be the same as one another.

Specific examples of the divalent hydrocarbon group formed by combining R ⁹ and R ¹⁰ , or R ¹¹ and R ¹² together, include alkylidene groups such as an ethylidene group, a propylidene group, and an isopropylidene group.

When ^R9 or ^R10 and ^R11 or ^R12 form a ring together, the ring formed may be a monocyclic or polycyclic ring, a polycyclic ring having a bridge, a ring having a double bond, or a ring consisting of a combination of these rings. These rings may have a substituent such as a methyl group.

Specific examples of the substituted norbornene represented by the general formula (A) are 5-methyl-bicyclo[2.2.1]hept-2-ene, 5,5-dimethyl-bicyclo[2.2.1]hept-2-ene, 5-ethyl-bicyclo[2.2.1]hept-2-ene, 5-butyl-bicyclo[2.2.1]hept-2-ene, 5-ethylidene-bicyclo[2.2.1]hept-2-ene, 5-hexyl-bicyclo[2.2 .1]hept-2-ene, 5-octyl-bicyclo[2.2.1]hept-2-ene, 5-octadecyl-bicyclo[2.2.1]hept-2-ene, 5-methylidene-bicyclo[2.2.1]hept-2-ene, 5-vinyl-bicyclo[2.2.1]hept-2-ene, 5-propenyl-bicyclo[2.2.1]hept-2-ene, and other bicyclic olefins; tricyclo[4.3.0.1]hept-2-ene, 5-octyl-bicyclo[2.2.1]hept-2-ene, 5-octadecyl-bicyclo[2.2.1]hept-2-ene, 5-methylidene-bicyclo[2.2.1]hept-2-ene, 5-vinyl-bicyclo[2.2.1]hept-2-ene, 5-propenyl-bicyclo[2.2.1]hept-2-ene, and other bicyclic olefins; tricyclo ^[ 4.4.0.1 2,5 ] undeca-3,7-diene (common name: dicyclopentadiene), tricyclo[4.3.0.1 ^2,5 ] deca-3-ene; tricyclo[4.4.0.1 ^2,5 ] undeca-3,7-diene or tricyclo[4.4.0.1 ^2,5 ] undeca-3,8-diene or their partial hydrogenated products (or an adduct of cyclopentadiene and cyclohexene), tricyclo[4.4.0.1 ^2,5 ] undec-3-ene; three-ring cyclic olefins such as 5-cyclopentyl-bicyclo[2.2.1]hept-2-ene, 5-cyclohexyl-bicyclo[2.2.1]hept-2-ene, 5-cyclohexenylbicyclo[2.2.1]hept-2-ene, and 5-phenyl-bicyclo[2.2.1]hept-2-ene; tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene (also simply called tetracyclododecene), 8-methyltetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethyltetracyclo[ ^4.4.0.1 2,5 . 1 ^7,10 ] dodec-3-ene, and 8-methylidenetetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3 ^- ene, 8-ethylidenetetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-vinyltetracyclo[4,4.0.1 2,5 . 1 7,10 ] dodec-3-ene ^, 8-propenyl-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene; 8-cyclopentyl-tetracyclo[ ^{4.4.0.1 2,5} . 1 ^7,10 ] dodec-3-ene, 8-cyclohexyl-tetracyclo[4.4.0.1 2,5 . ^{1 7,10} ] dodec-3-ene, 8-cyclohexenyl-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-phenyl-cyclopentyl-tetracyclo[4.4.0.1 ^2,5 . ^{1 7,10} ] dodec-3-ene; tetracyclo[7.4.1 ^3,6 . ^{0 1,9} . ^{0 2,7} ] tetradeca-4,9,11,13-tetraene (also called 1,4-methano-1,4,4a,9a-tetrahydrofluorene), tetracyclo[8.4.1 ^4,7 . ^{0 1,10} . 0 ^3,8 ] pentadeca-5,10,12,14-tetraene (also called 1,4-methano-1,4,4a,5,10,10a-hexahydroanthracene); pentacyclo[6.6.1.1 ^3,6 . ^{0 2,7} . 0 ^9,14 ]-4-hexadecene, pentacyclo[6.5.1.1 ^3,6 . 0 ^2,7 . ^{0 9,13} ]-4-pentadecene, pentacyclo[7.4.0.0 2,7 . 1 ^3,6 . 1 ^10,13 ]-4-pentadecene; heptacyclo[8.7.0.1 ^2,9 . 1 ^4,7 . 1 ^11,17 . 0 ^3,8 . 0 ^12,16 ]-5-eicosene, heptacyclo[8.7.0.1 ^2,9 . 0 ^3,8 . 1 ^4,7 . 0 ^{12,17 . 1 13,16} ]-14-eicosene; and polycyclic cyclic olefins such as cyclopentadiene tetramers.

Among these, alkyl-substituted norbornenes (e.g., bicyclo[2.2.1]hept-2-ene substituted with one or more alkyl groups) and alkylidene-substituted norbornenes (e.g., bicyclo[2.2.1]hept-2-ene substituted with one or more alkylidene groups) are preferred, and 5-ethylidene-bicyclo[2.2.1]hept-2-ene (common name: 5-ethylidene-2-norbornene, or simply ethylidenenorbornene) is more preferred.

Examples of the α-olefin having 4 to 12 carbon atoms constituting the copolymer of an α-olefin having 4 to 12 carbon atoms and a cyclic olefin include an α-olefin having 4 to 12 carbon atoms and an α-olefin having 4 to 12 carbon atoms having at least one substituent such as a halogen atom, and an α-olefin having 4 to 12 carbon atoms is preferred.

The α-olefin having 4 to 12 carbon atoms is not limited, but examples thereof include 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, and 1-dodecene. Of these, 1-hexene, 1-octene, and 1-decene are preferred.

In the copolymer of an α-olefin having 4 to 12 carbon atoms and a cyclic olefin according to the present embodiment, when the total amount of repeating units contained in the copolymer is taken as 100 mol %, the proportion of repeating units derived from an α-olefin having 4 to 12 carbon atoms is preferably 10 mol % or more and 90 mol % or less, more preferably 15 mol % or more and 80 mol % or less, and even more preferably 20 mol % or more and 70 mol % or less.
Furthermore, in the copolymer of an α-olefin having 4 to 12 carbon atoms and a cyclic olefin according to this embodiment, when the total number of repeating units contained in the copolymer is taken as 100 mol %, the proportion of repeating units derived from the cyclic olefin is preferably 10 mol % or more and 90 mol % or less, more preferably 20 mol % or more and 85 mol % or less, and even more preferably 30 mol % or more and 80 mol % or less.

The conditions for the polymerization process to obtain a copolymer of an α-olefin having 4 to 12 carbon atoms and a cyclic olefin are not limited as long as the desired copolymer is obtained, and known conditions can be used, with the polymerization temperature, polymerization pressure, polymerization time, etc. being adjusted as appropriate.

The cyclic olefin (co)polymer (n) may also contain a ring-opening polymer of a cyclic olefin (n2).
Examples of the ring-opened polymer (n2) of a cyclic olefin include a ring-opened polymer of a norbornene-based monomer, a ring-opened polymer of a norbornene-based monomer and another monomer capable of ring-opening copolymerization with the norbornene-based monomer, and hydrogenated products thereof.

Examples of norbornene monomers include bicyclo[2.2.1]hept-2-ene (common name: norbornene) and its derivatives (having a substituent on the ring), tricyclo[4.3.0 ^1,6 . 1 ^2,5 ]deca-3,7-diene (common name: dicyclopentadiene) and its derivatives, 7,8-benzotricyclo[4.3.0.1 ^2,5 ]deca-3-ene (common name: methanotetrahydrofluorene, also called 1,4-methano-1,4,4a,9a-tetrahydrofluorene) and its derivatives, tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene (common name: tetracyclododecene) and its derivatives, and the like.
Examples of the substituents substituted on the rings of these derivatives include alkyl groups, alkylene groups, vinyl groups, alkoxycarbonyl groups, and alkylidene groups. The substituents may be one or more. Examples of derivatives having a substituent on the ring include 8-methoxycarbonyl-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodec-3-ene, 8-methyl-8-methoxycarbonyl-tetracyclo[4.4.0.1 ^2,5 . ^{1 7,10} ]dodec-3-ene, and 8-ethylidene-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodec-3-ene.
These norbornene monomers may be used alone or in combination of two or more.

A ring-opening polymer of a norbornene-based monomer, or a ring-opening polymer of a norbornene-based monomer and another monomer capable of ring-opening copolymerization therewith, can be obtained by polymerizing the monomer components in the presence of a known ring-opening polymerization catalyst.
The ring-opening polymerization catalyst can include, for example, a catalyst consisting of a halide of a metal such as ruthenium or osmium, a nitrate or an acetylacetone compound, and a reducing agent; a catalyst consisting of a halide of a metal such as titanium, zirconium, tungsten, or molybdenum, or an acetylacetone compound, and an organoaluminum compound; and the like.
Examples of other monomers capable of ring-opening copolymerization with norbornene monomers include monocyclic olefin monomers such as cyclohexene, cycloheptene, and cyclooctene.

Hydrogenated ring-opening polymers of norbornene-based monomers and hydrogenated ring-opening polymers of norbornene-based monomers and other monomers capable of ring-opening copolymerization with them can be obtained, for example, by adding a known hydrogenation catalyst containing a transition metal such as nickel or palladium to a polymerization solution of the ring-opening polymer and hydrogenating the carbon-carbon unsaturated bonds.

In this embodiment, the cyclic olefin (co)polymer (n) may be used alone or in combination of two or more types.

PPE content When the adhesive resin composition of the present embodiment contains polyphenylene ether, the content of polyphenylene ether is preferably 0.5 mass% or less, more preferably 0.1 mass% or less, even more preferably 0.05 mass% or less, and even more preferably 0.01 mass% or less, when the adhesive resin composition as a whole excluding the solvent is 100 mass%. There is no lower limit for the content of polyphenylene ether, but it is, for example, 0 mass% or more, preferably 0 mass%. This can further improve the transparency of the adhesive resin composition.

[Binder resin]
The adhesive resin composition of the present embodiment may further contain a binder resin. By containing a binder resin, the shape stability of a film or sheet containing the adhesive resin composition and/or its crosslinked product is further improved.
When the adhesive resin composition of the present embodiment contains a binder resin, the content of the binder resin in the adhesive resin composition of the present embodiment is, relative to 100 parts by mass of the thermosetting cyclic olefin copolymer (m), preferably 10 parts by mass or more, more preferably 20 parts by mass or more, even more preferably 30 parts by mass or more, even more preferably 50 parts by mass or more, even more preferably 80 parts by mass or more, and preferably 500 parts by mass or less, more preferably 400 parts by mass or less, even more preferably 300 parts by mass or less, even more preferably 200 parts by mass or less, even more preferably 180 parts by mass or less, and even more preferably 150 parts by mass or less.

The binder resin preferably contains a modified polyolefin, and more preferably contains an acid-modified polyolefin, which will be described later.
The binder resins may be used alone or in combination of two or more.
When the adhesive resin composition of the present embodiment contains a modified polyolefin, the content of the modified polyolefin in the adhesive resin composition of the present embodiment is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, even more preferably 30 parts by mass or more, even more preferably 50 parts by mass or more, even more preferably 80 parts by mass or more, and preferably 500 parts by mass or less, more preferably 400 parts by mass or less, even more preferably 300 parts by mass or less, even more preferably 200 parts by mass or less, even more preferably 180 parts by mass or less, even more preferably 150 parts by mass or less, based on 100 parts by mass of the thermosetting cyclic olefin copolymer (m). When the content of the modified polyolefin is within this range, the shape stability of the film and sheet containing the adhesive resin composition and/or its crosslinked product is further improved.

Here, modified polyolefin is a general term for polyolefins to which functional groups have been introduced, such as acid-modified polyolefins in which an olefin resin precursor has been graft-modified with an acid or an acid anhydride. Examples of acid-modified polyolefins include those in which an olefin resin has been reacted with an unsaturated carboxylic acid or an unsaturated carboxylic anhydride (hereinafter sometimes referred to as "unsaturated carboxylic acid, etc.") to introduce a carboxyl group or a carboxylic anhydride group (graft modification).

An olefin resin is a polymer containing repeating units derived from an olefin monomer. The olefin resin may be a polymer consisting only of repeating units derived from an olefin monomer, or may be a polymer consisting of repeating units derived from an olefin monomer and repeating units derived from a monomer copolymerizable with the olefin monomer.

The olefin monomer is preferably an α-olefin having a carbon number of 2 to 8. These olefin monomers may be used alone or in combination of two or more.
Examples of monomers copolymerizable with olefin monomers include vinyl acetate, (meth)acrylic acid esters, styrene, etc. Here, "(meth)acrylic acid" is a general term for acrylic acid and methacrylic acid. These monomers copolymerizable with olefin monomers can be used alone or in combination of two or more.

Specific examples of olefin resins include very low density polyethylene, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene copolymer, olefin elastomer, ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, and ethylene-(meth)acrylic acid ester copolymer.

As described above, the modified polyolefin is an olefin resin graft-modified with an acid or an acid anhydride, etc., and is preferably a polyolefin containing structural units derived from an unsaturated carboxylic acid and/or a derivative thereof.
The unsaturated carboxylic acid to be reacted with the olefin resin is
Unsaturated carboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, tetrahydrophthalic acid, and aconitic acid;
Unsaturated carboxylic acid anhydrides such as maleic anhydride, itaconic anhydride, glutaconic anhydride, citraconic anhydride, aconitic anhydride, norbornene dicarboxylic anhydride, and tetrahydrophthalic anhydride;
Examples include:
These may be used alone or in combination of two or more.

The method of introducing the unsaturated carboxylic acid unit or the unsaturated carboxylic anhydride unit into the olefin resin is not limited. For example, the olefin resin and the unsaturated carboxylic acid are reacted by heating and melting the olefin resin at a temperature equal to or higher than the melting point of the olefin resin in the presence of a radical generator such as an organic peroxide or an azonitrile, or the olefin resin and the unsaturated carboxylic acid are dissolved in an organic solvent, and then heated and stirred in the presence of a radical generator to react with each other, thereby graft-copolymerizing the unsaturated carboxylic acid onto the olefin resin.

Commercially available modified polyolefins can also be used. Examples of commercially available products include Admer (registered trademark) (manufactured by Mitsui Chemicals, Inc.), Unistole (registered trademark) (manufactured by Mitsui Chemicals, Inc.), BondyRam (manufactured by Polyram Corporation), orevac (registered trademark) (manufactured by ARKEMA Corporation), and Modic (registered trademark) (manufactured by Mitsubishi Chemical Corporation).

[Silane coupling agent]
The adhesive resin composition of the present embodiment may further contain a silane coupling agent. By containing a silane coupling agent, the adhesive strength of the thermosetting adhesive film and sheet containing the adhesive resin composition and/or its crosslinked product is further improved.

Silane coupling agent can be known, and specifically, for example, silane coupling agent having one or more of the following substituents: epoxy group, amino group, (meth)acryloyl group, vinyl group, mercapto group, halogen group, imino group, isocyanate group, or ureido group.The hydrolyzable group bonded to silicon atom of silane coupling agent can be alkoxy group, alkylcarboxyl group, halogen group, etc., which may have two or more oxygen atoms.Among them, alkoxysilane compound having alkoxy group, which may have two or more oxygen atoms, is more preferred.
The silane coupling agents can be used alone or in combination of two or more.

Specific examples include silane coupling agents having an epoxy group, such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and γ-glycidoxypropylmethyldiethoxysilane;
silane coupling agents having an amino group, such as γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, bis[3-(trimethoxysilyl)propyl]amine, and bis[3-(trimethoxysilyl)propyl]ethylenediamine, or silane coupling agents consisting of hydrochlorides thereof;
Silane coupling agents having a (meth)acryloxy group, such as γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltris(methoxyethoxy)silane, and γ-acryloxypropyltrimethoxysilane;
Silane coupling agents having a vinyl group, such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris(β-methoxyethoxy)silane, styrylethyltrimethoxysilane, allyltriethoxysilane, and 3-(trimethoxysilyl)propyl methacrylate;
silane coupling agents having a mercapto group, such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, and γ-mercaptopropyltriethoxysilane;
Halogen-containing silane coupling agents, such as γ-chloropropyltrimethoxysilane and γ-chloropropyltriethoxysilane;
Silane coupling agents having an isocyanate group, such as γ-isocyanate propyl trimethoxy silane and γ-isocyanate propyl triethoxy silane;
Examples of the silane coupling agent include silane coupling agents having a ureido group, such as γ-(ureidopropyl)trimethoxysilane and γ-(ureidopropyl)triethoxysilane.

In particular, from the viewpoint of further improving the adhesive strength of the thermosetting adhesive film and sheet containing the adhesive resin composition and/or its crosslinked product, it is preferable to contain a silane coupling agent having a vinyl group, such as vinyltriethoxysilane, and it is more preferable to contain vinyltriethoxysilane.

When the adhesive resin composition of this embodiment contains a silane coupling agent, the content of the silane coupling agent in the adhesive resin composition of this embodiment is, from the viewpoint of keeping the adhesive strength in an appropriate range, preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, even more preferably 0.10 parts by mass or more, and preferably 1.0 parts by mass or less, more preferably 0.50 parts by mass or less, even more preferably 0.40 parts by mass or less, per 100 parts by mass of the thermosetting cyclic olefin copolymer (m).

The total content of the thermosetting cyclic olefin copolymer (m), the crosslinking agent (X) and the antioxidant (Y) in the adhesive resin composition of the present embodiment, when the entire adhesive resin composition excluding the solvent is taken as 100 mass%, is, from the viewpoint of further improving low dielectric properties and transparency in the high frequency range, preferably 10 mass% or more, more preferably 20 mass% or more, even more preferably 30 mass% or more, and even more preferably 35 mass% or more, and is preferably 100 mass% or less, more preferably 80 mass% or less, even more preferably 70 mass% or less, and even more preferably 60 mass% or less.
In addition, the total content of the thermosetting cyclic olefin copolymer (m), the cyclic olefin (co)polymer (n), the crosslinking agent (X), the antioxidant (Y), the binder resin and the silane coupling agent in the adhesive resin composition of this embodiment, when the entire adhesive resin composition excluding the solvent is taken as 100 mass%, is preferably 70 mass% or more, more preferably 80 mass% or more, even more preferably 90 mass% or more, still more preferably 95 mass% or more, and preferably 100 mass% or less, from the viewpoint of further improving the low dielectric properties and transparency in the high frequency range.

[Additive]
The adhesive resin composition of the present embodiment may further contain various additives depending on the purpose. The amount of the additives added is appropriately selected depending on the application within a range that does not impair the object of the present invention.
The additives include one or more additives selected from the group consisting of heat stabilizers, weather stabilizers, radiation resistance agents, plasticizers, lubricants, release agents, nucleating agents, friction and wear improvers, flame retardants, foaming agents, antistatic agents, colorants, antifogging agents, antiblocking agents, impact resistance agents, surface wetting improvers, fillers, hydrochloric acid absorbents, and metal deactivators.
For example, the heat stabilizers, light stabilizers, ultraviolet absorbers, radiation resistance agents, plasticizers, lubricants, release agents, nucleating agents, friction and wear improvers, flame retardants, foaming agents, antistatic agents, colorants, antifogging agents, antiblocking agents, impact resistance agents, surface wetting improvers, fillers, hydrochloric acid absorbers, metal deactivators, and the like described in paragraphs 0085 to 0120 of WO 2017/150218 can be used.

[varnish]
The adhesive resin composition of the present embodiment can be made into a varnish by mixing with a solvent.
Examples of the solvent include aromatic hydrocarbon solvents including benzene, toluene, and xylene, aliphatic hydrocarbon solvents including pentane, hexane, heptane, octane, nonane, and decane, alicyclic hydrocarbon solvents including cyclohexane, methylcyclohexane, and decahydronaphthalene, chlorinated hydrocarbon solvents including chlorobenzene, dichlorobenzene, trichlorobenzene, methylene chloride, chloroform, carbon tetrachloride, and tetrachloroethylene, 1-methyl-2-pyrrolidone, ethylene carbonate, propylene carbonate, γ-butyrolactone, N-methyl-2-pyrrolidone, propylene glycol monomethyl ether acetate, acetyl tributyl citrate, 2,4-pentadiene, dimethyl sulfoxide, n-alkyl adipate, 2,2, ketone-based solvents including 4-trimethyl-1,3-pentanediol diisobutyrate, 3-methoxy-3-methyl-1-butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, cyclohexanone, and the like; alcohols including benzyl alcohol, 1-butanol, 2-butanol, t-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-ethyl-1-hexanol, normal propyl alcohol, isopropyl alcohol, ethanol, and methanol, ether-based solvents including ethyl ether, ethylene glycol monomethyl ether, anisole, phenyl ether, dioxane, and tetrahydrofuran, and ester-based solvents including ethyl acetate and butyl acetate, and the like.
These solvents may be used alone or in combination of two or more. Among these, from the viewpoints of long-term stability, solubility, and versatility of the varnish, at least one selected from the group consisting of toluene, xylene, and cyclohexane is more preferred.

In this embodiment, the method for preparing the varnish may be carried out by any method, for example, including a step of mixing the adhesive resin composition and the solvent. The mixing of each component is not limited in order, and can be carried out in any manner, such as all at once or in portions. There is also no limitation on the apparatus for preparing the varnish, and any apparatus capable of stirring and mixing, such as a batch type or a continuous type, may be used. The temperature at which the varnish is prepared can be selected arbitrarily from room temperature to the boiling point of the solvent.
The reaction solution obtained when the thermosetting cyclic olefin copolymer (m) is obtained may be used as a solvent and the cyclic olefin (co)polymer (n) may be dissolved therein to prepare a varnish. Alternatively, the varnish may be prepared by mixing a varnish of the cyclic olefin (co)polymer (n) separately prepared with the reaction solution obtained when the thermosetting cyclic olefin copolymer (m) is obtained.

[Crosslinked product (Q)]
The crosslinked body (Q) can be obtained by crosslinking the thermosetting cyclic olefin copolymer (m) in the adhesive resin composition of this embodiment with a crosslinking agent (X).

[Film or sheet]
The adhesive resin composition or crosslinked body of this embodiment can be molded into a thermosetting adhesive film or sheet and used for various applications. Various known methods can be applied to the method of forming a thermosetting adhesive film or sheet using the adhesive resin composition or crosslinked body of this embodiment. For example, a method of forming the adhesive resin composition by applying a varnish-like adhesive resin composition onto a supporting substrate such as a thermoplastic resin film, drying, and then performing a heat treatment or the like to crosslink the adhesive resin composition can be mentioned. The method of applying the varnish-like adhesive resin composition to the supporting substrate is not limited, and examples thereof include application using a spin coater, application using a spray coater, and application using a bar coater.

[Laminate]
The thermosetting adhesive film or sheet according to the present embodiment can be laminated on a substrate and used for various applications as a laminate. Various known methods can be used as a method for forming the laminate according to the present embodiment.
For example, a laminate can be produced by laminating the thermosetting adhesive film or sheet produced by the above-mentioned method as an adhesive layer onto a substrate, and, if necessary, heat curing the adhesive layer by pressing or the like.
Alternatively, a laminate can be produced by laminating an adhesive layer containing the above-mentioned crosslinked product on a conductor layer, and then laminating an electrical insulating layer on the adhesive layer.

[Circuit boards, electronic devices]
As described above, the adhesive resin composition and crosslinked product (Q) of the present embodiment are excellent in adhesion, dielectric properties, heat resistance, mechanical properties, etc., and therefore can be suitably used for circuit boards.
The manufacturing method of the circuit board can be a generally known method, and is not limited thereto. For example, an adhesive layer containing the adhesive resin composition or crosslinked body of the present embodiment is formed on a conductor layer. Then, an electrical insulating layer is laminated on the obtained adhesive layer by a known method to prepare a laminate. Then, the conductor layer in the laminate is subjected to circuit processing or the like to obtain a circuit board.
The circuit board according to the present embodiment may also be a circuit board including an electrical insulating layer containing the adhesive resin composition according to the present embodiment or the crosslinked body according to the present embodiment, and a conductor layer provided on the electrical insulating layer.

Metals such as copper, aluminum, nickel, gold, silver, and stainless steel can be used as the metal for the conductor layer. Examples of methods for forming the conductor layer include a method in which the metal is made into a foil or the like and then laminated onto the electrical insulating layer via an adhesive layer made of the thermosetting adhesive film or sheet of this embodiment. The circuit board may be either a single-sided board or a double-sided board.

Such a circuit board can be used as an electronic device by mounting electronic components such as semiconductor elements, etc. Electronic devices can be manufactured based on publicly known information.
Examples of such electronic devices include ICT infrastructure equipment such as servers, routers, supercomputers, mainframes, and workstations; antennas such as GPS antennas, antennas for wireless base stations, millimeter-wave antennas, and RFID antennas; communication devices such as mobile phones, smartphones, PHS, PDAs, and tablet terminals; digital devices such as personal computers, televisions, digital cameras, digital video cameras, POS terminals, wearable terminals, and digital media players; in-vehicle electronic devices such as electronic control system devices, in-vehicle communication devices, car navigation devices, millimeter-wave radars, and in-vehicle camera modules; semiconductor testing equipment, high-frequency measuring equipment, and the like.

[Application]
The adhesive resin composition and crosslinked body (Q) of the present invention are excellent in adhesion, dielectric properties, transparency, solvent resistance, heat resistance and mechanical strength, so that a molded article made of the crosslinked body can be used as an adhesive material in, for example, optical fibers, optical waveguides, optical disk substrates, optical filters, lenses, optical filters for PDPs, organic electroluminescence, display parts, base film substrates for solar cells in the aerospace field, solar cells and thermal control systems, semiconductor elements, light-emitting diodes, electronic elements such as various memories, hybrid ICs, MCMs, circuit boards, prepregs and laminates used to form adhesive layers for circuit boards, medical instruments, automobile parts, lithium ion battery parts, semiconductor process parts, film capacitors, automobile parts, aerospace parts, semiconductor process materials, lithium ion battery parts, fuel cell parts, capacitor films, flexible displays, etc. It can also be used in adhesive applications in fields such as transparent adhesives, medical containers, medical catheter parts, waterproof sealants, and hard coat materials.
In particular, since the dielectric properties are excellent in stability over time, and the adhesiveness, transparency, solvent resistance, heat resistance, mechanical properties, etc., the composition can be suitably used in high frequency applications such as high frequency circuit boards.

Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various configurations other than those described above can also be adopted.
Furthermore, the present invention is not limited to the above-described embodiment, and modifications and improvements within the scope of the present invention that can achieve the object of the present invention are included in the present invention.

The present embodiment will be described in detail below with reference to examples. Note that the present embodiment is not limited to the description of these examples.

The following raw materials were used in the examples and comparative examples.

(raw materials)
Thermosetting cyclic olefin copolymer (m-1): Compound obtained in Synthesis Example 1 described later. Thermosetting cyclic olefin copolymer (m-2): Compound obtained in Synthesis Example 2 described later. Cyclic olefin copolymer (n-1): Copolymer of ethylene and tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene (product name: APEL 6509T, manufactured by Mitsui Chemicals, Inc.).
Polyphenylene ether resin 1: (SA9000, manufactured by SABIC Innovative Plastics)
Crosslinking aid 1: Triallyl isocyanurate (Tokyo Chemical Industry Co., Ltd.)
Radical initiator 1: Dicumyl peroxide (product name: Percumyl D, manufactured by NOF Corporation)
Antioxidant 1: Phenol-based antioxidant (pentaerythritol tetrakis[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate), product name: Irganox 1010, manufactured by BASF)
Binder resin 1: Acid-modified α-olefin polymer (product name: Unistole H-100, manufactured by Mitsui Chemicals, Inc.)
Silane coupling agent 1: Vinyltriethoxysilane (product name: KBE-1003, manufactured by Shin-Etsu Chemical Co., Ltd.)

The following raw materials were used to synthesize the thermosetting cyclic olefin copolymer (m):

Transition metal compound (1):
It was synthesized according to the method described in JP-A-2004-331965.

Modified methylaluminoxane (MMAO, manufactured by Tosoh Finechem Co., Ltd.)
Toluene (Fujifilm Wako Pure Chemical Industries, Ltd.: Wako special grade)
Bicyclo[2.2.1]-2-heptene (hereinafter also referred to as NB or 2-norbornene, manufactured by Tokyo Chemical Industry Co., Ltd.)
5-vinyl-2-norbornene (hereinafter referred to as VNB) (manufactured by Tokyo Chemical Industry Co., Ltd.)
Tetracyclo[ ^{4.4.0.12,5.17,10} ]-3- ^dodecene (hereinafter referred to as TD) (manufactured by Mitsui Chemicals, Inc.)
Acetone (Fujifilm Wako Pure Chemical Industries, Ltd.: Wako Special Grade)
Methanol (Fujifilm Wako Pure Chemical Industries, Ltd.: Wako special grade)

[Method for measuring the content of each structural unit constituting thermosetting cyclic olefin copolymer (m)]
The contents of the structural unit (A), the structural unit (B) and the structural unit (C) of the thermosetting cyclic olefin copolymer (m) were measured under the following conditions using a nuclear magnetic resonance apparatus "EXcalibur 270" manufactured by JEOL Ltd.
Number of accumulations: 16 to 64 Measurement temperature: room temperature From the ¹ H-NMR spectrum obtained in the above measurement, calculation was performed based on the intensity of the peak derived from hydrogen directly bonded to the double bond carbon and the peak derived from other hydrogen.

The number average molecular weight (Mn) of the thermosetting cyclic olefin copolymer (m) used in the synthesis examples, examples, and comparative examples was measured by GPC and calculated as a standard polystyrene equivalent. The GPC measurement was performed under the following conditions.
Apparatus: GPC HLC-8321 (manufactured by Tosoh Corporation)
Solvent: o-dichlorobenzene Column: TSKgel GMH6-HT x 2, TSKgel GMH6-HTL x 2 (both manufactured by Tosoh Corporation)
Flow rate: 1.0 ml/min Sample: 1 mg/mL o-dichlorobenzene solution Temperature: 140° C.

Thermosetting cyclic olefin copolymer (m):
[Synthesis Example 1: Thermosetting Cyclic Olefin Copolymer (m-1)]
In a SUS autoclave with a capacity of 1 L that had been thoroughly substituted with nitrogen, 433 mL of toluene, 15 mL of VNB, 52 mL of a 5M toluene solution of NB, 1.5 mmol of a hexane solution of MMAO in terms of Al, and 1480 mL of hydrogen were introduced into the system, and ethylene was introduced into the system until the total pressure reached 0.78 MPa. 4 μmol of transition metal compound (1) dissolved in toluene was added to initiate polymerization. After reacting at 35° C. for 40 minutes, 4 μmol of transition metal compound (1) was added, and the process of adding 4 μmol of transition metal compound (1) every 30 minutes was repeated twice more, and polymerization was performed for a total of 130 minutes. Then, a small amount of methanol was added to stop the polymerization.
After the polymerization was completed, ion-exchanged water was added to the obtained polymer solution and stirred for 1 hour, and then the organic layer was filtered with filter paper. The organic layer was poured into acetone to precipitate the polymer, which was stirred and then filtered with filter paper. The obtained polymer was dried under reduced pressure at 80°C for 10 hours to obtain an ethylene/NB/VNB copolymer, which is a cyclic olefin copolymer (m-1). The composition ratio of the NB-derived structure in the polymer determined by NMR was 33 mol%, the composition ratio of the VNB-derived structure was 10 mol%, and the number average molecular weight (Mn) determined by GPC measurement was 7,500.

[Synthesis Example 2: Thermosetting Cyclic Olefin Copolymer (m-2)]
Into a SUS autoclave with an internal volume of 1 L that had been thoroughly purged with nitrogen, 450 ml of toluene, 30 ml of VNB, 16 ml of TD, 0.9 mmol of MMAO in hexane in terms of Al, and 360 ml of hydrogen were charged, and ethylene was then introduced into the system until the total pressure reached 0.6 MPa. 0.028 mmol of transition metal compound (1) dissolved in toluene was added, and polymerization was carried out at 35° C. for 180 minutes. Thereafter, a small amount of methanol was added to terminate the polymerization.
After the polymerization was completed, ion-exchanged water was added to the obtained polymer solution and stirred for 1 hour, and then the organic layer was filtered with filter paper. The organic layer was poured into acetone to precipitate the polymer, which was stirred and then filtered with filter paper. The obtained polymer was dried under reduced pressure at 80°C for 10 hours to obtain an ethylene/TD/VNB copolymer, which is a cyclic olefin copolymer (m-2). The composition ratio of the TD-derived structure in the polymer determined by NMR was 12 mol%, the composition ratio of the VNB-derived structure was 26 mol%, and the number average molecular weight (Mn) determined by GPC measurement was 21,000.

[Example 1]
(Preparation of Varnish)
The thermosetting cyclic olefin copolymer (m-1) obtained in Synthesis Example 1 and toluene as a solvent were weighed according to the composition shown in Table 1. The weighed sample was stirred until fully dissolved to obtain the desired varnish-like adhesive resin composition. The unit of the blending ratio of each raw material in Table 1 is parts by mass.

(Preparation of Thermosetting Adhesive Film)
The obtained varnish-like adhesive resin composition was applied to a release-treated PET film at a speed of 10 mm/sec, and then dried at 150°C for 4 minutes in a nitrogen gas flow blower. Two of the obtained films were stacked so that the adhesive resin composition-coated surfaces faced each other, and pressurized to 3.5 MPa by a vacuum press, heated at a constant rate from room temperature (25°C), and held at 180°C for 120 minutes to obtain a thermosetting adhesive film. The obtained thermosetting adhesive film was subjected to dielectric loss tangent measurement and visual evaluation of the film appearance according to the following procedure. The obtained results are shown in Table 1.

Dielectric loss tangent evaluation: For the thermosetting adhesive films obtained in the examples and comparative examples, the dielectric loss tangent Df at 10 GHz was measured by a cylindrical cavity resonator method and evaluated as follows.
Those with a dielectric loss tangent Df of less than 0.0010 were rated as "A" for excellent low dielectric properties in the high frequency range, while those with a dielectric loss tangent Df of 0.0010 or more were rated as "B" for poor low dielectric properties in the high frequency range.
Appearance evaluation: The transparency of the thermosetting adhesive films obtained in the examples and comparative examples was evaluated. The film appearance was visually observed, and if it was colorless and transparent, it was rated as "transparent", and if it was colored brown, it was rated as "brown". The results are shown in Table 1.

[Example 2 and Comparative Example 1]
A varnish and a thermosetting adhesive film were prepared and evaluated in the same manner as in Example 1, except that the blending compositions were changed to those shown in Table 1. The obtained results are shown in Table 1.

Claims (13)

A thermosetting cyclic olefin copolymer (m);
A crosslinking agent (X);
An antioxidant (Y);
An adhesive resin composition comprising:
The thermosetting cyclic olefin copolymer (m) is
(A) one or more olefin-derived repeating units represented by the following general formula (I),
(B) one or more repeating units derived from a cyclic non-conjugated diene represented by the following general formula (III),
(C) one or more repeating units derived from a cyclic olefin represented by the following general formula (V):

[In the above general formula (I), R ³⁰⁰ represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms.]

[In the above general formula (III), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, R ⁶¹ to R ⁷⁶ as well as R ^a1 and R ^b1 may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, R ¹⁰⁴ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, t is a positive integer of 0 to 10, and R ⁷⁵ and R ⁷⁶ may be bonded to each other to form a monocycle or polycycle.]

[In the above general formula (V), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, R ⁶¹ to R ⁷⁸ as well as R ^a1 and R ^b1 may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and R ⁷⁵ to R ⁷⁸ may be bonded to each other to form a monocycle or multiple rings.] The thermosetting cyclic olefin copolymer (m) further comprises a cyclic olefin (co)polymer (n) different from the thermosetting cyclic olefin copolymer (m),
The cyclic olefin (co)polymer (n) comprises at least one selected from a copolymer (n1) of ethylene or an α-olefin with a cyclic olefin (provided that the copolymer (n1) does not contain a repeating unit derived from a cyclic non-conjugated diene represented by the general formula (III)) and a ring-opening polymer (n2) of a cyclic olefin,
When the total amount of the thermosetting cyclic olefin copolymer (m) and the cyclic olefin (co)polymer (n) is taken as 100 mass%,
The content of the thermosetting cyclic olefin copolymer (m) is 5% by mass or more and 95% by mass or less,
The adhesive resin composition according to claim 1, wherein the content of the cyclic olefin (co)polymer (n) is from 5% by mass to 95% by mass. The adhesive resin composition according to claim 1 or 2, further comprising a binder resin. The adhesive resin composition according to claim 3, wherein the binder resin contains a modified polyolefin. When the total mole number of repeating units in the thermosetting cyclic olefin copolymer (m) is taken as 100 mol %,
The content of the repeating unit (A) derived from the olefin is 10 mol % or more and 90 mol % or less,
The adhesive resin composition according to any one of claims 1 to 4, wherein the content of the repeating unit (B) derived from the cyclic non-conjugated diene is 1 mol% or more and 40 mol% or less, and the content of the repeating unit (C) derived from the cyclic olefin is 1 mol% or more and 50 mol% or less. The adhesive resin composition according to any one of claims 1 to 5, wherein the cyclic non-conjugated diene constituting the repeating unit (B) derived from the cyclic non-conjugated diene includes 5-vinyl-2-norbornene. The adhesive resin composition according to any one of claims 1 to 6, ^wherein the cyclic olefin constituting the cyclic olefin-derived repeating unit (C) includes at least one selected from the group consisting of tetracyclo[ ^{4.4.0.12,5.17,10} ]-3-dodecene and bicyclo[2.2.1]-2-heptene. A crosslinked product of the adhesive resin composition according to any one of claims 1 to 7. A thermosetting adhesive film or sheet comprising the adhesive resin composition according to any one of claims 1 to 7 or the crosslinked body according to claim 8. A laminate in which the thermosetting adhesive film or sheet according to claim 9 is laminated onto a substrate. A circuit board comprising an electrical insulating layer containing the adhesive resin composition according to any one of claims 1 to 7 or the crosslinked body according to claim 8, and a conductor layer provided on the electrical insulating layer. A circuit board comprising an electrical insulating layer, a conductor layer, and an adhesive layer for bonding the electrical insulating layer and the conductor layer, the adhesive layer comprising the adhesive resin composition according to any one of claims 1 to 7 or the crosslinked body according to claim 8. An electronic device equipped with the circuit board according to claim 11 or 12.