Cyclic olefin copolymers, resin compositions, varnishes, prepregs, cured products, films, laminates, metal-clad laminates, printed circuit boards, and electronic devices

Abstract

This invention provides a cyclic olefin copolymer with an improved balance between heat resistance and solvent solubility. [Solution] A cyclic olefin copolymer comprising (A) repeating units derived from one or more olefins and (B) repeating units derived from a cyclic non-conjugated diene represented by general formula (III), wherein the content of the repeating units derived from the cyclic non-conjugated diene (B) exceeds 39 mol% when the total number of moles of repeating units is 100 mol%. TIFF2026068532000018.tif58124

Description

Technical Field

[0001] The present invention relates to a cyclic olefin copolymer, a resin composition, a varnish, a prepreg, a cured product, a film, a laminate, a metal-clad laminate, a printed wiring board, and an electronic device.

Background Art

[0002] Recently, in addition to the increase in wireless communication devices using high-frequency bands, the communication speed has been increased, and inevitably, a higher frequency band has often been used. Along with this, in order to reduce transmission loss at high frequencies to the limit, a small dielectric tangent is required for the material constituting the printed wiring board.

[0003] Patent Document 1 aims to obtain a crosslinked product excellent in the temporal stability and heat resistance of dielectric properties, and also excellent in transparency, mechanical properties, dielectric properties, and gas barrier properties. A cyclic olefin copolymer having a crosslinkable group is provided, and further, as a problem, (A) one or more repeating units derived from an olefin represented by a specific chemical formula (I), (B) a repeating unit derived from a cyclic non-conjugated diene represented by a specific chemical formula (III), and (C) one or more repeating units derived from a cyclic olefin represented by a specific chemical formula (V), and when the total molar number of the repeating units is 100 mol%, the repeating unit (B) derived from the cyclic non-conjugated diene contains 19 mol% to 36 mol%. A cyclic olefin copolymer having a crosslinkable group is described.

[0004] Furthermore, Patent Document 2 addresses the objective of providing a resin composition that can yield a crosslinked material suitable for circuit boards, such as an interlayer insulating film (also called an interlayer insulating layer in a circuit board) for a circuit board for a highly integrated computing device, and excellent dielectric properties, heat resistance, and mechanical properties in the high-frequency range, and is a cyclic olefin copolymer resin composition comprising a cyclic olefin copolymer (M) and a maleimide compound (L), wherein the cyclic olefin copolymer (M) comprises a cyclic olefin copolymer (m) comprising one or more repeating units derived from an olefin represented by a specific chemical formula (I), one or more repeating units derived from a cyclic non-conjugated diene represented by a specific chemical formula (III), and one or more repeating units derived from a cyclic olefin represented by a specific chemical formula (V), and the maleimide compound (L) has a solubility parameter (SP value) of 19 J as determined by the Fedors method. 1 / 2 / cm 3 / 2 Above, 26J 1 / 2 / cm 3 / 2 The following describes a cyclic olefin copolymer resin composition comprising a maleimide compound (l), which is a bismaleimide compound having at least two maleimide groups in its molecule, wherein 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. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] International Publication No. 2012 / 046443 [Patent Document 2] International Publication No. 2020 / 110958 [Overview of the project] [Problems that the invention aims to solve]

[0006] This invention provides a cyclic olefin copolymer with an improved balance between heat resistance and solvent solubility.

Means for Solving the Problem

[0007] As a result of intensive studies to solve the above problems, the inventors of the present invention have found that by specifying the composition of the repeating units contained in the cyclic olefin copolymer, a cyclic olefin copolymer having an improved balance between heat resistance and solvent solubility while satisfying the dielectric properties in the high-frequency region required for circuit boards can be obtained, and the present invention has been completed.

[0008] The present invention is as follows. [1] (A) One or more repeating units derived from olefins represented by the following general formula (I), and (B) Repeating units derived from cyclic non-conjugated dienes represented by the following general formula (III), and including, when the total number of moles of the repeating units is 100 mol%, a cyclic olefin copolymer in which the content of the repeating units (B) derived from the cyclic non-conjugated diene exceeds 39 mol%.

Chemical formula

Chemical formula

[10] The resin composition according to [9], comprising the radical initiator bibenzyl compounds.

[11] A resin composition according to any one of [8] to

[10] , further comprising an antioxidant.

[12] The storage modulus of the cured resin composition at 250°C is 1.0 × 10⁻⁶. 8 A resin composition according to any one of [8] to

[11] , which exceeds Pa.

[13] The resin composition according to any one of [8] to

[12] , wherein the dielectric loss tangent of the cured resin composition at 10 GHz is less than 0.0030.

[14] A varnish comprising a resin composition described in any of [8] to

[13] and a solvent.

[15] The varnish according to

[14] , wherein when the total amount of the varnish is 100 parts by mass, the content of the resin composition in the varnish is 5 parts by mass or more.

[16] A prepreg comprising a fibrous substrate impregnated with a resin composition described in any of [8] to

[13] or a varnish described in any of

[14] to

[15] .

[17] A cured product of any of the resin compositions described in [8] to

[13] .

[18] A film comprising the resin composition described in any of [8] to

[13] or the cured product described in

[17] .

[19] A laminate comprising the prepreg described in

[16] or the film described in

[18] .

[20] A metal-clad laminate comprising a metal foil on at least one side of the laminate described in

[19] . [twenty one] A printed circuit board manufactured using the prepreg described in

[16] or the metal-clad laminate described in

[20] . [twenty two] An electronic device comprising the cured product described in

[17] or the printed circuit board described in

[21] . [twenty three] The electronic device described in

[22] includes a high-speed communication module. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a cyclic olefin copolymer with an improved balance between heat resistance and solvent solubility. [Modes for carrying out the invention]

[0010] The present invention will be described below based on embodiments. In these embodiments, unless otherwise specified, "A~B" indicating a numerical range represents A or greater and B or less.

[0011] 1. Cyclic olefin copolymer (m) The cyclic olefin copolymer of this embodiment (hereinafter also referred to as cyclic olefin copolymer (m)) will be described in detail below.

[0012] First, the cyclic olefin copolymer (m) is a cyclic olefin copolymer comprising (A) one or more repeating units derived from an olefin represented by the following general formula (I), and (B) repeating units derived from a cyclic non-conjugated diene represented by the following general formula (III).

[0013] [ka] [In the above general formula (I), R 300 This represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms.

[0014] [ka] [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 ~R 76 Furthermore, R a1 and R b1 These 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 from 0 to 10, and R 75 and R 76 These may be bonded to each other to form a monocycle or polycycle.

[0015] Furthermore, when the total number of moles of repeating units is set to 100 mol%, the content of repeating units (B) derived from the cyclic non-conjugated diene is greater than 39 mol%, preferably 40 mol% or more, more preferably 42 mol% or more, even more preferably 44 mol% or more, and even more preferably 45 mol% or more. When the content of repeating units (B) derived from cyclic non-conjugated dienes is above the lower limit mentioned above, the balance between the heat resistance and solvent solubility of the cyclic olefin copolymer is improved. Furthermore, a cyclic olefin copolymer with improved dielectric properties can be obtained. Although the mechanism by which the above-mentioned cyclic olefin copolymer (m) solves the above-mentioned problems is not clear, it is thought that if the cyclic olefin copolymer (m) has repeating units (A) derived from the olefin and repeating units (B) derived from the cyclic non-conjugated diene, and the content of the repeating units (B) derived from the cyclic non-conjugated diene is within a predetermined range, the polarity of the cyclic olefin copolymer (m) can be controlled to an extent that enables solvent solubility. Furthermore, since the structure of the repeating units (B) derived from the cyclic non-conjugated diene is thought to contribute to the thermosetting properties of the composition containing the cyclic olefin copolymer (m), it is presumed that the heat resistance can be improved if the content of the repeating units (B) derived from the cyclic non-conjugated diene is within a predetermined range. From the above, it is considered that the cyclic olefin copolymer (m) of this embodiment can improve the balance between heat resistance and solvent solubility.

[0016] 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 (B) derived from the cyclic non-conjugated diene is preferably 70 mol% or less, more preferably 65 mol% or less, even more preferably 60 mol% or less, even more preferably 55 mol% or less, and even more preferably 53 mol% or less, from the viewpoint of further improving the balance between heat resistance and solvent solubility. Furthermore, when the total number of moles of repeating units in the cyclic olefin copolymer (m) is set to 100 mol%, the content of repeating units (B) derived from the cyclic non-conjugated diene is preferably more than 39 mol% and 70 mol% or less, more preferably 40 mol% to 65 mol%, even more preferably 42 mol% to 60 mol%, even more preferably 44 mol% to 55 mol%, and even more preferably 45 mol% to 53 mol%, from the viewpoint of further improving the balance between heat resistance and solvent solubility.

[0017] When the total number of moles of repeating units in the cyclic olefin copolymer (m) is taken as 100 mol%, the content of the olefin-derived repeating units (A) is preferably 30 mol% or more and less than 61 mol%, more preferably 35 mol% or more and 60 mol%, even more preferably 40 mol% or more and 58 mol%, and even more preferably 45 mol% or more and 56 mol%, from the viewpoint of further improving the balance between heat resistance and solvent solubility.

[0018] The molar ratio ((A) / (B)) of the content of repeating units (A) derived from the olefin to the content of repeating units (B) derived from the cyclic non-conjugated diene in the cyclic olefin copolymer (m) is preferably 0.43 or more and less than 1.56, more preferably 0.50 or more and 1.55 or less, and even more preferably 0.70 or more and 1.53 or less, or 0.90 or more and 1.52 or less, from the viewpoint of further improving the balance between heat resistance and solvent solubility.

[0019] Furthermore, the cyclic olefin copolymer (m) may further contain one or more repeating units (C) derived from cyclic olefins represented by the following general formula (V). [ka] [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 Furthermore, R a1 and R b1 These 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 75 ~R 78 These may be bonded to each other to form a monocycle or polycycle.

[0020] From the viewpoint of further improving the balance between heat resistance and solvent solubility, the content of repeating units (C) derived from the cyclic olefin in the cyclic olefin copolymer (m) is preferably 0 mol% or more and less than 31 mol%, more preferably 0 mol% or more and 25 mol%, even more preferably 0 mol% or more and 20 mol%, even more preferably 0 mol% or more and 15 mol%, even more preferably 0 mol% or more and 10 mol%, even more preferably 0 mol% or more and 5 mol%, even more preferably 0 mol% or more and 3 mol%, and even more preferably 0 mol% or more and 1 mol%.

[0021] An olefin monomer that can be used as a copolymerizing raw material for a cyclic olefin copolymer (m) is a monomer that undergoes addition copolymerization to give a skeleton represented by the above general formula (I), and can be an olefin represented by the following general formula (Ia).

[0022] [ka]

[0023] 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 olefins 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 cured product with superior heat resistance, mechanical properties, dielectric properties, transparency, and gas barrier properties, one or two of these, consisting of ethylene and propylene, are preferred, with ethylene being more preferred. Two or more types of olefin monomers represented by the above formula (Ia) may be used.

[0024] A cyclic non-conjugated diene monomer, which can be one of the copolymerization raw materials for a cyclic olefin copolymer (m), can be subjected to addition copolymerization to form a structural unit represented by the above general formula (III). Specifically, a cyclic non-conjugated diene represented by the following general formula (IIIa), which corresponds to the above general formula (III), can be used.

[0025] [ka]

[0026] In the above general formula (IIIa), u is 0 or 1, v is 0 or a positive integer, preferably an integer between 0 and 2, more preferably 0 or 1, w is 0 or 1, R 61 ~R 76 Furthermore, R a1 and R b1 These 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 from 0 to 10, and R 75 and R 76 These elements may be bonded to each other to form a monocycle or polycycle.

[0027] The cyclic non-conjugated dienes represented by the above general formula (IIIa) are not limited to, but examples include the cyclic non-conjugated dienes represented by the following chemical formulas. Among these, the cyclic non-conjugated dienes represented by the general formula (IIIa), i.e., the cyclic non-conjugated dienes that constitute the repeating unit (B) derived from the cyclic non-conjugated diene, are 5-vinyl-2-norbornene and 8-vinyl-9-methyltetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene, 5-allyl-2-norbornene and 8-vinyl-tetracyclo[4.4.0.1 2,5 .1 7,10It is preferable to include at least one selected from the group consisting of ]-3-dodecene, more preferably at least one selected from the group consisting of 5-vinyl-2-norbornene and 5-allyl-2-norbornene, and even more preferably 5-vinyl-2-norbornene.

[0028] [ka]

[0029] [ka]

[0030] When a cyclic olefin copolymer (m) contains repeating units (C) derived from a cyclic olefin, a cyclic olefin monomer, which can be one of the copolymerization raw materials for the cyclic olefin copolymer (m), can be added copolymerized to form a constituent unit represented by the above general formula (V). Specifically, a cyclic olefin monomer represented by the following general formula (Va), which corresponds to the above general formula (V), can be used.

[0031] [ka]

[0032] In the above general formula (Va), u is 0 or 1, v is 0 or a positive integer, preferably an integer between 0 and 2, more preferably 0 or 1, w is 0 or 1, R 61 ~R 78 Furthermore, R a1 and R b1 These 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 75 ~R 78 These elements may be bonded to each other to form a monocycle or polycycle.

[0033] For specific examples of cyclic olefins represented by the above general formula (Va), compounds described in International Publication No. 2006 / 118261 can be used. The cyclic olefin represented by the above general formula (Va), that is, the cyclic olefin constituting the repeating unit (C) derived from the cyclic olefin, is bicyclo[2.2.1]-2-heptene (also called norbornene) and tetracyclo[4.4.0.1 2,5 .1 7,10 Preferably, it contains at least one selected from the group consisting of ]-3-dodecene (also called tetracyclododecene), and tetracyclo[4.4.0.1 2,5 .1 7,10 It is more preferable to include ]-3-dodecene.

[0034] The number-average molecular weight (Mn) of the cyclic olefin copolymer (m), measured by gel permeation chromatography on a polystyrene basis, is preferably 1,000 or more, more preferably 3,000 or more, and even more preferably 5,000 or more, from the viewpoint of further improving the balance between heat resistance and solvent solubility. Furthermore, from the viewpoint of further improving moldability, such as impregnation into the fiber substrate and wiring embedding properties during the fabrication of printed circuit boards, it is preferably 100,000 or less, more preferably 80,000 or less, even more preferably 60,000 or less, even more preferably 40,000 or less, even more preferably 30,000 or less, and even more preferably 25,000 or less. The number-average molecular weight (Mn) of a cyclic olefin copolymer (m) can be controlled by polymerization conditions such as polymerization catalyst, co-catalyst, H2 addition amount, and polymerization temperature.

[0035] The cyclic olefin copolymer (m) of this embodiment can be produced, for example, by the method described in Japanese Patent Application Publication No. 2004-331965.

[0036] 2.Resin composition The resin composition of this embodiment contains a cyclic olefin copolymer (m).

[0037] [Radical initiator] The resin composition of this embodiment preferably further contains a radical initiator, and from the viewpoint of obtaining a cured product with an even better balance between heat resistance and electrical properties, the radical initiator preferably contains bibenzyl compounds, and more preferably contains a compound represented by the following general formula (1).

[0038] [ka]

[0039] In general formula (1), R1 to R 10 Each of these is independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or a halogenated alkyl group having 1 to 20 carbon atoms, and R 11 From R 14 Each of these is independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or a halogenated alkyl group having 1 to 20 carbon atoms, and R 11 From R 14 At least one of these is, independently, an alkyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or a halogenated alkyl group having 1 to 20 carbon atoms.

[0040] In general formula (1), R1 to R 10 From the viewpoint of obtaining a cured product with even greater heat resistance, preferably each element is independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and more preferably a hydrogen atom.

[0041] In general formula (1), R 11 From R 14From the viewpoint of obtaining a cured product with even greater heat resistance, preferably each is independently an alkyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or a halogenated alkyl group having 1 to 20 carbon atoms; more preferably each is independently an alkyl group having 1 to 20 carbon atoms; even more preferably each is independently an alkyl group having 1 to 4 carbon atoms; and even more preferably each is independently a methyl group or an ethyl group.

[0042] The content of the radical initiator in the resin composition of this embodiment is preferably 0.02 parts by mass or more and 20.0 parts by mass or less, more preferably 0.05 parts by mass or more and 20.0 parts by mass or less, even more preferably 0.1 parts by mass or more and 20.0 parts by mass or less, even more preferably 0.51.0 parts by mass or more and 10.0 parts by mass or less, even more preferably 1.5 parts by mass or more and 10.0 parts by mass or less, even more preferably 2.0 parts by mass or more and 10.0 parts by mass or less, even more preferably 2.5 parts by mass or more and 5.0 parts by mass or less, even more preferably 3.0 parts by mass or more and 5.0 parts by mass or less, and even more preferably 3.5 parts by mass or more and 5.0 parts by mass or less, from the viewpoint of obtaining a cured product with an even better balance of heat resistance and solvent solubility per 100 parts by mass of cyclic olefin copolymer (m).

[0043] [Antioxidant] The resin composition of this embodiment preferably further contains an antioxidant. The antioxidant preferably includes one or more selected from the group consisting of phenolic antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, and thioether-based antioxidants, and more preferably includes a phenolic antioxidant. This further improves the storage stability of the resin composition during storage and after it has been formed into a film.

[0044] Examples of phenolic antioxidants include acrylate-based phenolic compounds described in Japanese Patent Publication No. 63-179953 and Japanese Patent Publication No. 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, 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] Alkyl-substituted phenolic compounds such as undecane, 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-trimethyl-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., pentaerythrimethyl-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; 6 At least one triazine group-containing phenolic compounds such as -(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 can be selected from the group consisting of these. 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.

[0045] Examples of phosphorus-based antioxidants include triphenyl phosphite, diphenylisodecyl 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, and 2,2-methylenebis(4,6-di-t-butylphenyl) Monophosphine compounds such as cultyl 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(diphenylmonoalkyl(C12~C15) phosphite), 1,1,3-tris(2-methyl-4-di-tridecylphosphite-5-t-butylphenyl)butane, tetrakis(2,4-di-t-butylphenyl)-4,4'-biphenylenediphosphite, cyclic neopentanetetraylbis(iso) At least one compound selected from the group consisting of diphosphite compounds such as decyl phosphite, cyclic neopentanetetraylbis(nonylphenyl phosphite), cyclic neopentanetetraylbis(2,4-di-t-butylphenyl phosphite), cyclic neopentanetetraylbis(2,4-dimethylphenyl phosphite), and cyclic neopentanetetraylbis(2,6-di-t-butylphenyl phosphite) is mentioned. Among these, monophosphite compounds are preferred, and at least one compound selected from the group consisting of tris(nonylphenyl) phosphite, tris(dinonylphenyl) phosphite, and tris(2,4-di-t-butylphenyl) phosphite is more preferred.

[0046] Examples of sulfur-based antioxidants 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 thioether-based antioxidants 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.

[0047] If the resin composition of this embodiment contains an antioxidant, the amount of antioxidant in the resin composition of this embodiment is preferably 0.001 parts by mass or more, more preferably 0.005 parts by mass or more, even more preferably 0.01 parts by mass or more, even more preferably 0.02 parts by mass or more, and preferably 1.0 part by mass or less, more preferably 0.50 parts by mass or less, even more preferably 0.30 parts by mass or less, even more preferably 0.20 parts by mass or less, and even more preferably 0.10 parts by mass or less, based on 100 parts by mass of the cyclic olefin copolymer (m).

[0048] [Additives] The resin composition of this embodiment may further contain various additives depending on the purpose. The amount of additives added is appropriately selected according to the application, within a range that does not impair the purpose of the present invention. The above-mentioned additives include one or more additives selected from the group consisting of heat stabilizers, weather stabilizers, radiation stabilizers, plasticizers, lubricants, mold release agents, nucleating agents, friction wear improvers, flame retardants, foaming agents, antistatic agents, colorants, antifogging agents, antiblocking agents, impact resistant agents, surface wetting improvers, fillers, hydrochloric acid absorbers, and metal deactivators. For example, heat stabilizers, light stabilizers, ultraviolet absorbers, radiation resistant agents, plasticizers, lubricants, mold release agents, nucleating agents, friction wear improvers, flame retardants, foaming agents, antistatic agents, colorants, antifogging agents, antiblocking agents, impact resistant agents, surface wetting improvers, fillers, hydrochloric acid absorbers, metal deactivators, etc., as described in paragraphs 0085 to 0120 of International Publication No. 2017 / 150218, can be used.

[0049] The resin composition of this embodiment can be prepared, for example, by mixing a cyclic olefin copolymer (m) with other components as needed. Mixing methods include melt blending using an extruder or the like, or solution blending by dissolving and dispersing in a suitable solvent, such as saturated hydrocarbons like heptane, hexane, decane, or cyclohexane; or aromatic hydrocarbons like toluene, benzene, or xylene.

[0050] The dielectric loss tangent of the cured resin composition of this embodiment at 10 GHz is preferably less than 0.0030, more preferably less than 0.0025, even more preferably less than 0.0020, even more preferably less than 0.0018, even more preferably less than 0.0015, even more preferably less than 0.0012, and even more preferably 0.0010 or less, for example, it may be 0.0001 or more, 0.0003 or more, or 0.0005 or more.

[0051] The dielectric loss tangent of the cured resin composition of this embodiment at 10 GHz can be obtained by the following <Method 1>. <Method 1> First, the resin composition of this embodiment is coated onto a release-treated PET film at a speed of 10 mm / second, and then dried in a forced-air dryer under a nitrogen flow at 150°C for 4 minutes to obtain a laminated film of the PET film and the resin composition of this embodiment. The two resulting laminated films are stacked so that the resin compositions are in contact with each other, and then pressurized to 3.5 MPa using a vacuum press. The temperature is raised at a constant rate from room temperature (25°C) and held at 180°C for 60 minutes. After that, the film is peeled off the PET film to obtain a pre-cured laminated film. Next, the pre-curing laminated film is sandwiched between polyimide films, pressurized to 3.5 MPa using a vacuum press, heated at a constant rate from room temperature (25°C), held at 220°C for 120 minutes, and then peeled off from the polyimide films to obtain the post-curing laminated film. Next, the dielectric loss tangent Df of the cured laminated film at 10 GHz is measured using the cylindrical cavity resonator method.

[0052] From the viewpoint of further improving the balance between low dielectric properties, heat resistance, and solvent solubility in the high-frequency range, the storage modulus of the cured resin composition of this embodiment at 250°C is preferably 1.0 × 10⁻⁶. 8 Pa exceeded 1.0×10 10 Pa or less, more preferably 1.3 × 10 8 Pa or more 5.0×10 9 Pa or less, more preferably 1.5 × 10 8 Pa or more 2.0×10 9 Pa or less, more preferably 2.0 × 10 8 Pa or more 1.5×10 9 Pa or less, more preferably 2.5 × 10 8 Pa or more 1.0×10 9 Pa or less, more preferably 3.0 × 10 8 Pa or more 3.0×10 9 It is below Pa.

[0053] The storage modulus at 250°C of the cured product obtained by heating the resin composition of this embodiment at 220°C can be obtained by the following <Method 2>. <Method 2> The solid viscoelastic temperature dispersion measurement of the cured laminated film obtained by the above-mentioned Method 1 was performed under the following conditions, and the storage modulus at 250°C was determined. Deformation mode: Tension Temperature range: 25℃~300℃ Heating rate: 3°C / min Frequency: 1Hz Setting distortion: 0.1% Environment: Under a nitrogen atmosphere

[0054] 3. Varnish The varnish of this embodiment comprises the resin composition of this embodiment and a solvent.

[0055] The solvent of this embodiment includes, for example, one or more selected from the group consisting of saturated hydrocarbons such as heptane, hexane, octane, and decane; alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, and decahydronaphthalene; aromatic hydrocarbons such as toluene, benzene, xylene, mesitylene, and pseudocumene; alcohols such as methanol, ethanol, isopropyl alcohol, butanol, pentanol, hexanol, propanediol, and phenol; ketone solvents such as acetone, methyl isobutyl ketone, methyl ethyl ketone, pentanone, hexanone, cyclohexanone, isophorone, and acetophenone; cellsolves such as methyl cellsolve and ethyl cellsolve; esters such as methyl acetate, ethyl acetate, butyl acetate, methyl propionate, and butyl formate; and halogenated hydrocarbons such as trichloroethylene, dichloroethylene, and chlorobenzene. The solvent in this embodiment preferably comprises one or more selected from the group consisting of heptane, decane, cyclohexane, methylcyclohexane, decahydronaphthalene, toluene, benzene, xylene, mesitylene, and pseudocumene, and more preferably comprises toluene, from the viewpoint of further improving the solubility and availability of the resin composition. Furthermore, when the total amount of the varnish of this embodiment is 100 parts by mass, the content of the resin composition of this embodiment in the varnish is preferably 5 parts by mass or more and 80 parts by mass or less, more preferably 10 parts by mass or more and 70 parts by mass or less, even more preferably 15 parts by mass or more and 60 parts by mass or less, and even more preferably 18 parts by mass or more and 55 parts by mass or less.

[0056] In this embodiment, the method for preparing the varnish may be any method, but for example, it may include a step of mixing the resin composition and the solvent. There are no restrictions on the order in which the components are mixed, and it can be done in any way, such as all at once or in stages. There are also no restrictions on the apparatus for preparing the varnish, and it may be carried out using any batch or continuous apparatus capable of stirring and mixing. The temperature when preparing the varnish can be arbitrarily selected within the range from room temperature to the boiling point of the solvent. Alternatively, the varnish may be prepared by using the reaction solution obtained when the cyclic olefin copolymer (m) is obtained as the solvent.

[0057] 4. Prepreg The prepreg of this embodiment is obtained by impregnating a fibrous substrate with the resin composition or varnish of this embodiment.

[0058] The prepreg of this embodiment is preferably formed by compounding the resin composition of this embodiment with a sheet-like fibrous substrate. The method for manufacturing the prepreg is not particularly limited, and various known methods can be applied. For example, one method includes the steps of impregnating a sheet-like fibrous substrate with the aforementioned varnish to obtain an impregnated body, and heating the obtained impregnated body to dry the solvent contained in the varnish. The impregnation of a sheet-like fibrous substrate with varnish can be carried out, for example, by applying a predetermined amount of varnish to the sheet-like fibrous substrate using known methods such as spray coating, dip coating, roll coating, curtain coating, die coating, or slit coating, and if necessary, by placing a protective film on top and pressing it from above with a roller or the like. Furthermore, the process of heating the impregnated material and drying the solvent contained in the varnish is not particularly limited, but examples of methods include drying in air or nitrogen using a forced-air dryer in a batch process, or drying by passing it through a heating furnace in a continuous process. After impregnating a sheet-like fibrous substrate with varnish, the resulting impregnated material is heated to a predetermined temperature, causing the solvent contained in the varnish to evaporate and yielding a prepreg.

[0059] The fibers constituting the sheet-like fibrous substrate can be inorganic or organic, and are not particularly limited. Examples include organic fibers such as PET (polyethylene terephthalate) fibers, polystyrene fibers, aramid fibers, ultra-high molecular weight polyethylene fibers, polyamide (nylon) fibers, and liquid crystal polyester fibers; and 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. Among these, preferably at least one selected from the group consisting of organic fibers and glass fibers, and more preferably at least one selected from the group consisting of aramid fibers, liquid crystal polyester fibers, and glass fibers. Examples of glass fibers include E glass, NE glass, S glass, D glass, H glass, T glass, etc. The impregnation of the sheet-like fibrous substrate with varnish is carried out, for example, by dipping and coating. Impregnation may be repeated multiple times as needed. These sheet-like fibrous substrates can be used individually or in combination of two or more types. The amount used can be appropriately selected as desired, but is, for example, 10% by mass or more, preferably 20% by mass or more, more preferably 30% by mass or more, and also, for example, 90% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less, in the prepreg or laminate. Within this range, the dielectric properties and mechanical strength of the resulting laminate are well balanced and therefore preferable.

[0060] The thickness of the prepreg is appropriately selected depending on the intended use, but is, for example, 0.001 mm or more, preferably 0.005 mm or more, more preferably 0.01 mm or more, and also, for example, 10 mm or less, preferably 1 mm or less, more preferably 0.5 mm or less. Within this range, the shapeability during lamination and the properties such as mechanical strength and toughness of the resulting laminate are fully exhibited, making it suitable.

[0061] 5. Cured products and films The film of this embodiment includes the resin composition of this embodiment or a cured product of the resin composition of this embodiment.

[0062] The cured product obtained by curing the resin composition of this embodiment can be formed into a film and used for various applications. In this embodiment, "film" is a general term for planar molded products and includes sheets, membranes, tapes, etc. Various known methods can be applied to cure the resin composition of this embodiment into a cured product and form it into a film. For example, one method involves applying the above-mentioned varnish to a support substrate such as a thermoplastic resin film, drying it, and then crosslinking the resin composition by heat treatment or the like to obtain a cured product and form a film made of the resin composition of this embodiment. As the thermoplastic resin film, PET film, polyimide resin film, etc., can be used. The method of applying the varnish to the support substrate is not particularly limited, but examples include application using a spin coater, application using a spray coater, application using a bar coater, etc. Another method involves melt-molding the resin composition of this embodiment to obtain a film, and then curing the resin composition by crosslinking it through heat treatment or the like to form a film made of the resin composition of this embodiment.

[0063] 6. Laminate The laminate of this embodiment includes the prepreg of this embodiment or the film of this embodiment.

[0064] The film or prepreg of this embodiment can be laminated onto a substrate and used as a laminate for various applications. For example, it can be used as an organic insulating film requiring low dielectric properties, or as a curable adhesive sheet for devices having an adhesive layer. Various known methods can be applied to form the laminate in this embodiment. For example, a laminate can be produced by laminating a film manufactured by the above method onto a substrate and then heat-curing it by pressing or other means as needed. Furthermore, a laminate can also be fabricated by laminating an electrical insulating layer containing the aforementioned cured material onto a conductive layer.

[0065] The cured product obtained by curing the resin composition of this embodiment may be formed on the surface layer of various multilayer molded articles or multilayer laminated films. Examples of various multilayer molded articles or multilayer laminated films include, for example, a multilayer molded article for optical lenses in which the film of this embodiment is formed on the surface of a resin optical lens, and a multilayer gas barrier film in which the film 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.

[0066] 7.Metal clad laminate The metal-clad laminate of this embodiment includes a metal foil on at least one side of the laminate of this embodiment.

[0067] The laminate of this embodiment may be a metal-clad laminate obtained by laminating a metal foil onto at least one surface of the laminate of this embodiment and then heat-curing it by lamination pressing or the like. Alternatively, the metal foil may be bonded to both sides of the laminate. Examples of metal foils include copper foil, aluminum foil, nickel foil, gold foil, silver foil, and stainless steel foil. From the viewpoint of economy, processability, thermal conductivity, and electrical conductivity, electrolytic copper foil is preferred. Various known methods can be applied to produce the metal-clad laminate of this embodiment. For example, a metal-clad laminate can be produced by laminating a metal foil onto the laminate of this embodiment and then heat-curing it by pressing or other means as needed.

[0068] The metal-clad laminate of this embodiment uses a cured product obtained by curing the resin composition of this embodiment, and therefore has an improved balance of low dielectric properties and heat resistance in the high-frequency range, making it suitable for printed circuit boards. Therefore, the metal-clad laminate of this embodiment can be suitably used as an insulating layer material for printed circuit boards.

[0069] 8. Printed circuit board The printed circuit board of this embodiment is manufactured using the prepreg of this embodiment or the metal-clad laminate of this embodiment.

[0070] The cured product obtained by curing the resin composition of this embodiment has an improved balance of low dielectric properties and heat resistance in the high-frequency range, and therefore can be suitably used in printed circuit boards. A generally known method can be used as the manufacturing method for a printed circuit board, and is not particularly limited. For example, a film or laminate manufactured by the aforementioned method is heat-cured by lamination press or the like to form an electrical insulating layer. Next, a conductor layer is laminated onto the obtained electrical insulating layer by a known method to create a laminate. After that, a printed circuit board can be obtained by processing the conductor layer in the laminate into a circuit.

[0071] Examples of metals that can be used for the conductive layer include copper, aluminum, nickel, gold, silver, and stainless steel. Methods for forming the conductive layer include, for example, heat-sealing the metals in foil form onto the electrical insulating layer, bonding the metals in foil form onto the electrical insulating layer using an adhesive, or forming a conductive layer made of the metals on the electrical insulating layer by sputtering, vapor deposition, plating, etc. The printed circuit board can be either single-sided or double-sided.

[0072] 9.Electronic equipment The electronic device of this embodiment includes the cured product of this embodiment or the printed circuit board of this embodiment.

[0073] The electronic device of this embodiment 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, base station antennas, millimeter-wave antennas, and RFID antennas; communication devices such as mobile phones, smartphones, PHS phones, PDAs, and tablet terminals; digital devices such as personal computers, televisions, digital cameras, digital video cameras, POS terminals, wearable devices, and digital media players; in-vehicle electronic equipment such as electronic control systems, in-vehicle communication equipment, car navigation equipment, millimeter-wave radar, and in-vehicle camera modules; semiconductor testing equipment, high-frequency measuring equipment, etc.; and high-speed communication modules.

[0074] The electronic device of this embodiment preferably includes a high-speed communication module.

[0075] The high-speed communication module of this embodiment is a high-speed communication module manufactured using the cured product of this embodiment or the printed circuit board of this embodiment. The high-speed communication module of this embodiment is, for example, a communication module formed by mounting semiconductor chips on the printed circuit board of this embodiment, and is particularly suitable for applications that utilize high-frequency signals such as wireless communication equipment and network infrastructure equipment, and have a large amount of information to communicate and high speed.

[0076] The cured product obtained by curing the resin composition of this embodiment has a good balance of low dielectric properties and heat resistance in the high-frequency range, and can therefore be used in applications such as optical fibers, optical waveguides, optical disc substrates, optical filters, lenses, optical adhesives, optical filters for PDPs, coating materials for organic ELs, base film substrates for solar cells in the aerospace field, coating materials for solar cells and thermal control systems, semiconductor elements, light-emitting diodes, various memory devices and other electronic elements, hybrid ICs, MCMs, printed circuit boards, prepregs and laminates used to form insulating layers of printed circuit boards, overcoat materials or interlayer insulating materials for display components, substrates for liquid crystal displays and solar cells, medical devices, automotive components, resin modifiers, transparent substrates for displays, gas barrier coating materials, aerospace components, semiconductor process materials, wire coating materials, lithium-ion battery components, fuel cell components, capacitor films, flexible display components, anchor coating materials, transparent adhesives, and hard coating materials. In particular, the cured product obtained by curing the resin composition of this embodiment has excellent heat resistance, low dielectric properties in the high-frequency range, and a good balance of performance such as insulation and mechanical properties, so it can be suitably used in printed circuit boards, and is even more suitably used in high-frequency applications such as high-frequency printed circuit boards.

[0077] The embodiments of the present invention have been described above, but these are merely examples, and various other configurations can also be adopted. Furthermore, the present invention is not limited to the embodiments described above, and any modifications, improvements, etc., that do not impair the effects of the present invention are included in the present invention. [Examples]

[0078] This embodiment will be described in detail below with reference to examples and other relevant information. However, this embodiment is not limited in any way to the descriptions of these examples.

[0079] (raw materials) Cyclic olefin copolymer (m): Synthesis method will be described later. Radical initiator 1: 2,3-dimethyl-2,3-diphenylhexane (manufactured by Acros Organics) Antioxidant 1: Phenolic antioxidant (Pentaerythritol = Tetrakis[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate), Product name: Irganox 1010, manufactured by BASF)

[0080] The following raw materials were used for the synthesis of the cyclic olefin copolymer (m). Transition metal compounds (1): It was synthesized by the method described in Japanese Patent Publication No. 2004-331965.

[0081] [ka]

[0082] Modified methylaluminoxane (MMAO, manufactured by Tosoh Finechem Co., Ltd.) Toluene (manufactured by Wako Pure Chemical Industries, Ltd.: Wako Special Grade) Cyclohexane (manufactured by Wako Pure Chemical Industries, Ltd.: Reagent grade) Hexane (manufactured by Wako Pure Chemical Industries, Ltd.: Reagent Grade) 5-Vinyl-2-norbornene (hereinafter referred to as VNB) (manufactured by Tokyo Chemical Industry Co., Ltd.) Tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-Dodecene (hereinafter, TD) (manufactured by Mitsui Chemicals, Inc.) Isobutyl alcohol (manufactured by Tokyo Chemical Industry Co., Ltd.) Methanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.: Wako Special Grade)

[0083] Method for measuring the content of each structural unit constituting a cyclic olefin copolymer. The content of structural unit (A), structural unit (B), and structural unit (C) was measured using a JEOL Ltd. "EXcalibur270" nuclear magnetic resonance spectrometer under the following conditions. Cumulative number of times: 16-64 Measurement temperature: room temperature The above measurements 1The peaks originating from hydrogen directly bonded to the double bond carbon and those from other hydrogen atoms were calculated from the 1H-NMR spectrum.

[0084] Furthermore, the molecular weight of the cyclic olefin copolymer (m) used in the synthesis example, the example, and the comparative example was measured by the method described below.

[0085] <Number average molecular weight (Mn)> The number-average molecular weight (Mn) of the cyclic olefin copolymer (m) was measured by GPC and determined as a value equivalent to standard polystyrene. The GPC measurement was performed under the following conditions. Equipment: GPC HLC-8321 (manufactured by Tosoh Corporation) Solvent: o-dichlorobenzene Columns: TSKgel GMH6-HT x 2, TSKgel GMH6-HTL x 2 (both manufactured by Tosoh Corporation) Flow rate: 1.0mL / min Sample: 1 mg / mL o-dichlorobenzene solution Temperature: 140℃

[0086] [Synthesis Example 1 (Cyclic Olefin Copolymer (m-1)] A 0.5 L glass autoclave, thoroughly purged with nitrogen, was charged with 250 mL of toluene and 8.0 mL of 5-vinyl-2-norbornene (VNB). The liquid and gas phases were saturated with ethylene gas at a flow rate of 100 L / h and hydrogen gas at a flow rate of 30 L / h. Then, 1.0 mmol (in terms of Al) of MMAO hexane solution was added to the autoclave, followed by 5 μmol of transition metal compound (1). The reaction was carried out at 25°C and atmospheric pressure under the ethylene / hydrogen gas atmosphere for 20 minutes, after which polymerization was stopped by adding a small amount of isobutyl alcohol. After polymerization was complete, deionized water was added to the resulting polymer solution and stirred for 1 hour, after which the organic layer was filtered through filter paper. This organic layer was placed in acetone to precipitate the polymer, stirred, and then filtered through filter paper. The resulting polymer was dried under reduced pressure at 80°C for 10 hours to obtain an ethylene / VNB copolymer. The composition ratio of VNB-derived structures in the polymer, as determined by NMR, was 40 mol%, and the number-average molecular weight, as determined by GPC, was 17,000.

[0087] [Synthesis Example 2 (Cyclic Olefin Copolymer (m-2))] A 0.5 L glass autoclave, thoroughly purged with nitrogen, was charged with 150 mL of cyclohexane / hexane (volume ratio, 9 / 1) mixed solvent and 150 mL of 5-vinyl-2-norbornene (VNB). The liquid and gas phases were saturated with ethylene gas at a flow rate of 50 L / h and hydrogen gas at a flow rate of 30 L / h. Then, 1.0 mmol (Al equivalent) of MMAO hexane solution was added to the autoclave, followed by 5 μmol of transition metal compound (1). The reaction was carried out at 25°C and atmospheric pressure under the ethylene / hydrogen gas atmosphere for 20 minutes, after which polymerization was stopped by adding a small amount of isobutyl alcohol. After polymerization was complete, deionized water was added to the resulting polymer solution and stirred for 1 hour, after which the organic layer was filtered through filter paper. This organic layer was placed in acetone to precipitate the polymer, stirred, and then filtered through filter paper. The resulting polymer was dried under reduced pressure at 80°C for 10 hours to obtain an ethylene / VNB copolymer. The composition ratio of VNB-derived structures in the polymer, as determined by NMR, was 50 mol%, and the number-average molecular weight, as determined by GPC, was 6,000.

[0088] [Synthesis Example 3 (Cyclic Olefin Copolymer (m-3))] A 0.5 L glass autoclave, thoroughly purged with nitrogen, was charged with 250 mL of toluene and 6.0 mL of 5-vinyl-2-norbornene (VNB). The liquid and gas phases were saturated with ethylene gas at a flow rate of 100 L / h and hydrogen gas at a flow rate of 30 L / h. Then, 1.0 mmol (in terms of Al) of MMAO hexane solution was added to the autoclave, followed by 5 μmol of transition metal compound (1). The reaction was carried out at 25°C and atmospheric pressure under the ethylene / hydrogen gas atmosphere for 20 minutes, after which polymerization was stopped by adding a small amount of isobutyl alcohol. After polymerization was complete, deionized water was added to the resulting polymer solution and stirred for 1 hour, after which the organic layer was filtered through filter paper. This organic layer was placed in acetone to precipitate the polymer, stirred, and then filtered through filter paper. The resulting polymer was dried under reduced pressure at 80°C for 10 hours to obtain an ethylene / VNB copolymer. The composition ratio of VNB-derived structures in the polymer, as determined by NMR, was 30 mol%, and the number-average molecular weight, as determined by GPC, was 19,000.

[0089] [Synthesis Example 4 (Cyclic Olefin Copolymer (m-4))] In a 1 L stainless steel autoclave that has been thoroughly purged with nitrogen, add 380 mL of toluene, 94 mL of 5-vinyl-2-norbornene (VNB), and tetracyclo[4.4.0.1 2,5 .1 7,10 26 mL of ]-3-dodecene (TD), 1.5 mmol (in terms of Al) of MMAO hexane solution, and 870 mL of hydrogen were added to the system, and then ethylene was introduced into the system until the total pressure reached 0.78 MPa. 33 μmol of transition metal compound (1) dissolved in toluene was added, and polymerization was carried out at 35°C for 180 minutes. After polymerization was complete, deionized water was added to the obtained polymer solution and stirred for 1 hour, and then the organic layer was filtered through filter paper. This organic layer was placed in acetone to precipitate the polymer, stirred, and then filtered through filter paper. The obtained polymer was dried under reduced pressure at 80°C for 10 hours to obtain an ethylene / TD / VNB copolymer. The composition ratio of TD-derived structures in the polymer, as determined by NMR, was 6.5 mol%, the composition ratio of VNB-derived structures was 35.9 mol%, and the number-average molecular weight, as determined by GPC, was 11,900.

[0090] [Example 1] (Varnish preparation) The cyclic olefin copolymer (m-1) obtained in Synthesis Example 1 was dissolved in toluene to a solid content of 20% by mass. Then, according to the formulation composition in Table 1, the mixture was stirred until antioxidant 1 and radical initiator 1 were sufficiently dissolved to obtain the desired varnish-like cyclic olefin copolymer composition. In Table 1, the unit of the blending ratio of each raw material is parts by mass, and the amount of antioxidant 1 and radical initiator 1 added is the value when the total amount of cyclic olefin copolymer (m-1) is 100 parts by mass.

[0091] (Fabrication of laminated films) The resulting varnish-like cyclic olefin copolymer resin composition was coated onto a release-treated PET film at a speed of 10 mm / second, and then dried in a forced-air dryer under a nitrogen atmosphere at 150°C for 4 minutes. Two of the resulting films were stacked so that the resin compositions were in contact with each other, and then pressurized to 3.5 MPa using a vacuum press. The temperature was raised at a constant rate from room temperature (25°C) and held at 180°C for 60 minutes. The films were then removed and separated from the PET film to obtain a pre-cured laminated film. Next, the obtained pre-cured laminated film was sandwiched between polyimide films, pressurized to 3.5 MPa using a vacuum press, heated at a constant rate from room temperature (25°C), held at 220°C for 120 minutes, and then peeled off from the polyimide films to obtain the cured laminated film. The resulting cured laminated film was evaluated for dielectric loss tangent, heat resistance, and solvent solubility according to the following procedure. The results are shown in Table 1.

[0092] (Evaluation of dielectric loss tangent) The dielectric loss tangent Df at 10 GHz was measured for the obtained cured laminated film using the cylindrical cavity resonator method, and evaluated as follows. Materials with a dielectric loss tangent of less than 0.0012 were classified as "A" for their excellent low dielectric properties in the high-frequency range, those between 0.0012 and 0.0030 were classified as "B", and those with a dielectric loss tangent of 0.0030 or more were classified as "C" for their inferior low dielectric properties in the high-frequency range.

[0093] (Heat resistance evaluation) The heat resistance of the obtained cured laminated film was evaluated by performing a solid viscoelastic temperature dispersion measurement under the following conditions: Storage modulus at 250°C was 1.0 × 10⁻⁶. 8 Those exceeding Pa are designated as "A" for superior heat resistance, and 1.0 × 10 8 Those with a Pa rating below Pa were classified as "B" due to their inferior heat resistance. Equipment: RSA-III (manufactured by T.A. Instruments Corporation) Deformation mode: Tension Temperature range: 25℃~300℃ Heating rate: 3°C / min Frequency: 1Hz Setting distortion: 0.1% Environment: Under a nitrogen atmosphere

[0094] (Solubility evaluation) As described below, solutions of cyclic olefin copolymers with two different solid content concentrations were prepared and their solubility was evaluated. A cyclic olefin copolymer solution with a solid content of 20% by mass; In the varnish preparation process described above, samples in which the cyclic olefin copolymer (m-1) dissolved without any problems in toluene were designated as "A," while samples in which undissolved material remained after stirring overnight were designated as "B." A cyclic olefin copolymer solution with a solid content of 50% by mass; When 1 g of the cyclic olefin copolymer (m-1) obtained in Synthesis Example 1 was mixed with 1 g of toluene and stirred overnight, the product that dissolved without any problems was designated as "a", and the product that remained undissolved after stirring overnight was designated as "b".

[0095] [Example 2 and Comparative Examples 1-3] Except for the changes in the compound composition shown in Table 1, varnish and cured laminated films were prepared and evaluated in the same manner as in Example 1. The results obtained are shown in Table 1.

[0096] [Table 1]

[0097] The resin composition of the example yielded a cured product with improved heat resistance in addition to solvent solubility at high solid content. This indicates that the cyclic olefin copolymer of this embodiment can achieve an improved balance between heat resistance and solvent solubility.

Claims

1. (A) One or more repeating units derived from olefins represented by the following general formula (I), (B) Repeating units derived from cyclic non-conjugated dienes represented by the following general formula (III), Includes, When the total number of moles of repeating units is set to 100 mol%, A cyclic olefin copolymer having a content of more than 39 mol% of repeating units (B) derived from the cyclic non-conjugated diene. 【Chemistry 1】 [In the above general formula (I), R ３００ This 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, R ６１ ~R ７６ And R ａ１ and R ｂ１ These 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 from 0 to 10, and R ７５ and R ７６ These may be bonded to each other to form a monocycle or polycycle.

2. The cyclic olefin copolymer according to claim 1, wherein the content of repeating units (B) derived from the cyclic non-conjugated diene is 70 mol% or less.

3. The cyclic olefin copolymer according to claim 1, wherein the content of the repeating unit (A) derived from the olefin is 30 mol% or more and less than 61 mol%.

4. The cyclic olefin copolymer according to claim 1, wherein the molar ratio ((A) / (B)) of the content of repeating units (A) derived from the olefin to the content of repeating units (B) derived from the cyclic non-conjugated diene is 0.43 or more and less than 1.

56.

5. The cyclic olefin copolymer according to claim 1, wherein the content of one or more repeating units (C) derived from a cyclic olefin represented by the following general formula (V) is 0 mol% or more and less than 31 mol%. 【Transformation 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 as well as R ａ１ and R ｂ１ may be the same as 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, and R ７５ ~R ７８ may be bonded to each other to form a monocyclic or polycyclic ring.〕

6. The cyclic non-conjugated diene constituting the repeating unit (B) derived from the cyclic non-conjugated diene is 5-vinyl-2-norbornene, 8-vinyl-9-methyltetracyclo[4.4.0.1 ２，５ 1. ７，１０ ]-3-dodecene, 5-allyl-2-norbornene and 8-vinyl-tetracyclo[4.4.0.1 ２，５ 1. ７，１０ The cyclic olefin copolymer according to claim 1, comprising at least one selected from the group consisting of ]-3-dodecene.

7. The cyclic olefin constituting the repeating unit (C) derived from the cyclic olefin is bicyclo[2.2.1]-2-heptene and tetracyclo[4.4.0.1 ２，５ 1. ７，１０ The cyclic olefin copolymer according to claim 5, comprising at least one selected from the group consisting of ]-3-dodecene.

8. A resin composition comprising the cyclic olefin copolymer described in claim 1.

9. The resin composition according to claim 8, further comprising a radical initiator.

10. The resin composition according to claim 9, wherein the radical initiator comprises bibenzyl compounds.

11. The resin composition according to claim 8, further comprising an antioxidant.

12. The storage modulus of the cured resin composition at 250°C is 1.0 × 10⁻⁶. ８ The resin composition according to claim 8, wherein the Pa is greater than the limit.

13. The resin composition according to claim 8, wherein the dielectric loss tangent of the cured resin composition at 10 GHz is less than 0.0030.

14. A varnish comprising the resin composition according to claim 8 and a solvent.

15. The varnish according to claim 14, wherein when the total amount of the varnish is 100 parts by mass, the content of the resin composition in the varnish is 5 parts by mass or more.

16. A prepreg comprising a fibrous substrate impregnated with the resin composition described in claim 8 or a varnish containing the resin composition and a solvent.

17. A cured product of the resin composition according to claim 8.

18. A film comprising the resin composition described in claim 8 or a cured product of the resin composition.

19. A laminate comprising the prepreg described in claim 16 or the film described in claim 18.

20. A metal-clad laminate containing a metal foil on at least one side of the laminate according to claim 19.

21. A printed circuit board manufactured using the metal-clad laminate described in claim 20.

22. An electronic device comprising the cured product according to claim 17.

23. The electronic device according to claim 22, wherein the electronic device includes a high-speed communication module.

Images