Cyclic olefin copolymer resin composition, varnish, and crosslinked product

Abstract

To provide a cyclic olefin-based copolymer composition having an excellent balance between dielectric properties and transparency.SOLUTION: A cyclic olefin-based copolymer resin composition containing a cyclic olefin-based copolymer (M) and a maleimide compound (L). The cyclic olefin-based copolymer (M) includes a cyclic olefin-based copolymer (m) containing repeating units represented by a specific general formula, and the maleimide compound (L) is a monomaleimide compound having one maleimide group in a molecule represented by a specific general formula. When the total of the cyclic olefin-based copolymer (M) and the maleimide compound (L) is 100 parts by mass, the content of the maleimide compound (L) is 1 part by mass or more and 50 parts by mass or less.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a cyclic olefin copolymer composition, a varnish, and a crosslinked product. [Background technology]

[0002] Recently, in addition to an increase in wireless communication devices that use high-frequency bands, the use of higher frequency bands has inevitably become more common due to faster communication speeds. Accordingly, there is a demand for circuit board materials with high insulation properties and small dielectric tangent in order to minimize transmission loss at high frequencies.

[0003] Examples of resin materials used in such circuit boards include cyclic olefin copolymers copolymerized with dienes, as described in Patent Documents 1 and 2.

[0004] Patent Document 1 discloses a styrene-based polymer using a monofunctional maleimide compound. Furthermore, Patent Document 2 discloses a resin composition containing polyphenylene ether. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2019-194307 A [Patent Document 2] JP 2020-200434 A Summary of the Invention [Problem to be solved by the invention]

[0006] According to the study by the present inventors, the crosslinked product of the styrene-based polymer described in Patent Document 1 has low dielectric properties and high heat resistance, but is not suitable for applications requiring transparency. Also, the polyphenylene ether-containing resin composition described in Patent Document 2 has improved electrical properties, heat resistance, and toughness, but is not suitable for applications requiring transparency.

[0007] The present invention has been made in view of the above circumstances, and provides a cyclic olefin copolymer composition having an excellent balance between dielectric properties and transparency. [Means for solving the problem]

[0008] The present invention has been made in view of the above circumstances, and has been completed based on the discovery that the balance between dielectric properties and transparency can be improved.

[0009] That is, according to the present invention, there are provided a cyclic olefin copolymer composition, a varnish, and a crosslinked product as shown below.

[0010] [1] A cyclic olefin copolymer resin composition comprising a cyclic olefin copolymer (M) and a maleimide compound (L), The cyclic olefin copolymer (M) is One or more olefin-derived repeating units represented by the following general formula (I), One or more repeating units derived from a cyclic non-conjugated diene represented by the following general formula (III), and one or more repeating units derived from cyclic olefins represented by the following general formula (V), The maleimide compound (L) is It is a monomaleimide compound having one maleimide group in the molecule represented by the following general formula (X), A cyclic olefin copolymer resin composition, in which the content of the maleimide compound (L) is 1 part by mass or more and 50 parts by mass or less, when the total amount of the cyclic olefin copolymer (M) and the maleimide compound (L) is 100 parts by mass. [ka] [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. [ka] [In the above general formula (III), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, and R 61 ~R 76 And R a1 and R b1 may be the same or different, and each is 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 monocyclic or polycyclic ring. [ka] [In the above general formula (V), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, and R 61 ~R 78 And R a1 and R b1 may be the same or different, and each is 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 75 ~R 78 may be bonded to each other to form a monocyclic or polycyclic ring. [ka] [In the above general formula (X), R is an alkyl group having 1 to 20 carbon atoms; 3 ~20 cycloalkyl groups or carbon atoms6 is an aryl group having a molecular weight of 1 to 20. [2] The cyclic olefin copolymer resin composition according to [1], wherein the content of the repeating unit derived from the cyclic non-conjugated diene is in the range of 19 mol % or more and 40 mol % or less, when the total number of moles of the repeating units in the cyclic olefin copolymer (m) is 100 mol %. [3] In the cyclic olefin copolymer (m), the cyclic non-conjugated diene constituting the repeating unit derived from the cyclic non-conjugated diene contains 5-vinyl-2-norbornene, and the cyclic olefin constituting the repeating unit derived from the cyclic olefin is tetracyclo[4.4.0.1 2,5 .1 7,10 The cyclic olefin copolymer resin composition according to [1] or [2], which contains 1-3-dodecene. [4] The cyclic olefin copolymer resin composition according to [3], The composition further comprises a cyclic olefin copolymer (n) different from the cyclic olefin copolymer (m), The cyclic olefin copolymer (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 cyclic olefin copolymer (m) and the cyclic olefin copolymer (n) is 100 mass%, A cyclic olefin copolymer resin composition, wherein the content of the cyclic olefin copolymer (m) is 5% by mass or more and 95% by mass or less, and the content of the cyclic olefin copolymer (n) is 5% by mass or more and 95% by mass or less. [5] The cyclic olefin copolymer resin composition according to any one of [1] to [4], wherein the monomaleimide compound is N-phenylmaleimide or N-cyclohexylmaleimide. [6] A varnish comprising the cyclic olefin copolymer resin composition according to any one of [1] to [5] and a solvent. [7] A crosslinked body obtained by crosslinking the cyclic olefin copolymer resin composition according to any one of [1] to [5]. [8] A film or sheet comprising the crosslinked product according to [7]. [9] A laminate comprising the crosslinked body described in [7].

[10] A circuit board comprising an electrical insulating layer containing the crosslinked body according to [7], and a conductor layer provided on the electrical insulating layer.

[11] An electronic device comprising the circuit board described in

[10] .

[12] A prepreg comprising the cyclic olefin copolymer resin composition according to any one of [1] to [5] and a sheet-like fiber substrate. Effect of the Invention

[0011] According to the present invention, it is possible to provide a cyclic olefin copolymer resin composition having an excellent balance between dielectric properties and transparency. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] Hereinafter, the present invention will be described based on the embodiments. In the present embodiments, "A to B" indicating a numerical range means A or more and B or less unless otherwise specified.

[0013] First, a cyclic olefin copolymer resin composition according to an embodiment of the present invention will be described. The cyclic olefin copolymer resin composition according to this embodiment contains a cyclic olefin copolymer (M) and a maleimide compound (L). The cyclic olefin copolymer (M) is One or more olefin-derived repeating units represented by the following general formula (I), One or more repeating units derived from a cyclic non-conjugated diene represented by the following general formula (III), and one or more repeating units derived from cyclic olefins represented by the following general formula (V), The maleimide compound (L) is It is a monomaleimide compound having one maleimide group in the molecule represented by the following general formula (X), When the total amount of the cyclic olefin copolymer (M) and the maleimide compound (L) is taken as 100 parts by mass, the content of the maleimide compound (L) is 1 part by mass or more and 50 parts by mass or less.

[0014] In addition, when the total amount of the cyclic olefin copolymer (M) and the maleimide compound (L) contained in the cyclic olefin copolymer resin composition according to this embodiment is 100 parts by mass, the content of the maleimide compound (L) is 1 part by mass or more and 50 parts by mass or less, preferably 1 part by mass or more and 40 parts by mass or less, more preferably 1 part by mass or more and 30 parts by mass or less, and even more preferably 1 part by mass or more and 25 parts by mass or less.

[0015] According to the cyclic olefin copolymer resin composition of this embodiment, the cyclic olefin copolymer (M) contains the cyclic olefin copolymer (m) of the above embodiment, the maleimide compound (L) contains the monomaleimide compound of the above embodiment, and the blending amounts of the cyclic olefin copolymer (M) and the maleimide compound (L) are within the above numerical ranges, whereby a cyclic olefin copolymer resin composition can be obtained that has a good balance between excellent dielectric properties and transparency of the cyclic olefin copolymer.

[0016] [Cyclic olefin copolymer (M)] First, the cyclic olefin copolymer (M) according to the present embodiment will be described. As described above, the cyclic olefin copolymer (M) according to the present embodiment includes the cyclic olefin copolymer (m). In addition, the cyclic olefin copolymer resin composition according to the present embodiment can also further include the cyclic olefin copolymer (n) different from the cyclic olefin copolymer (m). First, the cyclic olefin copolymer (m) according to an embodiment of the present invention will be described below.

[0017] [Cyclic olefin copolymer (m)] The cyclic olefin copolymer (m) according to this embodiment is One or more olefin-derived repeating units represented by the following general formula (I), One or more repeating units derived from a cyclic non-conjugated diene represented by the following general formula (III), The copolymer is a cyclic olefin copolymer having a crosslinkable group containing one or more repeating units derived from cyclic olefins represented by the following general formula (V).

[0018] When the total number of moles of repeating units in the cyclic olefin copolymer (m) is taken as 100 mol%, the content of repeating units derived from the cyclic non-conjugated diene is preferably 19 mol% or more and 40 mol% or less, more preferably 20 mol% or more and 39 mol% or less, and more preferably 23 mol% or more and 38 mol% or less. When the content of the repeating unit derived from the cyclic non-conjugated diene is within the above range, the crosslinked body obtained from the cyclic olefin copolymer (m) has excellent stability of dielectric properties over time and excellent heat resistance.Furthermore, the crosslinked body can be obtained that is excellent in mechanical properties, dielectric properties, transparency and gas barrier properties.In other words, the crosslinked body can be obtained that has a good balance of these physical properties. When the content of the repeating unit derived from the cyclic non-conjugated diene is equal to or less than the upper limit, the moldability and solubility of the cyclic olefin copolymer (m) are improved, and the stability of the dielectric properties of the crosslinked body over time is improved.When the content of the repeating unit derived from the cyclic non-conjugated diene is equal to or more than the lower limit, the heat resistance and mechanical properties of the crosslinked body obtained by crosslinking the cyclic olefin copolymer (m) are improved.

[0019] The number average molecular weight Mn of the cyclic olefin copolymer (m) is at least 3,000, preferably at least 4,500, and more preferably at least 6,000. When the number average molecular weight Mn of the cyclic olefin copolymer (m) is at least the above lower limit, the crosslinked body obtained by crosslinking the cyclic olefin copolymer (m) or the cyclic olefin copolymer resin composition according to this embodiment can have good dielectric properties, heat resistance, and mechanical properties. The number average molecular weight Mn of the cyclic olefin copolymer (m) is not more than 30,000, preferably not more than 25,000, more preferably not more than 20,000. When the number average molecular weight Mn of the cyclic olefin copolymer (m) is not more than the above upper limit, the cyclic olefin copolymer (m) or the cyclic olefin copolymer resin composition according to this embodiment can have good moldability, such as impregnation property into a fiber substrate and wiring embedding property, during the production of a circuit board. The number average molecular weight Mn of the cyclic olefin copolymer (m) can be controlled by the polymerization conditions such as the polymerization catalyst, the cocatalyst, the amount of H2 added, and the polymerization temperature.

[0020] When the number average molecular weight Mn of the cyclic olefin copolymer (m) is within the above range, the cyclic olefin copolymer (m) has excellent dielectric properties, while having good fluidity, mechanical properties, and moldability, such as impregnation into a fiber base material and wiring embedding properties, during the production of a circuit board. Here, in the case of conventional cyclic olefin copolymers, if the number average molecular weight is within the above range, the molecular weight is relatively low, and the heat resistance, dielectric properties, mechanical properties, etc. of the obtained crosslinked body tend to be reduced. However, even if the number average molecular weight Mn of the cyclic olefin copolymer (m) according to the present embodiment is within the above range, the impregnation into the fiber substrate is good, and the mixability with additives such as inorganic fillers and flame retardants is improved, so that the decrease in mechanical strength can be suppressed.

[0021] In the cyclic olefin copolymer (m) according to this embodiment, when the total number of moles of repeating units in the cyclic olefin copolymer (m) is 100 mol%, the sum of the content of repeating units derived from a cyclic non-conjugated diene and the content of repeating units derived from a cyclic olefin is preferably less than 60 mol%, more preferably less than 50 mol%, and even more preferably less than 48 mol%. The lower limit of the total content of the repeating units derived from the cyclic non-conjugated diene and the repeating units derived from the cyclic olefin is not particularly limited, but is, for example, 20 mol % or more, and preferably 26 mol % or more.

[0022] [ka]

[0023] 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.

[0024] [ka]

[0025] In the above general formula (III), u is 0 or 1, v is 0 or a positive integer, preferably an integer of 0 or more and 2 or less, more preferably 0 or 1, w is 0 or 1, R 61 ~R 76 And R a1 and R b1 may be the same or different, and each is 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 monocyclic or polycyclic ring.

[0026] [ka]

[0027] In the above general formula (V), u is 0 or 1, v is 0 or a positive integer, preferably an integer of 0 or more and 2 or less, more preferably 0 or 1, w is 0 or 1, R 61 ~R 78 And R a1 and R b1may be the same or different, and each is 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 75 ~R 78 may be bonded to each other to form a monocyclic or polycyclic ring.

[0028] In the cyclic olefin copolymer (m), when the total number of moles of repeating units in the cyclic olefin copolymer (m) is taken as 100 mol%, the content of repeating units derived from olefins is preferably 20 mol% to 80 mol%, more preferably 30 mol% to 75 mol%, even more preferably 40 mol% to 70 mol%, and particularly preferably 50 mol% to 70 mol%; the content of repeating units derived from cyclic non-conjugated dienes is 19 mol% to 40 mol%, preferably 20 mol% to 39 mol%, more preferably 23 mol% to 38 mol%, and the content of repeating units derived from cyclic olefins is preferably 1 mol% to 30 mol%, more preferably 2 mol% to 25 mol%, and even more preferably 3 mol% to 20 mol%. When the content of each repeating unit in the cyclic olefin copolymer (m) is within the above range, the crosslinked body obtained from the cyclic olefin copolymer (m) has excellent stability of dielectric properties over time and excellent heat resistance.Furthermore, the crosslinked body can be obtained that is excellent in mechanical properties, dielectric properties, transparency and gas barrier properties.In other words, the crosslinked body can be obtained that has a good balance of these physical properties.

[0029] The olefin monomer, which is one of the copolymerization raw materials for the cyclic olefin copolymer (m), is a monomer that provides the skeleton represented by the above formula (I) through addition copolymerization, and is an olefin represented by the following general formula (Ia).

[0030] [ka]

[0031] 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 the 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 body having better heat resistance, mechanical properties, dielectric properties, transparency, and gas barrier properties, ethylene and propylene are preferred, and ethylene is particularly preferred. Two or more kinds of olefin monomers represented by the above formula (Ia) may be used.

[0032] The cyclic non-conjugated diene monomer, which is one of the copolymerization raw materials of the cyclic olefin copolymer (m), undergoes addition copolymerization to form the constitutional unit represented by the above formula (III). Specifically, the cyclic non-conjugated diene represented by the following general formula (IIIa) corresponding to the above general formula (III) is used.

[0033] [ka]

[0034] In the above general formula (IIIa), u is 0 or 1, v is 0 or a positive integer, preferably an integer of 0 or more and 2 or less, more preferably 0 or 1, w is 0 or 1, R 61 ~R 76 And R a1 and R b1 may be the same or different, and each is 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 104is 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 monocyclic or polycyclic ring.

[0035] The cyclic non-conjugated diene represented by the above general formula (IIIa) is not particularly limited, but examples thereof include cyclic non-conjugated dienes represented by the following chemical formulas. Among these, 5-vinyl-2-norbornene, 8-vinyl-9-methyltetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene is preferred, and 5-vinyl-2-norbornene is particularly preferred.

[0036] [ka]

[0037] [ka]

[0038] The cyclic non-conjugated diene represented by the above general formula (IIIa) can also be specifically represented by the following general formula (IIIb).

[0039] [ka]

[0040] In general formula (IIIb), n is an integer of 0 to 10, R1 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R2 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

[0041] The cyclic olefin copolymer (m) of the present 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 a side chain portion, i.e., a portion other than the main chain of the copolymer.

[0042] The cyclic olefin monomer, which is one of the copolymerization raw materials of the cyclic olefin copolymer (m), undergoes addition copolymerization to form the constitutional unit represented by the above formula (V). Specifically, the cyclic olefin monomer represented by the following general formula (Va) corresponding to the above general formula (V) is used.

[0043] [ka]

[0044] In the above general formula (Va), u is 0 or 1, v is 0 or a positive integer, preferably an integer of 0 or more and 2 or less, more preferably 0 or 1, w is 0 or 1, R 61 ~R 78 And R a1 and R b1 may be the same or different, and each is 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 75 ~R 78 may be bonded to each other to form a monocyclic or polycyclic ring.

[0045] Specific examples of the cyclic olefin represented by the above general formula (Va) include the compounds described in WO 2006 / 118261. Examples of the cyclic olefin represented by the above general formula (Va) include bicyclo[2.2.1]-2-heptene (also called norbornene), tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene (also called tetracyclododecene) is preferred, and tetracyclo[4.4.0.1 2,5 .1 7,10 These cyclic olefins have the advantage that the elastic modulus of the copolymer and crosslinked body is easily maintained because they have a rigid ring structure, and crosslinking can be easily controlled because they do not contain a hetero double bond structure.

[0046] By using the olefin monomer represented by the general formula (Ia) or the cyclic olefin monomer represented by the general formula (Va) as the copolymerization components, the solubility of the cyclic olefin copolymer (m) in a solvent is further improved, resulting in good moldability and improved product yield.

[0047] The cyclic olefin copolymer (m) may be composed of one or more repeating units derived from olefins represented by general formula (I), one or more repeating units derived from cyclic non-conjugated dienes represented by general formula (III), and one or more repeating units derived from cyclic olefins represented by general formula (V), as well as repeating units derived from cyclic non-conjugated dienes represented by general formula (III) and cyclic olefins other than the cyclic olefins represented by general formula (V), and / or linear polyenes. In this case, as the copolymerization raw materials for the 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. Such cyclic olefin monomers and linear polyene monomers are cyclic olefins represented by the following general formula (VIa) or (VIIa), or linear polyenes represented by the following general formula (VIIIa): Two or more different types of these cyclic olefins and linear polyenes may be used.

[0048] [ka]

[0049] In the general formula (VIa), x and d are 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 are 0, 1, or 2, and R 81 ~R 99may be the same or different, and each is 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; R 89 and R 90 and the carbon atom to which R is bonded. 93 or the carbon atom to which R is attached 91 may be bonded directly or 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.

[0050] [ka]

[0051] In general formula (VIIa), R 100 and R 101 may be the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and f is 1≦f≦18.

[0052] [ka]

[0053] In general formula (VIIIa), R 201 From R 206 may be the same or different and are each a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and P is a linear or branched hydrocarbon group having 1 to 20 carbon atoms which may contain a double bond and / or a triple bond.

[0054] Specific examples of the cyclic olefin represented by general formula (VIa) and general formula (VIIa) that can be used include the compounds described in paragraphs 0037 to 0063 of WO 2006 / 118261.

[0055] Specific examples of the linear 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, 1,5-hexadiene, etc. Cyclizable polyenes cyclized from polyenes such as 1,3-butadiene and 1,5-hexadiene may also be used.

[0056] When the 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 olefin other than the cyclic non-conjugated diene represented by the general formula (III) and the cyclic olefin represented by the general formula (V) [e.g., general formula (VIa) and general formula (VIIa)], the content of the structural unit is usually 0.1 to 100 mol%, 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).

[0057] By using the olefin monomer represented by the general formula (Ia), the cyclic olefin represented by the general formula (VIa) or (VIIa), and the chain polyene represented by the general formula (VIIIa) as the copolymerization components, the effect according to the present embodiment can be obtained, and the solubility of the cyclic olefin copolymer in the solvent is improved, so that the moldability is good and the product yield is improved. 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 copolymer and the crosslinked body 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.

[0058] The comonomer content and glass transition temperature (Tg) of the cyclic olefin copolymer (m) can be controlled by the monomer charging ratio according to the intended use. The Tg of the cyclic olefin copolymer (m) is usually 300°C or less, preferably 250°C or less, more preferably 200°C or less, even more preferably 170°C or less, and particularly preferably 150°C or less. When the Tg is equal to or less than the upper limit, the melt moldability of the cyclic olefin copolymer (m) and its solubility in a solvent when it is made into a varnish are improved.

[0059] [Production method of cyclic olefin copolymer (m)] The 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.

[0060] (Cyclic olefin copolymer (n)) The cyclic olefin copolymer (n) is a cyclic olefin copolymer different from the cyclic olefin copolymer (m). Specifically, the cyclic olefin copolymer (n) includes at least one selected from the copolymer (n1) of ethylene or α-olefin and cyclic olefin, and the ring-opening polymer (n2) of cyclic olefin. The cyclic olefin copolymer resin composition of the present embodiment includes the cyclic olefin copolymer (n), so that the dielectric properties of the crosslinked body obtained by crosslinking the cyclic olefin copolymer resin composition can be further improved. 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 %.

[0061] As the copolymer (n1) of ethylene or an α-olefin and a cyclic olefin, for example, the polymers described in paragraphs 0030 to 0123 of WO 2008 / 047468 can be used.

[0062] For example, it is a polymer having an alicyclic structure in at least a part of the repeating structural units (hereinafter, also simply referred to as a "polymer having an alicyclic structure"), and it is sufficient that at least a part 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 (13).

[0063] [ka]

[0064] (In formula (13), x and y represent a copolymerization ratio 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 for 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. R a , R b , R c and Q may each be one type, or two or more types in any ratio.)

[0065] In addition, in the above general formula (13), R ais 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 (17) when n=0, and most preferably a divalent group in which p is 0 or 1 in the following general formula (17). a The structure may be used alone or in combination of two or more.

[0066] [ka]

[0067] In the formula (17), p is an integer of 0 to 2.

[0068] 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 (14): For example, it comprises 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.

[0069] [ka]

[0070] (In formula (14), 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. R a and R b may each be one type, or may contain two or more types in any ratio. x and y 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.

[0071] 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 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 are preferred, and bicyclo[2.2.1]-2-heptene and tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene is more preferable. The copolymer (n1) of ethylene or an α-olefin with a cyclic olefin may be a polymer having one or more structures represented by the above general formula (13) or a polymer obtained by subjecting a cyclic olefin copolymer represented by the above general formula (14) to a hydrogenation treatment.

[0072] Furthermore, as the copolymer (n1) of ethylene or α-olefin and cyclic olefin, a copolymer of α-olefin and cyclic olefin having 4 to 12 carbon atoms is also preferred. As the copolymer of α-olefin and cyclic olefin having 4 to 12 carbon atoms, for example, the polymers described in paragraphs 0056 to 0070 of WO 2015 / 178145 can be used. 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.

[0073] The substituted norbornene is not particularly 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).

[0074] [ka]

[0075] (In the formula, R 1 ~R 12 may be the same or different and are selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group; R 9 and R 10 , R 11 and R 12 may combine together to form a divalent hydrocarbon group, R 9 or R 10 And, R 11 or R 12 may form a ring together. n is 0 or a positive integer, and when n is 2 or more, R 5 ~R 8 may be the same or different in each repeating unit. However, when n=0, R 1 ~R 4 and R 9 ~R 12 At least one of is not a hydrogen atom.)

[0076] The substituted norbornene represented by the general formula (A) will be described. R in the general formula (A) 1 ~R 12 may be the same or different and are selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group.

[0077] R 1 ~R 8 Specific examples of the alkyl group 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 be the same as one another.

[0078] Also, R 9 ~R 12Specific examples of the alkyl group 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. These may be different from each other, may be partially different, or may be the same in all.

[0079] R 9 and R 10 , or R 11 and R 12 Specific examples of the divalent hydrocarbon group formed by combining with each other include alkylidene groups such as an ethylidene group, a propylidene group, and an isopropylidene group.

[0080] R 9 or R 10 And, R 11 or R 12 When these rings form a ring, the ring formed may be a monocyclic ring or a 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.

[0081] Specific examples of the substituted norbornene represented by the general formula (A) include 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 two-ring cyclic 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, and 5-propenyl-bicyclo[2.2.1]hept-2-ene; 2,5 ]Deca-3,7-diene (common name: dicyclopentadiene), tricyclo[4.3.0.1 2,5 ]dec-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 partially hydrogenated products thereof (or an adduct of cyclopentadiene and cyclohexene) 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-cyclohexenyl-bicyclo[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 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, 8-methylidenetetracyclo[4.4.0.1 2,5 .1 7,10 ]dodec-3-ene, 8-ethylidenetetracyclo[4.4.0.1 2,5 .17,10 ]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, a 4-ring cyclic olefin; 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 .012,17 .1 13,l6 ]-14-eicosene; and polycyclic olefins such as a tetramer of cyclopentadiene.

[0082] 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 particularly preferred.

[0083] 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.

[0084] The α-olefin having 4 to 12 carbon atoms is not particularly limited, and 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, 1-dodecene, etc. Among these, 1-hexene, 1-octene, and 1-decene are preferred.

[0085] 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 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.

[0086] The conditions for the polymerization step for obtaining a copolymer of an α-olefin having 4 to 12 carbon atoms and a cyclic olefin are not particularly 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 appropriately adjusted.

[0087] As the cyclic olefin copolymer (n), a ring-opening polymer (n2) of a cyclic olefin can be used. Examples of the ring-opening polymer (n2) of a cyclic olefin include a ring-opening polymer of a norbornene-based monomer, a ring-opening polymer of a norbornene-based monomer and another monomer capable of ring-opening copolymerization with the norbornene-based monomer, and hydrogenated products thereof.

[0088] Examples of norbornene monomers include bicyclo[2.2.1]hept-2-ene (common name: norbornene) and its derivatives (those having a substituent on the ring), tricyclo[4.3.0 1,6 .1 2,5 ]Deca-3,7-diene (commonly known as dicyclopentadiene) and its derivatives, 7,8-benzotricyclo[4.3.0.1 2,5 ]dec-3-ene (commonly known as methanotetrahydrofluorene: 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, etc. The substituents on the rings of these derivatives include alkyl groups, alkylene groups, vinyl groups, alkoxycarbonyl groups, and alkylidene groups. The derivatives may have one or more substituents. 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, 8-ethylidene-tetracyclo[4.4.0.1 2,5 .1 7,10 ]dodec-3-ene and the like. These norbornene monomers may be used alone or in combination of two or more.

[0089] 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. Examples of the ring-opening polymerization catalyst that can be used include catalysts consisting of a halide of a metal such as ruthenium or osmium, a nitrate or an acetylacetone compound, and a reducing agent; and catalysts consisting of a halide of a metal such as titanium, zirconium, tungsten, or molybdenum, or an acetylacetone compound, and an organoaluminum compound. Examples of other monomers capable of undergoing ring-opening copolymerization with norbornene monomers include monocyclic olefin monomers such as cyclohexene, cycloheptene, and cyclooctene.

[0090] A hydrogenated ring-opening polymer of a norbornene-based monomer or a hydrogenated ring-opening polymer of a norbornene-based monomer and another monomer capable of ring-opening copolymerization with the norbornene-based monomer can usually be obtained 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.

[0091] In the present embodiment, the cyclic olefin copolymer (n) may be used alone or in combination of two or more kinds.

[0092] [Maleimide compound (L)] Next, the maleimide compound (L) according to this embodiment will be described. The maleimide compound (L) in the present invention is a monomaleimide compound having one maleimide group in the molecule, represented by the following general formula (X). By including the monomaleimide compound of the above embodiment, the cyclic olefin copolymer resin composition can be a composition containing a cyclic olefin polymer and a maleimide compound while the blending components are sufficiently dissolved, and further, in the crosslinked product obtained by crosslinking the cyclic olefin copolymer resin composition, it becomes possible to improve heat resistance while satisfying dielectric properties and transparency in the high frequency range suitable for circuit boards and the like.

[0093] [ka]

[0094] In the above general formula (X), R represents an alkyl group having 1 to 20 carbon atoms; 3 ~20 cycloalkyl groups or carbon atoms 6 is an aryl group having a molecular weight of 20 or less.

[0095] [Monomaleimide compounds] Specific examples of monomaleimide compounds include N-phenylmaleimide, N-cyclohexylmaleimide, o-methylphenylmaleimide, N-dodecylmaleimide, and o-chlorophenylmaleimide. Among these, N-phenylmaleimide and N-cyclohexylmaleimide are particularly preferred. Two or more types of monomaleimide compounds may be used in combination. This improves compatibility with the cyclic olefin copolymer (m).

[0096] Hereinafter, other components that may be contained in the cyclic olefin copolymer resin composition according to this embodiment will be described.

[0097] (Additives) Various additives may be added to the cyclic olefin copolymer resin composition according to the present embodiment depending on the purpose. The amount of the additive 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, friction and wear improvers, flame retardants, foaming agents, impact resistance agents, fillers, hydrochloric acid absorbents, and metal deactivators.

[0098] Examples of the heat stabilizer include hindered phenol-based heat stabilizers, sulfur-based heat stabilizers, and amine-based heat stabilizers. These may be used alone or in combination of two or more. Among these, phosphite-based heat stabilizers and hindered phenol-based heat stabilizers are preferred. Examples of the additives that can be used include heat stabilizers, light stabilizers, antioxidants, 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, and metal deactivators described in paragraphs 0085 to 0120 of WO 2017 / 150218.

[0099] (Method for preparing cyclic olefin copolymer resin composition) The cyclic olefin copolymer resin composition according to the present embodiment can be prepared by mixing the cyclic olefin copolymer (M), the maleimide compound (L), and, if necessary, an elastomer or various additives. As a mixing method, a melt blending method using an extruder or the like, or a solution blending method in which the copolymer is dissolved and dispersed in a suitable solvent, etc., can be adopted. The solvent will be described in detail below.

[0100] [varnish] The varnish according to this embodiment may contain the cyclic olefin copolymer resin composition and a solvent. The solvent preferably comprises at least one non-polar solvent (X). Examples of the non-polar solvent (X) include saturated hydrocarbons such as heptane, hexane, octane, and decane; alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, and decahydronaphthalene; and aromatic hydrocarbons such as toluene, benzene, xylene, mesitylene, and pseudocumene.

[0101] The non-polar solvent (X) preferably contains at least one selected from toluene, xylene, cyclohexane, and decahydronaphthalene.

[0102] Among these, from the viewpoints of long-term stability, solubility, and versatility of the varnish, it is particularly preferable to contain at least toluene as the non-polar solvent (X). As long as the stability and performance of the varnish are not impaired, the polar solvent (Y) may further contain methyl isobutyl ketone, methyl ethyl ketone, diisobutyl ketone, methyl propyl ketone, and cyclohexanone.

[0103] In this embodiment, the method for preparing the varnish may be carried out by any method, but usually includes a step of mixing the cyclic olefin copolymer resin composition with a solvent. The mixing order of each component is not limited, and it 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 it may be carried out by any apparatus capable of stirring and mixing, such as a batch type or a continuous type. The temperature at which the varnish is prepared can be selected arbitrarily within the range from room temperature to the boiling point of the solvent. The reaction solution obtained when the cyclic olefin copolymer (m) is obtained may be used as a solvent and the cyclic olefin copolymer (n) may be dissolved therein to prepare a varnish. Alternatively, the varnish may be prepared by mixing a varnish of the cyclic olefin copolymer (n) separately prepared with the reaction solution obtained when the cyclic olefin copolymer (m) is obtained.

[0104] [Method of manufacturing crosslinked body] The crosslinked product is the crosslinked product of the cyclic olefin copolymer resin composition according to the present embodiment, and is obtained by crosslinking the cyclic olefin copolymer (M) in the above-mentioned cyclic olefin copolymer resin composition. There is no particular limitation on the method for crosslinking the cyclic olefin copolymer (M), and examples thereof include a method of crosslinking while or after molding into any shape using a radical polymerization initiator, sulfur, a hydrosilyl group-containing compound, electron beam or other radiation.

[0105] Crosslinking with a radical polymerization initiator can be performed by the same method as that used for polyolefins. That is, a radical polymerization initiator such as dicumyl peroxide is mixed into the cyclic olefin copolymer resin composition, and the composition is heated and crosslinked. The mixing ratio of the radical polymerization initiator is not particularly limited, but is usually 0.02 to 20 parts by mass, preferably 0.05 to 10 parts by mass, and more preferably 0.5 to 10 parts by mass per 100 parts by mass of the cyclic olefin copolymer (m). When the mixing ratio of the radical polymerization initiator is equal to or less than the upper limit, the dielectric properties of the crosslinked body are improved, and when the mixing ratio is equal to or more than the lower limit, the heat resistance and mechanical properties of the crosslinked body can be improved.

[0106] The radical polymerization initiator may be a known thermal radical polymerization initiator, a photoradical polymerization initiator, or a combination of these. When using a thermal radical polymerization initiator among these radical polymerization initiators, the initiator has a 10-hour half-life temperature of usually 80° C. or higher, preferably 120° C. or higher, from the viewpoint of storage stability. 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). peroxy ketals such as bis(t-butylperoxy)isophthalate, t-butyl peroxybenzoate, t-butyl peroxyacetate, etc.; hydroperoxides such as t-butyl hydroperoxide, t-hexyl hydroperoxide, cumin hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, etc.; bibenzyl compounds such as 2,3-dimethyl-2,3-diphenylbutane, etc.; 3,3,5,7,7-pentamethyl-1,2,4-trioxepane, etc.

[0107] Among the radical polymerization initiators, specific examples of the photoradical polymerization initiator 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 polymerization initiators. Examples of the sensitizer 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.

[0108] When crosslinking with sulfur or the like, a sulfur-based compound, and if necessary, a vulcanization accelerator and a vulcanization acceleration aid are mixed into the cyclic olefin copolymer resin composition, and then heated to carry out a crosslinking reaction. The amount of the sulfur-based compound is not particularly limited, but it is usually used in the range of 0.1 to 10 parts by mass, 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 economical standpoint, and when a vulcanization accelerator or a vulcanization acceleration aid is used in combination, it is usually used in the range of 0.1 to 20 parts by mass, 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 reaction products; butyraldehyde-aniline condensates; aldehyde amines such as hexamethylenetetramine and acetaldehyde ammonia; and aldehyde-ammonia. ammonium-based compounds; imidazoline-based compounds such as 2-mercaptoimidazoline; thiourea-based compounds such as thiocarbanilide, diethylthiourea, dibutylthiourea, trimethylthiourea, and diorthothylthiourea; 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 vulcanization accelerators include metal oxides such as zinc oxide, active zinc oxide, zinc carbonate, complex zinc oxide, magnesium oxide, litharge, red lead, and basic lead carbonate; fatty acid compounds such as stearic acid, oleic acid, lauric acid, and lead stearate; and organic amines and glycols such as triethanolamine and diethylene glycol.

[0109] The temperature for crosslinking the cyclic olefin copolymer resin composition with both radical polymerization initiator crosslinking and sulfur crosslinking is usually 100 to 300°C, preferably 120 to 250°C, 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 be sufficiently advanced. If the temperature is equal to or lower than the upper limit, coloring of the crosslinked body 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 high-temperature crosslinking conditions such as 300°C.

[0110] The cyclic olefin copolymer resin composition according to the present embodiment can also be crosslinked using a hydrosilyl group-containing compound having at least two hydrosilyl groups in one molecule. Crosslinking using a hydrosilyl group-containing compound can be carried out, for example, according to the method described in JP-A-2015-193680. Details are omitted here.

[0111] The method of crosslinking using electron beams or other radiation has the advantage that there are no restrictions on temperature or fluidity during molding, and examples of radiation include electron beams, gamma rays, UV rays, and the like.

[0112] In any of the methods using a radical polymerization initiator, sulfur, a hydrosilyl group-containing compound, etc., and the method using radiation, crosslinking can be carried out in the presence of a crosslinking assistant.

[0113] The crosslinking aid is not particularly 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. These crosslinking aids may be used alone or in combination.

[0114] The crosslinking reaction can be carried out by preparing a mixture of the cyclic olefin copolymer resin composition and the above-mentioned radical polymerization initiator, sulfur, hydrosilyl group-containing compound, or the like in a molten state, or by dissolving or dispersing the mixture in a solvent in a solution state, or by volatilizing the solvent from the solution state in which the mixture is dissolved in a solvent, forming the mixture into any desired shape such as a film or coating, and then allowing the crosslinking reaction to proceed further.

[0115] 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, a Banbury mixer, an extruder, a kneader, a continuous mixer, etc. In addition, the crosslinking reaction can be further carried out after molding by any method.

[0116] When the reaction is carried out in a solution state, the same solvents as those used in the above solution blending method can be used as the solvent.

[0117] When the crosslinking reaction is carried out using electron beams, other radiation, or UV, the reaction can be carried out after shaping by any method.

[0118] [Film or Sheet] The crosslinked product of the cyclic olefin copolymer resin composition according to the present embodiment can be formed into a film or sheet and used for various applications. Various known methods can be applied as a method for forming a film or sheet using the cyclic olefin copolymer resin composition according to the present embodiment. For example, a method of forming the film or sheet by applying the above-mentioned varnish to a supporting substrate such as a thermoplastic resin film, drying, and then performing a heat treatment or the like to crosslink the cyclic olefin copolymer resin composition can be mentioned. The method of applying the varnish to the supporting substrate is not particularly limited, and examples thereof include application using a spin coater, application using a spray coater, and application using a bar coater. Another example is a method in which the cyclic olefin copolymer resin composition according to this embodiment is melt molded to obtain a film or sheet.

[0119] [Laminate] The film or sheet according to this embodiment can be laminated on a substrate to form a laminate for various applications. Various known methods can be used as a method for forming the laminate according to this embodiment. For example, a laminate can be produced by laminating the film or sheet produced by the above-mentioned method onto a substrate, and, if necessary, heat curing the laminate by a press or the like. Furthermore, a laminate can be produced by laminating an electrical insulating layer containing the above-mentioned crosslinked body onto a conductor layer.

[0120] [Multi-layer molded body or multi-layer laminated film] The cyclic olefin copolymer resin composition according to the present embodiment may be formed on the surface layer of various multi-layer molded articles or multi-layer laminated films. In this case, the resin layer formed by the cyclic olefin copolymer resin composition is preferably 100 μm or less. Examples of various multilayer molded articles or multilayer laminated films include a multilayer molded article for an optical lens in which the cyclic olefin copolymer resin composition of this embodiment is formed on the surface of a resin optical lens, and a multilayer gas barrier film in which the cyclic olefin copolymer resin composition of this embodiment is formed on the surface of a resin film such as a PET film or a PE film to impart gas barrier properties.

[0121] [Prepreg] The prepreg according to the present embodiment is formed by combining the cyclic olefin copolymer resin composition according to the present embodiment with a sheet-like fiber substrate. The method for producing the prepreg is not particularly limited, and various known methods can be applied. For example, there is a method including a step of impregnating a sheet-like fiber substrate with the above-mentioned varnish to obtain an impregnated body, and a step of heating the obtained impregnated body to dry the solvent contained in the above-mentioned varnish. The above-mentioned varnish can be impregnated into the sheet-like fiber substrate by, for example, applying a predetermined amount of varnish to the sheet-like fiber substrate by a known method such as spray coating, dip coating, roll coating, curtain coating, die coating, or slit coating, and, if necessary, placing a protective film on top of it and pressing from above with a roller or the like. The process of heating the impregnated body and drying the solvent contained in the varnish is not particularly limited, but examples of the process include drying in air or nitrogen using a blower dryer in a batch process, or drying by passing through a heating furnace in a continuous process.

[0122] In this embodiment, after the varnish is impregnated into the sheet-like fiber substrate, the obtained impregnated body is heated to a predetermined temperature, whereby the solvent contained in the varnish evaporates and a prepreg is obtained. The fibers constituting the sheet-like fiber substrate according to this embodiment can be inorganic and / or organic fibers, and are not particularly limited. For example, organic fibers such as PET (polyethylene terephthalate) fibers, aramid fibers, ultra-high molecular weight polyethylene fibers, polyamide (nylon) fibers, and liquid crystal polyester fibers; inorganic fibers such as glass fibers, carbon fibers, alumina fibers, tungsten fibers, molybdenum fibers, titanium fibers, steel fibers, boron fibers, silicon carbide fibers, and silica fibers; and the like can be mentioned. Among these, organic fibers and glass fibers are preferred, and aramid fibers, liquid crystal polyester fibers, and glass fibers are particularly preferred. Examples of glass fibers include E glass, NE glass, S glass, D glass, H glass, and T glass. The impregnation of the sheet-like fiber substrate with the varnish is carried out, for example, by immersion and coating. The impregnation may be repeated multiple times as necessary. These sheet-like fiber substrates can be used alone or in combination of two or more, and the amount used is selected appropriately as desired, but is usually in the range of 10 to 90 mass%, preferably 20 to 80 mass%, and more preferably 30 to 70 mass% in the prepreg or laminate. If it is in this range, the dielectric properties and mechanical strength of the obtained laminate are highly balanced, which is preferable.

[0123] The thickness of the prepreg according to the present embodiment is appropriately selected depending on the purpose of use, but is usually 0.001 to 10 mm, preferably 0.005 to 1 mm, and more preferably 0.01 to 0.5 mm. This range is preferable because it allows the shapeability during lamination and the properties such as mechanical strength and toughness of the laminate obtained by curing to be fully exhibited.

[0124] [Circuit board] As described above, the cyclic olefin copolymer resin composition according to the present embodiment is excellent in dielectric properties, heat resistance, mechanical properties, and the like, and therefore can be suitably used for circuit boards. The method for producing the circuit board can be a generally known method, and is not particularly limited. For example, the film, sheet, or prepreg produced by the above-mentioned method is heated and cured by a lamination press or the like to form an electrical insulating layer. Next, a conductor layer is laminated on the obtained electrical insulating layer by a known method to produce a laminate. Thereafter, the conductor layer in the laminate is subjected to circuit processing or the like to obtain a circuit board.

[0125] Metals that can be used for the conductor layer include metals such as copper, aluminum, nickel, gold, silver, stainless steel, etc. Methods for forming the conductor layer include, for example, a method in which the metal is made into a foil or the like and heat-fused onto the electrical insulating layer, a method in which the metal is made into a foil or the like and attached to the electrical insulating layer using an adhesive, or a method in which a conductor layer made of the metal is formed on the electrical insulating layer by a method such as sputtering, vapor deposition, plating, etc. The circuit board may be either a single-sided board or a double-sided board.

[0126] 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; on-vehicle electronic devices such as electronic control system devices, on-vehicle communication devices, car navigation devices, millimeter-wave radars, and on-vehicle camera modules; semiconductor testing equipment, high-frequency measuring equipment, and the like.

[0127] [Foam] In addition, the cyclic olefin copolymer resin composition according to the present embodiment can be crosslinked and foamed to form a foam. At this time, the above-mentioned foaming agent may be added to the cyclic olefin copolymer resin composition.

[0128] [Application] The cyclic olefin copolymer (m), cyclic olefin copolymer resin composition, and crosslinked body according to the present embodiment are excellent in solvent resistance, heat resistance, mechanical strength, and transparency, and thus molded articles made of the crosslinked body can be used in a wide range of applications, including, for example, optical fibers, optical waveguides, optical disk substrates, optical filters, lenses, optical adhesives, optical filters for PDPs, coating materials for organic EL, base film substrates for solar cells in the aerospace field, coating materials for solar cells and thermal control systems, semiconductor elements, light-emitting diodes, electronic elements such as various types of memories, hybrid ICs, MCMs, circuit boards, prepregs and laminates used to form insulating layers for circuit boards, display components, and the like. and the like, overcoat materials or interlayer insulating materials, substrates for liquid crystal displays and solar cells, medical instruments, automobile parts, release agents, resin modifiers, transparent substrates for displays, parts for lithium ion batteries, semiconductor process parts, film capacitors, gas barrier coating materials, electric wire covering materials, automobile parts, aerospace parts, semiconductor process materials, electric wire covering materials, parts for lithium ion batteries, parts for fuel cells, capacitor films, flexible display parts, anchor coating materials, transparent adhesives, modifiers, crosslinking assistants, medical containers, parts for medical catheters, waterproof sealants, release agents, hard coat materials, and foaming modifiers. In particular, since it has excellent stability over time in dielectric properties, and also has excellent solvent resistance, heat resistance, transparency, mechanical properties, etc., it can be suitably used in high frequency applications such as high frequency circuit boards, etc. Furthermore, since it has excellent gas barrier properties, it can be suitably used as a substrate, film, or sheet for liquid crystal displays and solar cells.

[0129] 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. EXAMPLES

[0130] The present invention will be described in more detail below with reference to Synthesis Examples and Examples, but the present invention is not limited thereto in any way.

[0131] The composition of the cyclic olefin copolymer (m) used in the Synthesis Examples, Examples, and Comparative Examples was measured by the method described below.

[0132] composition; 1 H-NMR measurement was performed, and the cyclic non-conjugated diene content was calculated from the intensity of the peak derived from hydrogen directly bonded to the double bond carbon and the peak of other hydrogen.

[0133] The laminates obtained in the examples and comparative examples were evaluated by the following methods.

[0134] The following raw materials were used in the experiment:

[0135] Transition metal compounds (1): It was synthesized according to the method described in JP-A-2004-331965.

[0136] [ka]

[0137] MMAO (manufactured by Tosoh Finechem) Toluene (Wako Pure Chemical Industries, Ltd.: Wako special grade) 5-vinyl-2-norbornene (Tokyo Chemical Industry Co., Ltd.) Tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-Dodecene (Mitsui Chemicals, Inc.) Acetone (Fujifilm Wako Pure Chemical Industries, Ltd.: Wako Special Grade) Methanol (Fujifilm Wako Pure Chemical Industries, Ltd.: Wako special grade) Cyclohexane (Fujifilm Wako Pure Chemical Industries, Ltd.: Wako Special Grade)

[0138] Maleimide compound (L): Compound l-1: N-phenylmaleimide represented by the following formula (l-1) (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0139] [ka]

[0140] Compound l-2: N-cyclohexylmaleimide represented by the following formula (l-2) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0141] [ka]

[0142] Compound l-3: A bismaleimide compound represented by the following formula (l-3) (manufactured by Daiwa Kasei, BMI-TMH)

[0143] [ka]

[0144] Cyclic olefin copolymers (n): Polymer 1: Ethylene and tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene copolymer (product name: APEL 6509T, manufactured by Mitsui Chemicals, Inc.)

[0145] Radical polymerization initiator: Radical polymerization initiator 1: Percumyl D (manufactured by NOF Corporation)

[0146] Heat stabilizer: Hindered phenolic compounds (G): Compound (G)-1: Irganox 1010 (BASF) Compound (G)-2: KEMISORB114 (manufactured by Chemipro Chemicals) Hindered amine compounds (H): Compound (H)-1: CHIMASSORB2020FDL (molecular weight 2600-3400) (manufactured by BASF) Compound (H)-2: CHIMASSORB944FDL (molecular weight 2000-3100) (manufactured by BASF)

[0147] Cyclic olefin copolymer (m): [Synthesis Example 1 (Cyclic Olefin Copolymer (m-1))] In a 1 L stainless steel autoclave that had been thoroughly purged with nitrogen, 450 ml of toluene, 30 ml of 5-vinyl-2-norbornene (hereinafter also referred to as VNB), tetracyclo[4.4.0.1 2,5 .1 7,10 After adding 16 ml of ]-3-dodecene (hereinafter also referred to as TD), 0.9 mmol of MMAO (manufactured by Tosoh Finechem Co., Ltd.) in hexane in terms of Al, and 360 ml of hydrogen, ethylene was introduced into the system until the total pressure reached 0.6 MPa. A toluene solution of 0.028 mmol of transition metal compound (1) was added, and polymerization was carried out at 35°C for 180 minutes. Thereafter, 1 ml of methanol was injected to terminate the polymerization. The intrinsic viscosity [η] of the obtained cyclic olefin copolymer (m-1) was 0.35 (dL / g), 1 The composition ratio of the VNB-derived structure in the polymer determined by H-NMR was 26 mol%, the composition ratio of the TD-derived structure was 12 mol%, and the glass transition temperature measured by differential scanning calorimetry (DSC) was 96°C.

[0148] [Example 1] (Preparation of Varnish 1) The cyclic olefin copolymer (m-1) obtained in Synthesis Example 1, compound l-1 as monomaleimide, compound (G)-1 as hindered phenol compound (G), radical polymerization initiator 1 as radical polymerization (crosslinking) initiator, and toluene / cyclohexane mixed solvent as solvent were used and weighed according to the blending composition in Table 1. The weighed sample was stirred until fully dissolved to obtain the desired varnish-like cyclic olefin copolymer resin composition. The blending ratio of each raw material in Table 1 is in parts by mass.

[0149] (Laminate film production) The obtained varnish-like cyclic olefin copolymer resin composition was applied to a release-treated PET film at a speed of 10 mm / sec, and then dried for 4 minutes at 150°C in a nitrogen gas flow blower. Two of the obtained films were stacked, 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 laminate. The obtained laminate was evaluated for total light transmittance, glass transition temperature Tg, relative dielectric constant, dielectric loss tangent, and heat resistance stability. The obtained results are shown in Table 1.

[0150] (Evaluation of glass transition temperature Tg) The laminate obtained under the following conditions was subjected to solid viscoelastic temperature dispersion measurement to evaluate the glass transition temperature Tg, which was defined as the peak temperature of the loss tangent (tan δ). Equipment: RSA-III (manufactured by TA Instruments) Deformation mode: tension Temperature range: 25℃~300℃ Heating rate: 3℃ / min Frequency: 1Hz Set distortion: 0.1% Environment: Nitrogen atmosphere

[0151] (Evaluation of dielectric constant, dielectric tangent and heat resistance stability) The laminates obtained in the examples and comparative examples were measured for the dielectric constant and dielectric loss tangent at 10 GHz by a cylindrical cavity resonator method. The laminates were heat-treated at 125°C for 1000 hours, and the dielectric loss tangent was measured before the heat treatment, after 500 hours of heating, and after 1000 hours of heating, and the heat resistance stability of the laminates was evaluated based on the change in the dielectric loss tangent before and after the heat treatment. In addition, when the dielectric loss tangent was 0.014 or less, the dielectric properties were evaluated as good, and when the difference in the dielectric loss tangent after 1000 hours of heating and before heating was 0.001 or less, the heat resistance stability was evaluated as good.

[0152] (Transparency Assessment) For the laminates obtained in the examples and comparative examples, the total light transmittance (%) was measured using a haze meter according to a method conforming to JIS K 7136. Laminates with a total light transmittance of 80% or more were evaluated as transparent.

[0153] [Examples 2 and 3] According to the formulation in Table 1, the cyclic olefin copolymer (m-1) obtained in Synthesis Example 1, polymer 1 as the cyclic olefin copolymer (n), compound l-1 as the maleimide compound (L), (G)-2 as the hindered phenol compound (G), and compound (H)-1 as the hindered amine compound (H) were added, and a varnish and a laminate were produced and evaluated in the same manner as in Example 1. The obtained results are shown in Table 1.

[0154] [Examples 4, 5 and 6] Laminates 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. That is, polymer 1 was added as the cyclic olefin copolymer (n), compound l-2 was added instead of compound l-1 as the maleimide compound (L), (G)-2 was added as the hindered phenol compound (G), and compound (H)-1 was added as the hindered amine compound (H). The results are shown in Table 1.

[0155] [Comparative Example 1] A laminate was prepared and evaluated in the same manner as in Example 1, except that the blending composition was changed to that shown in Table 1. That is, the maleimide compound (L) was not added, and only the cyclic olefin copolymer (m-1) obtained in Synthesis Example 1 was added. The obtained results are shown in Table 1.

[0156] [Comparative Examples 2 and 3] Each laminate was produced 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.

[0157] [Comparative Example 4] A laminate was prepared and evaluated in the same manner as in Example 1, except that the composition was changed to that shown in Table 1. That is, the maleimide compound l-1 and the hindered phenol compound (G)-1 were not added, and the compound l-3 was added as the maleimide compound (L), and the compound (H)-2 was added as the hindered amine compound (H). The results are shown in Table 1.

[0158] [Table 1]

Claims

1. A cyclic olefin copolymer resin composition comprising a cyclic olefin copolymer (M) and a maleimide compound (L), The cyclic olefin copolymer (M) is One or more olefin-derived repeating units represented by the following general formula (I), One or more repeating units derived from a cyclic non-conjugated diene represented by the following general formula (III), and one or more repeating units derived from a cyclic olefin represented by the following general formula (V): The maleimide compound (L) is A monomaleimide compound having one maleimide group in the molecule, represented by the following general formula (X): a content of the maleimide compound (L) being 1 part by mass or more and 50 parts by mass or less, when the total amount of the cyclic olefin copolymer (M) and the maleimide compound (L) is 100 parts by mass. 【Chemistry 1】 [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. 【Chemistry 2】 [In the above general formula (III), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, and R ６１ ~R ７６ And R ａ１ and R ｂ１ may be the same or different, and each is 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 monocyclic or polycyclic ring. 【Chemistry 3】 [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 ~R ７８ And R ａ１ and R ｂ１ may be the same or different, and each is 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 ７５ ~R ７８ may be bonded to each other to form a monocyclic or polycyclic ring. 【Chemistry 4】 [In the above general formula (X), R is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.]

2. 2. The cyclic olefin copolymer resin composition according to claim 1, wherein the content of the repeating unit derived from the cyclic non-conjugated diene is in the range of 19 mol% or more and 40 mol% or less, when the total number of moles of the repeating units in the cyclic olefin copolymer (m) is 100 mol%.

3. In the cyclic olefin copolymer (m), the cyclic non-conjugated diene constituting the repeating unit derived from the cyclic non-conjugated diene contains 5-vinyl-2-norbornene, and the cyclic olefin constituting the repeating unit derived from the cyclic olefin is tetracyclo[4.4.0.1 ２，５ .1 ７，１０ 3. The cyclic olefin copolymer resin composition according to claim 1, further comprising ]-3-dodecene.

4. The cyclic olefin copolymer resin composition according to claim 3, The composition further comprises a cyclic olefin copolymer (n) different from the cyclic olefin copolymer (m), The cyclic olefin copolymer (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 cyclic olefin copolymer (m) and the cyclic olefin copolymer (n) is 100 mass%, A cyclic olefin copolymer resin composition, wherein the content of the cyclic olefin copolymer (m) is 5% by mass or more and 95% by mass or less, and the content of the cyclic olefin copolymer (n) is 5% by mass or more and 95% by mass or less.

5. The cyclic olefin copolymer resin composition according to any one of claims 1 to 4, wherein the monomaleimide compound is N-phenylmaleimide or N-cyclohexylmaleimide.

6. A varnish comprising the cyclic olefin copolymer resin composition according to any one of claims 1 to 5 and a solvent.

7. A crosslinked product obtained by crosslinking the cyclic olefin copolymer resin composition according to any one of claims 1 to 5.

8. A film or sheet comprising the crosslinked product according to claim 7.

9. A laminate comprising the crosslinked product according to claim 7.

10. A circuit board comprising an electrical insulating layer containing the crosslinked body according to claim 7 and a conductor layer provided on the electrical insulating layer.

11. An electronic device comprising the circuit board according to claim 10.

12. A prepreg comprising the cyclic olefin copolymer resin composition according to any one of claims 1 to 5 and a sheet-like fiber substrate.

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