Resin composition, varnish, prepreg, film, laminate, metal-clad laminate, printed wiring board, and electronic device

Abstract

Disclosed is a resin composition which contains a thermosetting cyclic olefin (co)polymer (m) that has a crosslinkable group (α), and a radical initiator (A), wherein the radical initiator (A) contains a compound represented by general formula (1). (In general formula (1), R1 to R10 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1-20 carbon atoms, a cycloalkyl group having 3-20 carbon atoms, an aromatic hydrocarbon group having 6-20 carbon atoms, or a halogenated alkyl group having 1-20 carbon atoms, R11 to R14 are each independently an alkyl group having 1-20 carbon atoms, a cycloalkyl group having 3-20 carbon atoms, an aromatic hydrocarbon group having 6-20 carbon atoms, or a halogenated alkyl group having 1-20 carbon atoms, and at least one of R11 to R14 is independently an alkyl group having 2-20 carbon atoms, a cycloalkyl group having 3-20 carbon atoms, an aromatic hydrocarbon group having 6-20 carbon atoms, or a halogenated alkyl group having 1-20 carbon atoms.)

Description

Resin composition, varnish, prepreg, film, laminate, metal clad laminate, printed wiring board and electronic device

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

[0002] Recently, the use of high-frequency bands has become more common due to an increase in wireless communication devices and faster communication speeds. Accordingly, in order to minimize transmission loss at high frequencies, materials that make up printed wiring boards are also required to have a small dielectric loss tangent.

[0003] Patent Document 1 describes a cyclic olefin copolymer having a crosslinkable group, which can give a crosslinked product having excellent stability over time of dielectric properties and heat resistance, and further excellent transparency, mechanical properties, dielectric properties, and gas barrier properties, and further provides a crosslinked product having excellent properties. The crosslinked olefin copolymer contains (A) repeating units derived from one or more olefins represented by a specific chemical formula (I), (B) repeating units derived from a cyclic non-conjugated diene represented by a specific chemical formula (III), and (C) repeating units derived from one or more cyclic olefins represented by a specific chemical formula (V), wherein the repeating units (B) derived from the cyclic non-conjugated diene account for 19 mol% to 36 mol% when the total number of moles of the repeating units is taken as 100 mol%. Patent Document 1 also describes that the invention described in Patent Document 1 has an object to provide a cyclic olefin copolymer having a crosslinkable group, which can give a crosslinked product having excellent stability over time of dielectric properties and heat resistance, and further excellent transparency, mechanical properties, dielectric properties, and gas barrier properties, and further provides a crosslinked product having excellent properties.

[0004] Furthermore, Patent Document 2 discloses a resin composition capable of producing a crosslinked body having excellent dielectric properties, heat resistance, and mechanical properties in a high frequency range, suitable for an interlayer insulating film (also referred to as an interlayer insulating layer in a circuit board) for a circuit board intended for a highly integrated arithmetic device, and for circuit boards, etc., as a material for circuit boards. The resin composition contains a cyclic olefin copolymer (M) and a maleimide compound (L), wherein the cyclic olefin copolymer (M) contains a cyclic olefin copolymer (m) containing one or more olefin-derived repeating units represented by a specific chemical formula (I), one or more cyclic non-conjugated diene-derived repeating units represented by a specific chemical formula (III), and one or more cyclic olefin-derived repeating units 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 and a cyclic olefin copolymer resin composition comprising a maleimide compound (l) which is a bismaleimide compound having at least two maleimide groups in the molecule, the content of the maleimide compound (L) being 1 part by mass or more and 50 parts by mass or less when the total of the cyclic olefin copolymer (M) and the maleimide compound (L) is 100 parts by mass. Patent Document 2 describes that the invention described in Patent Document 2 provides a resin composition which, as a circuit board material, can give an interlayer insulating film for circuit boards (also called an interlayer insulating layer in the circuit board) intended for highly integrated arithmetic devices, and a crosslinked product which has excellent dielectric properties, heat resistance, and mechanical properties in the high frequency range, which is suitable for circuit boards, etc.

[0005] International Publication No. WO 2012 / 046443 International Publication No. WO 2020 / 110958

[0006] The present invention provides a resin composition that can give a cured product at a crosslinking temperature of 200° C. or less, which has an improved balance between low dielectric properties in the high frequency range and heat resistance.

[0007] The present invention is as follows: 1. A resin composition comprising a thermosetting cyclic olefin (co)polymer (m) having a crosslinkable group (α) and a radical initiator (A), wherein the radical initiator (A) comprises a compound represented by the following general formula (1): [In general formula (1), R １ From R １０ are each independently a hydrogen atom, a halogen atom, an alkyl group having from 1 to 20 carbon atoms, a cycloalkyl group having from 3 to 20 carbon atoms, an aromatic hydrocarbon group having from 6 to 20 carbon atoms, or a halogenated alkyl group having from 1 to 20 carbon atoms; R １１ From R １４ are each 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; R １１ From R １４ and at least one of R 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. １ From R １０ 3. The resin composition according to 1., wherein R is each 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. １ From R １０ 4. The resin composition according to 2., wherein in the general formula (1), R １１ From R １４ and each independently represent an alkyl group having from 2 to 20 carbon atoms, a cycloalkyl group having from 3 to 20 carbon atoms, an aromatic hydrocarbon group having from 6 to 20 carbon atoms, or a halogenated alkyl group having from 1 to 20 carbon atoms. 5. In the general formula (1), R １１ From R １４6. The resin composition according to 4., wherein R is independently an alkyl group having 2 to 20 carbon atoms. １１ From R １４ is an ethyl group. 7. The resin composition according to any one of 1. to 6., wherein the content of the radical initiator (A) in the resin composition is 0.02 parts by mass or more and 20.0 parts by mass or less per 100 parts by mass of the thermosetting cyclic olefin (co)polymer (m). 8. The resin composition according to any one of 1. to 7., wherein the thermosetting cyclic olefin (co)polymer (m) comprises: (A) one or more repeating units derived from olefins represented by the following general formula (I), (B) one or more repeating units derived from cyclic non-conjugated dienes represented by the following general formula (III), and (C) one or more repeating units derived from cyclic olefins represented by the following general formula (V). [In the above general formula (I), R ３００ represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms. [In the above general formula (III), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, and R ６１ ~R ７６ and R ａ１ and R ｂ１ may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms; R １０４ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, t is a positive integer of 0 to 10, and R ７５ and R ７６ may be bonded to each other to form a monocyclic or polycyclic ring. [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 ｂ１may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms; R ７５ ~R ７８ may be bonded to each other to form a monocycle or polycycle.] 9. The resin composition according to 8., wherein, when the total number of moles of repeating units in the thermosetting cyclic olefin (co)polymer (m) is taken as 100 mol%, the content of the olefin-derived repeating unit (A) is 10 mol% or more and 90 mol% or less, the content of the cyclic non-conjugated diene-derived repeating unit (B) is 1 mol% or more and 40 mol% or less, and the content of the cyclic olefin-derived repeating unit (C) is 1 mol% or more and 50 mol% or less. 10. The resin composition according to 8. or 9., wherein the cyclic non-conjugated diene constituting the cyclic non-conjugated diene-derived repeating unit (B) includes 5-vinyl-2-norbornene. 11. The resin composition according to 8. or 9., wherein the cyclic olefin constituting the cyclic olefin-derived repeating unit (C) is tetracyclo[4.4.0.1 ２，５ .1 ７，１０ 12. The resin composition according to any one of items 1. to 11., further comprising an antioxidant (B). 13. The resin composition according to any one of items 1. to 12., wherein a cured product obtained by heating the resin composition at 200°C has a dielectric loss tangent at 10 GHz of less than 0.0020. 14. The resin composition according to any one of items 1. to 13., wherein ΔTg, represented by the following formula (10), is 30°C or higher. ΔTg=Tg １ -Tg ０ (10) [In formula (10), Tg ０ is the glass transition temperature of the thermosetting cyclic olefin (co)polymer (m), and Tg １is the glass transition temperature of a cured product obtained by heating the resin composition at 200°C.] 15. A varnish comprising the resin composition according to any one of 1. to 14. and a solvent. 16. A prepreg obtained by impregnating a fiber substrate with the resin composition according to any one of 1. to 14. or the varnish according to 15.. 17. A film comprising a cured product of the resin composition according to any one of 1. to 14.. 18. A laminate comprising the prepreg according to 16. or the film according to 17.. 19. A metal clad laminate comprising a metal foil on at least one surface of the laminate according to 18.. 20. A printed wiring board produced using the prepreg according to 16. or the metal clad laminate according to 19.. 21. An electronic device comprising the film according to 17. or the printed wiring board according to 20.. 22. The electronic device according to 21., wherein the electronic device includes a module compatible with high-speed communication.

[0008] According to the present invention, it is possible to provide a resin composition that can give a cured product having an improved balance of low dielectric properties and heat resistance in the high frequency range at a crosslinking temperature of 200° C. or less.

[0009] Hereinafter, the present invention will be described based on embodiments. In this embodiment, "A to B" indicating a numerical range means A or more and B or less unless otherwise specified. In this specification, "cyclic olefin (co)polymer" means at least one polymer selected from the group consisting of homopolymers of cyclic olefins and copolymers of cyclic olefins and monomer components other than cyclic olefins. Each monomer constituting the thermosetting cyclic olefin (co)polymer (m) according to the present invention may be a monomer obtained from a fossil raw material, a monomer obtained from an animal or plant raw material, or a monomer derived from biomass. In this embodiment, -CH=CH in the (meth)acrylic group ２ is not included in the vinyl group.

[0010] 1. Resin Composition The resin composition of this embodiment will be described below.

[0011] The resin composition of the present embodiment is a resin composition containing a thermosetting cyclic olefin (co)polymer (m) having a crosslinkable group (α) and a radical initiator (A), and the radical initiator (A) contains a compound represented by the following general formula (1):

[0012]

[0013] In general formula (1), R １ From R １０ are each independently a hydrogen atom, a halogen atom, an alkyl group having from 1 to 20 carbon atoms, a cycloalkyl group having from 3 to 20 carbon atoms, an aromatic hydrocarbon group having from 6 to 20 carbon atoms, or a halogenated alkyl group having from 1 to 20 carbon atoms; R １１ From R １４ are each 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; R １１ From R １４ At least one of the groups 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.

[0014] According to the studies of the present inventors, when producing the cured product described in Patent Document 1, crosslinking at a temperature exceeding 200° C. is required, and there is room for improvement at crosslinking temperatures of 200° C. or less. As a result of extensive studies, the present inventors have found that by using a resin composition in which a specific radical initiator is combined with a thermosetting cyclic olefin (co)polymer, it is possible to obtain a cured product with an improved balance of low dielectric properties and heat resistance in the high frequency range even at a crosslinking temperature of 200° C. or less, and have completed the present invention.

[0015] The components contained in the resin composition of this embodiment will be described below.

[0016] [Radical Initiator (A)] The radical initiator (A) contained in the resin composition of the present embodiment will be described below.

[0017] In general formula (1), R １ From R １０ are preferably each independently a hydrogen atom, an alkyl group having from 1 to 20 carbon atoms, a cycloalkyl group having from 3 to 20 carbon atoms, or an aromatic hydrocarbon group having from 6 to 20 carbon atoms, and more preferably a hydrogen atom, from the viewpoint of being able to obtain a cured product having an even better balance of low dielectric properties and heat resistance in the high frequency range at a crosslinking temperature of 200°C or less.

[0018] In general formula (1), R １１ From R １４ From the viewpoint of being able to obtain a cured product having an even better balance of low dielectric properties and heat resistance in the high frequency range at a crosslinking temperature of 200°C or less, each of them is preferably an alkyl group having from 2 to 20 carbon atoms, a cycloalkyl group having from 3 to 20 carbon atoms, an aromatic hydrocarbon group having from 6 to 20 carbon atoms, or a halogenated alkyl group having from 1 to 20 carbon atoms, more preferably each is independently an alkyl group having from 2 to 20 carbon atoms, and even more preferably an ethyl group. Examples of the radical initiator (A) include DEDPH (2,3-diethyl-2,3-diphenylhexane, manufactured by Fluorochem, １ From R １０ is a hydrogen atom, and R １１ From R １４ is an ethyl group.

[0019] The content of the radical initiator (A) in the resin composition is preferably 0.02 parts by mass or more, more preferably 0.05 parts by mass or more, even more preferably 0.1 parts by mass or more, even more preferably 0.5 parts by mass or more, even more preferably 1.0 parts by mass or more, even more preferably 1.5 parts by mass or more, even more preferably 2.0 parts by mass or more, even more preferably 2.1 parts by mass or more, even more preferably 2.5 parts by mass or more, even more preferably 3.0 parts by mass or more, even more preferably 3.5 parts by mass or more, even more preferably 4.0 parts by mass or more, and even more preferably 4.2 parts by mass or more, relative to 100 parts by mass of the thermosetting cyclic olefin (co)polymer (m), from the viewpoint of being able to obtain a cured product having an even better balance of low dielectric properties and heat resistance in the high-frequency range at a crosslinking temperature of 200°C or less; and from the viewpoint of further improving the dielectric properties of the cured product, it is preferably 20.0 parts by mass or less, more preferably 10.0 parts by mass or less, even more preferably 5.0 parts by mass or more. and, from the viewpoint of being able to obtain a cured product having an even more improved balance between low dielectric properties and heat resistance in the high frequency range at a crosslinking temperature of 200°C or less, the content 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 0.5 parts by mass or more and 20.0 parts by mass or less, even more preferably 1.0 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 2.1 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, even more preferably 3.5 parts by mass or more and 5.0 parts by mass or less, even more preferably 4.0 parts by mass or more and 5.0 parts by mass or less, and even more preferably 4.2 parts by mass or more and 5.0 parts by mass or less.

[0020] [Thermosetting Cyclic Olefin (Co)polymer (m) Having Crosslinking Group (α)] The resin composition of this embodiment contains a thermosetting cyclic olefin (co)polymer (m) having a crosslinkable group (α) (hereinafter, also simply referred to as "cyclic olefin (co)polymer (m)"). The cyclic olefin (co)polymer (m) can be any cyclic olefin (co)polymer that is thermosetting and contains a repeating unit derived from a cyclic olefin, and may be, for example, a ring-opening polymer of a cyclic olefin or an addition polymer of a monomer such as an α-olefin with a cyclic olefin. Furthermore, the cyclic olefin (co)polymer (m) has a crosslinkable group (α), which is a functional group that can be used in a crosslinking reaction, from the viewpoint of improving the heat resistance of the cured product obtained by forming a crosslinked structure. Examples of the crosslinkable group (α) include crosslinkable functional groups such as a vinyl group, a vinylidene group, a vinylene group, a vinyl group substituted with an alkyl group, a phenyl group, or an alkylphenyl group, a vinylidene group substituted with an alkyl group, a phenyl group, or an alkylphenyl group, a vinylene group substituted with an alkyl group, a phenyl group, or an alkylphenyl group, a maleimide group, a thiol group, a thienyl group, a silyl group, an epoxy group, an oxazoline group, a (meth)acrylic group, and a carboxyl group, and preferably a vinyl group. When the cyclic olefin (co)polymer (m) has a crosslinkable group (α), it can form a crosslinked structure with the crosslinking aid (A) described below, thereby further improving low thermal expansion. One molecule of the cyclic olefin (co)polymer (m) may contain one or more crosslinkable groups (α), and when one molecule has multiple crosslinkable groups (α), they may be of one type or two or more types.

[0021] The content of the thermosetting cyclic olefin (co)polymer (m) in the resin composition of this embodiment is preferably 50 parts by mass or more, more preferably 70 parts by mass or more, even more preferably 80 parts by mass or more, even more preferably 90 parts by mass or more, still more preferably 95 parts by mass or more, and for example, 99 parts by mass or less, per 100 parts by mass of the resin composition of this embodiment, from the viewpoint of being able to obtain a cured product having an even better balance of low dielectric properties and heat resistance in the high frequency range at a crosslinking temperature of 200°C or less.

[0022] The cyclic olefin (co)polymer (m) of the present embodiment preferably contains (A) one or more repeating units derived from olefins represented by the following general formula (I), (B) one or more repeating units derived from cyclic non-conjugated dienes represented by the following general formula (III), and (C) one or more repeating units derived from cyclic olefins represented by the following general formula (V).

[0023]

[0024] 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.

[0025]

[0026] In the 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, and R ６１ ~R ７６ and R ａ１ and R ｂ１ may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms; R １０４ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, t is a positive integer of 0 to 10, and R ７５ and R ７６ may be bonded to each other to form a monocyclic or polycyclic ring.

[0027]

[0028] 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, and R ６１ ~R ７８ and R ａ１ and R ｂ１may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms; R ７５ ~R ７８ may be bonded to each other to form a monocyclic or polycyclic ring.

[0029] When the cyclic olefin (co)polymer (m) is a (co)polymer (m) containing the repeating units (A) to (C), when the total number of moles of repeating units in the thermosetting cyclic olefin (co)polymer (m) is taken as 100 mol%, the content of the olefin-derived repeating unit (A) is preferably 10 mol% or more and 90 mol% or less, more preferably 20 mol% or more and 85 mol% or less, even more preferably 30 mol% or more and 80 mol% or less, even more preferably 40 mol% or more and 70 mol% or less, even more preferably 50 mol% or more and 70 mol% or less, and even more preferably 55 mol% or more and 65 mol% or less, and the content of the cyclic non-conjugated diene-derived repeating unit (B) is preferably 1 mol% or more and 40 mol% or less, more preferably The content of the repeating unit (C) derived from the cyclic olefin is preferably 1 mol% to 50 mol%, more preferably 3 mol% to 40 mol%, more preferably 5 mol% to 35 mol%, even more preferably 7 mol% to 30 mol%, even more preferably 10 mol% to 30 mol%, even more preferably 15 mol% to 30 mol%, and even more preferably 20 mol% to 30 mol%. The content of the repeating unit (C) derived from the cyclic olefin is preferably 1 mol% to 50 mol%, more preferably 3 mol% to 40 mol%, even more preferably 10 mol% to 35 mol%, even more preferably 10 mol% to 30 mol%, even more preferably 10 mol% to 25 mol%, even more preferably 10 mol% to 20 mol%, and even more preferably 10 mol% to 15 mol%. When the content of each repeating unit in the cyclic olefin (co)polymer (m) is within the above range, the cured product obtained from the resin composition can have improved dielectric properties and heat resistance. Furthermore, a cured product can be obtained with an improved balance of mechanical properties, dielectric properties, transparency, and gas barrier properties.

[0030] The olefin monomer that can be one of the copolymerization raw materials for the cyclic olefin (co)polymer (m) is a monomer that provides the skeleton represented by the above formula (I) upon addition copolymerization, and can be an olefin represented by the following general formula (Ia):

[0031]

[0032] In the above general formula (Ia), R ３００ represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms. Examples of the olefin represented by general formula (Ia) include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. From the viewpoint of obtaining a cured product having better heat resistance, mechanical properties, dielectric properties, transparency, and gas barrier properties, among these, one or both of the group consisting of ethylene and propylene are preferred, and ethylene is more preferred. Two or more types of olefin monomers represented by the above formula (Ia) may be used.

[0033] The cyclic non-conjugated diene monomer, which can be one of the copolymerization raw materials for the cyclic olefin (co)polymer (m), can be addition copolymerized to form the constituent unit represented by the above formula (III). Specifically, a cyclic non-conjugated diene represented by the following general formula (IIIa), which corresponds to the above general formula (III), can be used.

[0034]

[0035] 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, and R ６１ ~R ７６ and R ａ１ and R ｂ１may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms; R １０４ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, t is a positive integer of 0 to 10, and R ７５ and R ７６ may be bonded to each other to form a monocyclic or polycyclic ring.

[0036] The cyclic non-conjugated diene represented by the general formula (IIIa) is not limited to, but examples thereof include, for example, cyclic non-conjugated dienes represented by the following chemical formula: Among these, the cyclic non-conjugated diene represented by the general formula (IIIa), i.e., the cyclic non-conjugated diene constituting the repeating unit (B) derived from the cyclic non-conjugated diene, is 5-vinyl-2-norbornene and 8-vinyl-9-methyltetracyclo[4.4.0.1] ２，５ .1 ７，１０ ]-3-dodecene, and more preferably 5-vinyl-2-norbornene.

[0037]

[0038]

[0039] The cyclic non-conjugated diene represented by the above general formula (IIIa) can also be specifically represented by the following general formula (IIIb).

[0040]

[0041] In general formula (IIIb), n is an integer of 0 to 10, and R １ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ２ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

[0042] When the cyclic olefin (co)polymer (m) of the present embodiment contains a structural unit derived from a cyclic non-conjugated diene represented by general formula (III), it has a double bond in a side chain portion, i.e., a portion other than the main chain of the copolymer. The functional group containing the double bond can be one of the crosslinkable groups (α).

[0043] The cyclic olefin monomer, which can be one of the copolymerization raw materials for the cyclic olefin (co)polymer (m), can be addition copolymerized to form a constituent unit represented by the above 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.

[0044]

[0045] 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, and R ６１ ~R ７８ and R ａ１ and R ｂ１ may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms; R ７５ ~R ７８ may be bonded to each other to form a monocyclic or polycyclic ring.

[0046] Specific examples of the cyclic olefin represented by the general formula (Va) include the compounds described in WO 2006 / 118261. The cyclic olefin represented by the general formula (Va), i.e., the cyclic olefin constituting the cyclic olefin-derived repeating unit (C), include bicyclo[2.2.1]-2-heptene (also called norbornene) and tetracyclo[4.4.0.1]-2-heptene. ２，５ .1 ７，１０

[0033] These cyclic olefins have a rigid ring structure, which makes it easy to maintain the elastic modulus of the cured product made of the cyclic olefin (co)polymer (m) and the resin composition, and also have the advantage of being easy to control crosslinking because they do not contain a heterogeneous double bond structure.

[0047] By using the olefin monomer represented by the general formula (Ia) and the cyclic olefin represented by the general formula (Va) as copolymerization components, the solubility of the cyclic olefin (co)polymer (m) in a solvent is further improved, resulting in good moldability and an improved product yield.

[0048] The cyclic olefin (co)polymer (m) may be composed of (A) repeating units derived from one or more olefins represented by general formula (I), (B) repeating units derived from a cyclic non-conjugated diene represented by general formula (III), and (C) repeating units derived from one or more cyclic olefins represented by general formula (V), as well as repeating units derived from a cyclic olefin other than the cyclic non-conjugated diene represented by general formula (III) and the cyclic olefin represented by general formula (V), and / or a chain polyene. In this case, as copolymerization raw materials for the cyclic olefin (co)polymer (m), in addition to the olefin monomer represented by general formula (Ia), the cyclic non-conjugated diene monomer represented by general formula (IIIa), and the cyclic olefin monomer represented by general formula (Va), the cyclic non-conjugated diene monomer represented by general formula (IIIa) and the cyclic olefin monomer other than the cyclic olefin monomer represented by general formula (Va), and / or a chain polyene monomer can be used. As such a cyclic olefin monomer and a chain polyene monomer, a cyclic olefin represented by the following general formula (VIa) or (VIIa) or a chain polyene represented by the following general formula (VIIIa) can be used. Two or more different types of these cyclic olefins and chain polyenes may be used.

[0049]

[0050] In general formula (VIa), x and d each represent an integer of 0 or 1 or more, preferably an integer of 0 or more and 2 or less, more preferably 0 or 1, y and z each represent 0, 1, or 2, and R ８１ ~R ９９ may be the same or different and are 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 a carbon atom to which R ９３ or the carbon atom to which R 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.

[0051]

[0052] 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.

[0053]

[0054] 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.

[0055] Specific examples of the cyclic olefins represented by general formula (VIa) and general formula (VIIa) include the compounds described in paragraphs 0037 to 0063 of WO 2006 / 118261.

[0056] Specific examples of the chain polyene represented by 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.

[0057] When the cyclic olefin (co)polymer (m) contains a structural unit derived from a chain polyene represented by the general formula (VIIIa) above, 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) [for example, general formula (VIa) or general formula (VIIa)], the content of the structural unit is preferably 0.1 to 100 mol %, more preferably 0.1 to 50 mol %, based on the total molar number of repeating units derived from one or more olefins represented by the general formula (I) above, repeating units derived from one or more cyclic non-conjugated dienes represented by the general formula (III) above, and repeating units derived from one or more cyclic olefins represented by the general formula (V) above.

[0058] By using the olefin monomer represented by the general formula (I), the cyclic olefin represented by the general formula (VIa) or (VIIa), and the chain polyene represented by the general formula (VIIIa) as copolymerization components, the solubility of the cyclic olefin (co)polymer (m) in solvents is further improved, resulting in good moldability and improved product yield. Among these, the cyclic olefin represented by the general formula (VIa) or (VIIa) is preferred. These cyclic olefins have a rigid ring structure, which makes it easy to maintain the elastic modulus of the cured product made of the cyclic olefin (co)polymer (m) and the resin composition, and they also have the advantage of being free of heterogeneous double bond structures, making it easy to control crosslinking.

[0059] The comonomer content and glass transition temperature (Tg) of the cyclic olefin (co)polymer (m) can be controlled by adjusting the monomer charging ratio depending on the intended application. The Tg of the cyclic olefin (co)polymer (m) is, for example, 300°C or less, preferably 250°C or less, more preferably 200°C or less, even more preferably 170°C or less, even more preferably 150°C or less, even more preferably 120°C or less, and even more preferably 110°C or less. When the Tg is below the above upper limit, the melt moldability of the cyclic olefin (co)polymer (m) and its solubility in solvents when made into a varnish are improved. The lower limit of the Tg of the cyclic olefin (co)polymer (m) is not particularly limited, but may be, for example, 50°C or more, 70°C or more, or 90°C or more.

[0060] The number average molecular weight (Mn) of the cyclic olefin (co)polymer (m) measured by gel permeation chromatography in terms of polystyrene is preferably 5,000 or more, more preferably 10,000 or more, even more preferably 15,000 or more, and even more preferably 20,000 or more, from the viewpoint of further improving the balance of performance among dielectric properties, low thermal expansion, and mechanical properties, and 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, from the viewpoint of further improving moldability such as impregnation into a fiber substrate and wiring embedding ability during the production of a printed wiring board. The number average molecular weight (Mn) of the cyclic olefin (co)polymer (m) is determined by the addition of a polymerization catalyst, a co-catalyst, H ２ It can be controlled by adjusting the polymerization conditions such as the amount added and the polymerization temperature.

[0061] The cyclic olefin (co)polymer (m) of 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.

[0062] [Crosslinking Coagent] The resin composition of the present embodiment preferably further contains a crosslinking coagent.

[0063] The crosslinking aid contained in the resin composition of this embodiment preferably contains a crosslinkable compound (a) having three or more crosslinkable groups (β). The crosslinkable groups (β) preferably contain at least one functional group selected from the group consisting of a vinyl group and an allyl group.

[0064] The crosslinkable compound (a) preferably has 3 or more crosslinkable groups (β) from the viewpoint of further improving the balance of low dielectric constant, crosslinkability, and heat resistance in the high frequency range. The number of crosslinkable groups (β) is not particularly limited, and may be, for example, 10 or less, 8 or less, 6 or less, or 4 or less.

[0065] Furthermore, from the viewpoint of further improving the performance balance of low dielectric property, crosslinkability, and heat resistance in the high frequency region, the crosslinkable compound (a) preferably further has a heterocyclic structure, more preferably has a nitrogen-containing heterocyclic structure, and further preferably has one or more ring structures selected from the group consisting of an isocyanuric ring structure and a glycoluril ring structure.

[0066] The crosslinking aid contained in the resin composition of the present embodiment includes one or more compounds selected from the group consisting of glycoluril-based crosslinkable compounds, bisisocyanurate-based crosslinkable compounds, and isocyanurate-based crosslinkable compounds, from the viewpoint of further improving the performance balance of low dielectric properties, crosslinkability, and heat resistance in the high frequency range.

[0067] The glycoluril-based crosslinkable compound of this embodiment preferably includes a compound represented by the following formula (1): The bisisocyanurate-based crosslinkable compound and the isocyanurate-based crosslinkable compound of this embodiment preferably include a compound represented by the following formula (2-a):

[0068] In formula (1), R １ ~R ４ At least three of the above are organic groups containing a vinyl group and having 1 to 10 carbon atoms or organic groups containing an allyl group and having 1 to 10 carbon atoms, and preferably, R １ ~R ４At least three of the above are organic groups containing a vinyl group and having 1 to 5 carbon atoms or organic groups containing an allyl group and having 1 to 5 carbon atoms, and more preferably, R １ ~R ４ At least three of R are vinyl groups or allyl groups, and more preferably, R １ ~R ４ are all vinyl groups or allyl groups, and more preferably, R １ ~R ４ All of R are allyl groups. １ ~R ４ may be, for example, a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group. X's are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group, and are preferably hydrogen atoms.

[0069] In formula (2-a), X １ ~X ３ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a vinyl group, an allyl group, or an organic group represented by formula (2-b), and in formulas (2-a) and (2-b), X １ ~X ５ At least three of the above are organic groups containing a vinyl group and having 1 to 10 carbon atoms or organic groups containing an allyl group and having 1 to 10 carbon atoms, and preferably, X １ ~X ５ At least three of X are organic groups containing a vinyl group and having 1 to 5 carbon atoms or organic groups containing an allyl group and having 1 to 5 carbon atoms, and more preferably, X １ ~X ５ At least three of X are vinyl groups or allyl groups, and more preferably, X １ ~X ５ Four of X are vinyl groups or allyl groups, and more preferably, １ ~X ５ In formula (2-a), four of X are allyl groups. １ ~X ３ When none of the above groups contains an organic group represented by formula (2-b), X １ ~X ３are all organic groups containing a vinyl group and having 1 to 10 carbon atoms or organic groups containing an allyl group and having 1 to 10 carbon atoms, and preferably １ ~X ３ are all organic groups containing a vinyl group and having 1 to 5 carbon atoms or organic groups containing an allyl group and having 1 to 5 carbon atoms, and more preferably, X １ ~X ３ are all vinyl groups or allyl groups, and more preferably, X １ ~X ３ In addition, in formula (2-a), all of X １ ~X ３ is an organic group represented by formula (2-b), X １ ~X ５ At least three of the above are organic groups containing a vinyl group and having 1 to 10 carbon atoms or organic groups containing an allyl group and having 1 to 10 carbon atoms, and preferably, X １ ~X ５ At least three of X are organic groups containing a vinyl group and having 1 to 5 carbon atoms or organic groups containing an allyl group and having 1 to 5 carbon atoms, and more preferably, X １ ~X ５ At least three of X are vinyl groups or allyl groups, and more preferably, X １ ~X ５ Four of X are vinyl groups or allyl groups, and more preferably, １ ~X ５ Four of these are allyl groups. In formula (2-b), Y is, for example, a carbonyl group or a chain-like divalent group containing a hydrocarbon group having 2 or more carbon atoms (preferably 2 or more and 18 or less). The chain-like divalent group containing a hydrocarbon group having 2 or more carbon atoms (preferably 2 or more and 18 or less) may have an ether group in the main chain, or may have a hydroxy group in the side chain. Examples of the chain-like divalent group containing a hydrocarbon group having 2 or more carbon atoms (preferably 2 or more and 18 or less) are divalent groups represented by any of the following formulas (3-a) to (3-c):

[0070] In formula (3-a), m represents an integer of 2 or more, preferably an integer of 2 to 18. In formula (3-c), n represents an integer of 0 or 1 or more, preferably 0 or 1.

[0071] Examples of glycoluril-based crosslinkable compounds include 1,3,4,6-tetraallyl glycoluril (e.g., TA-G manufactured by Shikoku Chemical Industries, Ltd.), 1,3,4,6-tetraallyl-3a-methyl glycoluril, 1,3,4,6-tetraallyl-3a,6a-dimethyl glycoluril, and 1,3,4,6-tetraallyl-3a,6a-diphenyl glycoluril. Examples of bisisocyanurate-based crosslinkable compounds include bis(diallyl isocyanurate) compounds (e.g., DD-1 manufactured by Shikoku Chemical Industries, Ltd.). Examples of isocyanurate-based crosslinkable compounds include triallyl isocyanurate (e.g., TAIC manufactured by Mitsubishi Chemical Corporation).

[0072] When the resin composition of this embodiment contains a crosslinking aid, the content of the crosslinking aid in the resin composition of this embodiment is 6 parts by mass or more, preferably 7 parts by mass or more, more preferably 8 parts by mass or more, and even more preferably 9 parts by mass or more, relative to 100 parts by mass of the thermosetting cyclic olefin (co)polymer (m), from the viewpoint of further improving the performance balance of low dielectric constant, crosslinkability, and heat resistance in the high-frequency region. The upper limit of the content of the crosslinking aid in the resin composition of this embodiment is not particularly limited, but is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and even more preferably 30 parts by mass or less, and may be, for example, 20 parts by mass or less, 15 parts by mass or less, or 13 parts by mass or less.

[0073] The crosslinking aid contained in the resin composition of this embodiment may further contain a crosslinking aid other than the crosslinkable compound (a). Examples of the crosslinking aid include, but are not limited to, oximes such as p-quinone dioxime and p,p'-dibenzoylquinone dioxime; (meth)acrylates such as ethylene di(meth)acrylate, polyethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, cyclohexyl (meth)acrylate, acrylic acid / zinc oxide mixtures, and allyl (meth)acrylate; vinyl monomers such as divinylbenzene, vinyltoluene, and vinylpyridine; allyl compounds such as hexamethylene diallyl nadimide, diaryl itaconate, diallyl phthalate, diallyl isophthalate, and diallyl monoglycidyl isocyanurate; and maleimide compounds such as N,N'-m-phenylene bismaleimide and N,N'-(4,4'-methylenediphenylene)dimaleimide. These crosslinking aids may be used alone or in combination.

[0074] The content of the crosslinkable compound (a) in the crosslinking aid contained in the resin composition of the present embodiment is, relative to 100 parts by mass of the crosslinking aid contained in the resin composition of the present embodiment, preferably 50 parts by mass or more, more preferably 70 parts by mass or more, even more preferably 80 parts by mass or more, even more preferably 90 parts by mass or more, even more preferably 95 parts by mass or more, even more preferably 98 parts by mass or more, even more preferably 100 parts by mass or more, and preferably 100 parts by mass or less.

[0075] [Other Radical Initiators] The resin composition of the present embodiment may contain a radical initiator other than the radical initiator (A) (hereinafter referred to as the other radical initiator).

[0076] As other radical initiators, known thermal radical initiators and photoradical initiators can be used in combination. When using a thermal radical initiator among these radical initiators, from the viewpoint of storage stability, the initiator should have a 10-hour half-life temperature of, for example, 80° C. or higher, preferably 120° C. or higher. Examples of such initiators include dialkyl peroxides such as dicumyl peroxide, t-butylcumyl peroxide, 2,5-bis(t-butylperoxy)2,5-dimethylhexane, 2,5-bis(t-butylperoxy)2,5-dimethylhexyne-3, di-t-butyl peroxide, isopropylcumyl-t-butyl peroxide, and bis(α-t-butylperoxyisopropyl)benzene; 1,1-bis(t-butylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclododecane, n-butyl-4,4-bis(t-butylperoxy)valerate, ethyl-3,3-bis(t-butylperoxy)butyrate, 3,3,6,6,9,9-hexamethyl-1,2, peroxyketals such as 4,5-tetraoxycyclononane; peroxyesters such as bis(t-butylperoxy)isophthalate, t-butylperoxybenzoate, and t-butylperoxyacetate; hydroperoxides such as t-butyl hydroperoxide, t-hexyl hydroperoxide, cumin hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, diisopropylbenzene hydroperoxide, and p-menthane hydroperoxide; bibenzyl compounds such as hexaphenylethane, 1-t-butyl-3-[2-(4-t-butylphenyl)-1,1,2-trimethylpropyl]benzene, and 2,3-dimethyl-2,3-diphenylbutane; and 3,3,5,7,7-pentamethyl-1,2,4-trioxepane.

[0077] Among other radical initiators, examples of photoradical initiators include benzoin alkyl ether, benzil 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. Sensitizers can also be used in conjunction with these photoradical initiators. Examples of sensitizers include carbonyl compounds such as anthraquinone, 1,2-naphthoquinone, 1,4-naphthoquinone, benzanthrone, p,p'-tetramethyldiaminobenzophenone, and chloranil; nitro compounds such as nitrobenzene, p-dinitrobenzene, and 2-nitrofluorene; aromatic hydrocarbons such as anthracene and chrysene; sulfur compounds such as diphenyl disulfide; and nitrogen compounds such as nitroaniline, 2-chloro-4-nitroaniline, 5-nitro-2-aminotoluene, and tetracyanoethylene.

[0078] The other radical initiator preferably includes a thermal radical initiator, and more preferably includes a bibenzyl compound, which can further improve storage stability, dielectric properties, heat resistance, and mechanical properties.

[0079] When the resin composition of the present embodiment contains another radical initiator, the content of the other radical initiator in the resin composition of the present embodiment is, from the viewpoint of further improving the performance balance between the heat resistance and mechanical properties of the cured product, preferably 0.02 parts by mass or more, more preferably 0.05 parts by mass or more, even more preferably 0.1 parts by mass or more, even more preferably 0.5 parts by mass or more, even more preferably 1.0 parts by mass or more, even more preferably 1.5 parts by mass or more, even more preferably 2.0 parts by mass or more, even more preferably 2.5 parts by mass or more, even more preferably 3.0 parts by mass or more, and even more preferably 3.5 parts by mass or more, relative to 100 parts by mass of the thermosetting cyclic olefin (co)polymer (m), and from the viewpoint of further improving the dielectric properties of the cured product, is preferably 20.0 parts by mass or less, more preferably 10.0 parts by mass or less, and even more preferably 5.0 parts by mass or less.

[0080] [Antioxidant (B)] The resin composition of the present embodiment preferably further contains an antioxidant (B).

[0081] The antioxidant (B) preferably contains one or more selected from the group consisting of phenolic antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, and thioether-based antioxidants, and more preferably contains a phenolic antioxidant, which can further improve the storage stability of the resin composition during storage and after it is formed into a film.

[0082] Examples of the phenolic antioxidant include acrylate-based phenolic compounds described in JP-A-63-179953 and JP-A-1-168643, such as 2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate and 2,4-di-t-amyl-6-(1-(3,5-di-t-amyl-2-hydroxyphenyl)ethyl)phenyl acrylate; 2,6-di-t-butyl-4-methylphenol; 2,6-di-t-butyl-4-ethylphenol, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,2'-methylene-bis(4-methyl-6-t-butylphenol), 4,4'-butylidene-bis(6-t-butyl-m-cresol), 4,4'-thiobis(3-methyl-6-t-butylphenol), bis(3-cyclohexyl-2-hydroxy-5-methylphenyl)methane, 3,9-bis(2-(3-( 3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy)-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, tetrakis(methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionyloxy)-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, alkyl-substituted phenolic compounds such as pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), pentaerythritol tetrakis(3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, triethylene glycol bis(3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate), and tocopherol;At least one selected from the group consisting of triazine group-containing phenolic compounds such as 6-(4-hydroxy-3,5-di-t-butylanilino)-2,4-bisoctylthio-1,3,5-triazine, 6-(4-hydroxy-3,5-dimethylanilino)-2,4-bisoctylthio-1,3,5-triazine, 6-(4-hydroxy-3-methyl-5-t-butylanilino)-2,4-bisoctylthio-1,3,5-triazine, and 2-octylthio-4,6-bis-(3,5-di-t-butyl-4-oxyanilino)-1,3,5-triazine is preferred. Among these, at least one selected from the group consisting of acrylate-based phenolic compounds and alkyl-substituted phenolic compounds is preferred, with alkyl-substituted phenolic compounds being more preferred.

[0083] Examples of phosphorus-based antioxidants include triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, tris(nonylphenyl) phosphite, tris(dinonylphenyl) phosphite, tris(2,4-di-t-butylphenyl) phosphite, tris(2-t-butyl-4-methylphenyl) phosphite, tris(cyclohexylphenyl) phosphite, 2,2-methylenebis(4,6-di-t-butylphenyl) phosphite, Monophosphite compounds such as octyl phosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(3,5-di-t-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene; 4,4'-butylidene-bis(3-methyl-6-t-butylphenyl-di-tridecyl) bis(diphenyl monoalkyl (C12 to C15) phosphite), 4,4'-isopropylidene-bis(diphenyl monoalkyl (C12 to C15) phosphite), 1,1,3-tris(2-methyl-4-di-tridecyl phosphite-5-t-butylphenyl)butane, tetrakis(2,4-di-t-butylphenyl)-4,4'-biphenylene diphosphite, cyclic neopentane tetrayl bis(isodecyl phosphite), cyclic neopentane tetrayl bis(nonylphenyl phosphite), cyclic neopentane tetrayl bis(2,4-di-t-butylphenyl phosphite), cyclic neopentane tetrayl bis(2,4-dimethylphenyl phosphite), cyclic neopentane tetrayl bis(2,6-di-t-butylphenyl phosphite), and the like. Among these, monophosphite compounds are preferred, and at least one selected from the group consisting of tris(nonylphenyl)phosphite, tris(dinonylphenyl)phosphite, tris(2,4-di-t-butylphenyl)phosphite, and the like is more preferred.

[0084] 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 the thioether antioxidant include at least one selected from the group consisting of tetrakis{methylene-3-(laurylthio)propionate}methane, bis[methyl-4-{3-n-alkyl(C12 or C14)thiopropioniodyl}-5-t-butylphenyl]sulfide, and ditridecyl-3,3′-thiodipropionate.

[0085] When the resin composition of this embodiment contains an antioxidant (B), the content of the antioxidant (B) in the resin composition of this embodiment is, from the viewpoint of further improving storage stability, preferably 0.001 mass% or more, more preferably 0.005 mass% or more, even more preferably 0.01 mass% or more, and even more preferably 0.02 mass% or more, and is preferably 1.0 mass% or less, more preferably 0.50 mass% or less, even more preferably 0.30 mass% or less, even more preferably 0.20 mass% or less, and even more preferably 0.10 mass% or less, relative to the entire resin composition excluding the solvent. Furthermore, when the resin composition of this embodiment contains an antioxidant (B), the content of the antioxidant (B) in the resin composition of this embodiment is, from the viewpoint of further improving storage stability, preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and may be, for example, 1.0 parts by mass or less, 0.5 parts by mass or less, or 0.1 parts by mass or less, relative to 100 parts by mass of the thermosetting cyclic olefin (co)polymer (m).

[0086] [Additives] Various additives may be further added to the resin composition of this embodiment depending on the purpose. The amount of additive added is appropriately selected depending on the application within a range that does not impair the purpose of the present invention. The additives may be one or more additives selected from the group consisting of heat stabilizers, weather stabilizers, radiation resistant agents, plasticizers, lubricants, mold 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. For example, the heat stabilizers, light stabilizers, ultraviolet absorbers, radiation resistant agents, plasticizers, lubricants, release agents, nucleating agents, friction and wear improvers, flame retardants, foaming agents, antistatic agents, colorants, antifogging agents, antiblocking agents, impact resistance agents, surface wetting improvers, fillers, hydrochloric acid absorbers, metal deactivators, etc. described in paragraphs 0085 to 0120 of WO 2017 / 150218 can be used.

[0087] The resin composition of this embodiment can be prepared by mixing the thermosetting cyclic olefin (co)polymer (m) and the radical initiator (A), and optionally other components. Examples of the mixing method include melt blending using an extruder or the like, or solution blending in which the components are dissolved or dispersed in a suitable solvent, such as a saturated hydrocarbon (e.g., heptane, hexane, decane, or cyclohexane) or an aromatic hydrocarbon (e.g., toluene, benzene, or xylene).

[0088] The dielectric loss tangent at 10 GHz of the cured product obtained by heating the resin composition of the present embodiment at 200°C is, from the viewpoint of further improving the performance balance of low dielectric property, crosslinkability, and heat resistance in the high frequency range, preferably less than 0.0020, more preferably less than 0.0018, even more preferably less than 0.0016, even more preferably less than 0.0014, even more preferably less than 0.0013, and even more preferably less than 0.0012, and may be, for example, 0.0001 or more, 0.0003 or more, or 0.0005 or more.

[0089] The dielectric loss tangent at 10 GHz of the cured product obtained by heating the resin composition of this embodiment at 200°C 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 / sec, and then dried for 4 minutes at 150°C in a nitrogen gas flow in a blower dryer to obtain a laminated film of the PET film and the resin composition of this embodiment. Two of the obtained laminated films are stacked so that the resin compositions are in contact with each other, and a pressure of 3.5 MPa is applied using a vacuum press under a vacuum controlled to 20 kPa or less. The temperature is raised from room temperature (25°C) at a constant rate and maintained at 180°C for 60 minutes, after which the film is peeled off from the PET film to obtain a pre-cured laminated film. The obtained uncured laminate film is sandwiched between polyimide films, and a pressure of 3.5 MPa is applied using a vacuum press under a vacuum controlled to 20 kPa or less. The temperature is raised from room temperature (25°C) at a constant rate, and the film is held at 200°C for 120 minutes. The film is then peeled off from the polyimide films to obtain a cured laminate film. The dielectric loss tangent Df at 10 GHz of the obtained cured laminate film is measured using a cylindrical cavity resonator method.

[0090] In the resin composition of this embodiment, ΔTg represented by the following formula (10) is preferably 30° C. or higher, more preferably 35° C. or higher, even more preferably 38° C. or higher, even more preferably 40° C. or higher, and even more preferably 43° C. or higher, from the viewpoint of further improving the performance balance of low dielectric property, crosslinkability, and heat resistance in the high frequency region. The upper limit of ΔTg is not particularly limited, but is, for example, 80° C. or lower, or may be 70° C. or lower, or may be 60° C. or lower. ΔTg=Tg １ -Tg ０ (10) In formula (10), Tg ０ is the glass transition temperature of the thermosetting cyclic olefin (co)polymer (m) of this embodiment, and Tg １ is the glass transition temperature of the cured product obtained by heating the resin composition of this embodiment at 200°C.

[0091] Tg ０can be determined by the following <Method 2>. <Method 2> First, the thermosetting cyclic olefin (co)polymer (m) of the present embodiment is ２ An endothermic curve is obtained by DSC measurement under the following temperature conditions in a nitrogen atmosphere. Then, the temperature of the endothermic peak of the obtained endothermic curve is determined as Tg ０ <Temperature Conditions> The temperature is raised from 25°C to 200°C at a rate of 10°C / min, and then maintained at this temperature for 5 minutes, then lowered to -20°C at a rate of 10°C / min, and then maintained at this temperature for 5 minutes, and then raised to 200°C at a rate of 10°C / min.

[0092] Tg １ can be determined by the following <Method 3>. <Method 3> The solid viscoelastic temperature dispersion measurement of the cured laminate film obtained by the above <Method 1> is carried out under the following conditions, and the peak temperature of the loss tangent (tan δ) is determined by heating the resin composition of the present embodiment at 200°C, and the glass transition temperature of the cured product is determined by Tg １ Deformation mode: Tensile Temperature range: 25°C to 300°C Heating rate: 3°C / min Frequency: 1Hz Set strain: 0.1% Environment: Nitrogen atmosphere

[0093] The glass transition temperature Tg of the cured product obtained by heating the resin composition of this embodiment at 200°C １ From the viewpoint of further improving the balance of performance among low dielectric properties in the high frequency range, crosslinkability, and heat resistance, Tg is preferably 130°C or higher, more preferably 135°C or higher, and even more preferably 138°C or higher. １ The upper limit of the temperature is not particularly limited, but may be, for example, 200°C or less, 180°C or less, 170°C or less, or 160°C or less.

[0094] 2. Varnish The varnish of this embodiment will now be described.

[0095] The varnish of the present embodiment contains the resin composition of the present embodiment and a solvent.

[0096] The solvent for preparing the varnish is not limited as long as it does not impair the solubility or affinity of the thermosetting cyclic olefin (co)polymer (m) and the crosslinking aid.Preferred solvents include 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; cellosolves such as methyl cellosolve and ethyl cellosolve; esters such as methyl acetate, ethyl acetate, butyl acetate, methyl propionate, and butyl formate; halogenated hydrocarbons such as trichloroethylene, dichloroethylene, and chlorobenzene. From the viewpoint of further improving the solubility and availability of the resin composition, heptane, decane, cyclohexane, methylcyclohexane, decahydronaphthalene, toluene, benzene, xylene, mesitylene, and pseudocumene are more preferably used. These solvents can be used alone or in combination of two or more in any ratio. From the viewpoint of further improving the handleability and coatability of the varnish, the amount of solvent added to the resin composition is preferably 100 parts by mass or more, more preferably 120 parts by mass or more, and preferably 500 parts by mass or less, more preferably 450 parts by mass or less, and even more preferably 400 parts by mass or less, based on 100 parts by mass of the entire resin composition. Furthermore, the total content of the thermosetting cyclic olefin (co)polymer (m) and the crosslinking coagent in the varnish is preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, and preferably less than 100% by mass, more preferably 50% by mass or less.

[0097] In this embodiment, the method for preparing the varnish may be carried out by any method, for example, including a step of mixing a resin composition and a solvent. The order of mixing of the components is not limited, and any method, such as batch or portionwise mixing, may be used. The apparatus for preparing the varnish is also not limited, and any batch or continuous apparatus capable of stirring and mixing may be used. The temperature when preparing the varnish can be selected arbitrarily from the range of room temperature to the boiling point of the solvent. The varnish may also be prepared by using the reaction solution obtained when the thermosetting cyclic olefin (co)polymer (m) is obtained as it is as a solvent.

[0098] 3. Cured Product The cured product of this embodiment will now be described.

[0099] The cured product of this embodiment can be obtained by crosslinking the thermosetting cyclic olefin (co)polymer (m) in the resin composition of this embodiment. Crosslinking can be carried out, for example, by a crosslinking step in which the resin composition is crosslinked under a vacuum of 20 kPa or less at a temperature of 150°C or higher and a press pressure of 0.2 MPa or higher. The crosslinking temperature in the crosslinking step is preferably 150°C or higher, more preferably 160°C or higher, and even more preferably 170°C or higher, from the viewpoint of further improving the heat resistance of the resulting cured product. The crosslinking temperature in the crosslinking step is preferably 280°C or lower, more preferably 260°C or lower, even more preferably 250°C or lower, and even more preferably 240°C or lower, from the viewpoint of suppressing thermal decomposition of the thermosetting cyclic olefin (co)polymer (m) and the cured product. The press pressure in the crosslinking step is 0.2 MPa or higher, preferably 1 MPa or higher, more preferably 2 MPa or higher, and even more preferably 3 MPa or higher, from the viewpoint of ensuring the uniformity of the resulting cured product. In order to maintain the dielectric properties of the resulting cured product, the crosslinking step is carried out under a vacuum of 20 kPa or less, preferably 10 kPa or less, more preferably 5 kPa or less, and even more preferably 2 kPa or less.

[0100] The crosslinking step can be carried out with the resin composition of this embodiment in a molten state, or with the resin composition dissolved or dispersed in a solvent in a solution state. The crosslinking step can also be carried out by volatilizing the solvent from a solution state in which the resin composition is dissolved in a solvent, forming the resulting product into any desired shape such as a film or coating, and then allowing the crosslinking reaction to proceed. When the reaction is carried out in a molten state, a kneading device such as a mixing roll, a Banbury mixer, an extruder, a kneader, or a continuous mixer is used to melt-knead the mixture of raw materials and allow the reaction to proceed. The crosslinking reaction can also be carried out after molding by any method. When the reaction is carried out in a solution state, the same solvents as those used in the solution blending method can be used.

[0101] 4. Prepreg The prepreg of this embodiment will now be described.

[0102] The prepreg of the present embodiment is formed by impregnating a fiber substrate with the resin composition of the present embodiment or the varnish of the present embodiment.

[0103] The prepreg of this embodiment is preferably formed by combining the resin composition of this 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, a method including the steps of impregnating a sheet-like fiber substrate with the above-described varnish to obtain an impregnated body and heating the obtained impregnated body to dry the solvent contained in the varnish can be used. The impregnation of the sheet-like fiber substrate with the varnish can be carried out by applying a predetermined amount of varnish to the sheet-like fiber substrate by known methods such as spray coating, dip coating, roll coating, curtain coating, die coating, or slit coating, and then, if necessary, placing a protective film on top of the varnish and pressing it from above with a roller or the like. The process for heating the impregnated body and drying the solvent contained in the varnish is not particularly limited, but examples thereof include drying in air or nitrogen using a blower dryer in a batch process, or drying by passing the impregnated body through a heating furnace in a continuous process. After the varnish is impregnated into the sheet-like fiber substrate, the resulting impregnated body is heated to a predetermined temperature, whereby the solvent contained in the varnish evaporates and a prepreg is obtained.

[0104] The fibers constituting the sheet-like fiber substrate can be inorganic or organic fibers, 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, at least one fiber selected from the group consisting of organic fibers and glass fibers is preferred, and at least one fiber selected from the group consisting of aramid fibers, liquid crystal polyester fibers, and glass fibers is more 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 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 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 for example, 90% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less, of the prepreg or laminate. If it is in this range, the dielectric properties and mechanical strength of the resulting laminate are well balanced, which is preferable.

[0105] 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 is, for example, 10 mm or less, preferably 1 mm or less, more preferably 0.5 mm or less. This range is suitable because it allows the shapeability during lamination and the mechanical strength and toughness of the laminate obtained by curing to be fully exhibited.

[0106] 5. Film The film of this embodiment will now be described.

[0107] The film of this embodiment contains a cured product of the resin composition of this embodiment.

[0108] The cured product obtained by curing the resin composition of this embodiment can be molded into a film and used for various applications. In this embodiment, the term "film" is a general term for a planar molded product, and includes sheets, membranes, tapes, and the like. Various known methods can be used to cure the resin composition of this embodiment into a cured product and mold it into a film. For example, a method can be used in which the varnish described above is applied to a support substrate such as a thermoplastic resin film, dried, and then heat-treated or otherwise crosslinked to obtain a cured product, thereby forming a film made of the resin composition of this embodiment. Examples of thermoplastic resin films that can be used include PET film, polyimide resin film, and the like. The method for applying the varnish to the support substrate is not particularly limited, and examples include application using a spin coater, application using a spray coater, and application using a bar coater. Another example can be a method in which the resin composition of this embodiment is melt-molded to obtain a film, and then heat-treated or otherwise crosslinked to form a cured product, thereby forming a film made of the resin composition of this embodiment.

[0109] 6. Laminate The laminate of this embodiment will now be described.

[0110] The laminate of this embodiment includes the prepreg of this embodiment or the film of this embodiment.

[0111] The film or prepreg of this embodiment can be laminated to 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 a curable adhesive sheet for a device having an adhesive layer. Various known methods can be applied to form the laminate of this embodiment. For example, a laminate can be produced by laminating a film produced by the above-mentioned method to a substrate and, if necessary, heat-curing the film using a press or the like. A laminate can also be produced by laminating an electrical insulating layer containing the above-mentioned cured product to a conductor layer.

[0112] 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 laminate films. Examples of various multilayer molded articles or multilayer laminate films include multilayer molded articles for optical lenses in which the film of this embodiment is formed on the surface of a resin optical lens, and multilayer gas barrier films 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.

[0113] 7. Metal Clad Laminate Hereinafter, the metal clad laminate of this embodiment will be described.

[0114] The metal clad laminate of this embodiment includes a metal foil on at least one side of the laminate of this embodiment.

[0115] The laminate of this embodiment may be formed into a metal clad laminate by laminating a metal foil on at least one surface of the laminate of this embodiment and heat-curing the laminate using a lamination press or the like. Alternatively, the metal foil may be attached to both surfaces of the laminate. Examples of metal foil include copper foil, aluminum foil, nickel foil, gold foil, silver foil, and stainless steel foil. From the viewpoints of economy, processability, thermal conductivity, and electrical conductivity, electrolytic copper foil is preferred. Various known methods can be applied as a method for producing the metal clad laminate of this embodiment. For example, a metal clad laminate can be produced by laminating a metal foil on the laminate of this embodiment and, if necessary, heat-curing the laminate using a press or the like.

[0116] The metal clad laminate of the present embodiment uses a cured product obtained by curing the resin composition of the present embodiment, and therefore has an improved balance of low dielectric properties and heat resistance in the high frequency range, which is suitable for printed wiring boards. Therefore, the metal clad laminate of the present embodiment can be suitably used as an insulating layer material for printed wiring boards.

[0117] 8. Printed Wiring Board The printed wiring board of this embodiment will now be described.

[0118] The printed wiring board of this embodiment is manufactured using the prepreg of this embodiment or the metal clad laminate of this embodiment.

[0119] The cured product obtained by curing the resin composition of this embodiment has an improved balance between low dielectric constant and heat resistance in the high frequency range, and is therefore suitable for use in printed wiring boards. A commonly known method can be used as a method for producing a printed wiring board, and is not particularly limited. For example, a film or laminate produced by the above-mentioned method is heat-cured using a lamination press or the like to form an electrical insulating layer. A conductor layer is then laminated on the obtained electrical insulating layer using a known method to produce a laminate. The conductor layer in the laminate can then be subjected to circuit processing or the like to obtain a printed wiring board.

[0120] Examples of metals that can be used for the conductor layer include copper, aluminum, nickel, gold, silver, stainless steel, etc. Methods for forming the conductor layer include, for example, a method in which the above metals are made into foil or the like and heat-fused onto the electrical insulating layer, a method in which the above metals are made into 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 above metals is formed on the electrical insulating layer by a method such as sputtering, vapor deposition, or plating. The printed wiring board may be either a single-sided board or a double-sided board.

[0121] 9. Electronic Device The electronic device of this embodiment will now be described.

[0122] The electronic device of this embodiment includes the film of this embodiment or the printed wiring board of this embodiment.

[0123] The electronic device of this embodiment can be fabricated based on 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 phones, PDAs, and tablet terminals; digital devices such as personal computers, televisions, digital cameras, digital video cameras, POS terminals, wearable terminals, and digital media players; in-vehicle electronic devices such as electronic control system devices, in-vehicle communication devices, car navigation devices, millimeter-wave radars, and in-vehicle camera modules; semiconductor test equipment, high-frequency measurement equipment, and high-speed communication modules.

[0124] The electronic device of this embodiment preferably includes a high-speed communication compatible module.

[0125] The high-speed communication module of this embodiment is a high-speed communication module manufactured using the film of this embodiment or the printed wiring board of this embodiment. The high-speed communication module of this embodiment is, for example, a communication module in which a semiconductor chip or the like is mounted on the printed wiring board of this embodiment, and is particularly suitable for applications in which high-frequency signals are used, such as wireless communication devices and network infrastructure devices, and where the amount and speed of information communication is large.

[0126] 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 region, and therefore can be used in applications such as optical fibers, optical waveguides, optical disk substrates, optical filters, lenses, optical adhesives, optical filters for PDPs, coating materials for organic EL devices, 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, printed wiring boards, prepregs and laminates used to form insulating layers for printed wiring boards, overcoat materials or interlayer insulating materials for display components, substrates for liquid crystal displays and solar cells, medical instruments, automotive components, resin modifiers, transparent substrates for displays, gas barrier coating materials, aerospace components, semiconductor processing materials, electric 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 the present embodiment has an improved balance of low dielectric properties and heat resistance in the high frequency range, and also has a good balance of performance such as insulating properties and mechanical properties, so it can be suitably used for printed wiring boards, and can be more suitably used for high frequency applications such as high frequency printed wiring boards.

[0127] Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various other configurations may be adopted. Furthermore, the present invention is not limited to the above-described embodiments, and modifications and improvements that do not impair the effects of the present invention are included in the present invention.

[0128] The present embodiment will be described in detail below with reference to examples, etc. However, the present embodiment is not limited to the descriptions of these examples.

[0129] The raw materials used in preparing the resin composition are as follows.

[0130] [Thermosetting Cyclic Olefin (Co)polymer (m)] Thermosetting Cyclic Olefin Copolymer (m-1) (synthesis method will be described later)

[0131] [Radical initiator (A)] DEDPH (2,3-diethyl-2,3-diphenylhexane, manufactured by Fluorochem, R １ From R １０ is a hydrogen atom, and R １１ From R １４ is an ethyl group.)

[0132] [Other radical initiators] Percumyl D (dicumyl peroxide, product name: Percumyl D, manufactured by NOF Corporation) VR-110 (2,2'-azobis(2,4,4-trimethylpentane), product name: VR-110, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) DMDPB (2,3-dimethyl-2,3-diphenylbutane, manufactured by Acros Organics, in which R １ From R １０ is a hydrogen atom, and R １１ From R １４ is a methyl group.)

[0133] [Antioxidant (B)] Irganox 1010 (pentaerythritol tetrakis[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, product name: Irganox 1010, manufactured by BASF)

[0134] The following raw materials were used to synthesize the thermosetting cyclic olefin copolymer (m-1): Transition metal compound (1): Synthesized by the method described in JP-A-2004-331965.

[0135]

[0136] Modified methylaluminoxane (MMAO, manufactured by Tosoh Finechem Co., Ltd.) Toluene (manufactured by Wako Pure Chemical Industries, Ltd.: Wako special 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 referred to as TD) (manufactured by Mitsui Chemicals, Inc.) Methanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.: Wako special grade)

[0137] [Method for measuring the content of each structural unit constituting a cyclic olefin (co)polymer] The contents of the repeating unit (A), the repeating unit (B) and the repeating unit (C) were measured using a nuclear magnetic resonance spectrometer "EXcalibur 270" manufactured by JEOL Ltd. under the following conditions: Number of accumulations: 16 to 64 Measurement temperature: Room temperature (25°C) The values ​​obtained in the above measurement were １ From the H-NMR spectrum, it was calculated from the intensities of the peaks derived from hydrogen directly bonded to the double bond carbon and the peaks derived from other hydrogen.

[0138] [Glass transition temperature Tg of thermosetting cyclic olefin (co)polymer (m)] ０ First, the thermosetting cyclic olefin (co)polymer (m) was ２ An endothermic curve was obtained by DSC measurement under the following temperature conditions in a nitrogen atmosphere. The endothermic peak temperature of the obtained endothermic curve was then determined as the glass transition temperature Tg of the thermosetting cyclic olefin (co)polymer (m). ０ The DSC measurement device used was a DSC-6220 manufactured by Shimadzu Science Corporation. <Temperature conditions> The temperature was raised from 25°C to 200°C at a heating rate of 10°C / min, and then held for 5 minutes, then cooled to -20°C at a cooling rate of 10°C / min, and then held for 5 minutes, and then heated to 200°C at a heating rate of 10°C / min.

[0139] Synthesis Example 1 Into a 1 L SUS autoclave that had been thoroughly purged with nitrogen, 450 ml of toluene, 30 ml of VNB, 16 ml of TD, 0.9 mmol of a hexane solution of MMAO (calculated as Al), and 360 ml of hydrogen were charged, and ethylene was then 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. Ion-exchanged water was added to the resulting polymer solution, and the mixture was stirred for 1 hour. The organic layer was then filtered through filter paper. This organic layer was poured into acetone to precipitate a polymer, which was 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 / TD / VNB copolymer (hereinafter referred to as thermosetting cyclic olefin copolymer (m-1)), which is a thermosetting cyclic olefin (co)polymer (m). The compositional ratio of the TD-derived structure in the polymer determined by NMR of the obtained thermosetting cyclic olefin copolymer (m-1) was 12 mol %, the compositional ratio of the VNB-derived structure in the polymer was 26 mol %, and the number average molecular weight (Mn) determined by GPC measurement was 21,000 and the glass transition temperature Tg was 99°C.

[0140] [Example 1] (Preparation of Varnish) To the thermosetting cyclic olefin copolymer (m-1) obtained in Synthesis Example 1, a radical initiator and an antioxidant weighed according to the formulation in Table 1 were added, and toluene was added as a solvent. The mixture was stirred until fully dissolved, thereby obtaining the desired varnish-like cyclic olefin copolymer resin composition. The blending ratio of each raw material in Table 1 is expressed in parts by mass.

[0141] (Preparation of Cured Laminated Film) 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 in a blower dryer to obtain a laminated film of the PET film and the composition. Two laminated films were prepared. The two obtained laminated films were stacked so that the surfaces coated with the resin composition were in contact with each other, and the pressure was increased to 3.5 MPa under a vacuum controlled to 20 kPa or less using a vacuum press. The temperature was increased from room temperature (25 ° C.) at a constant rate, and the temperature was maintained at 180 ° C. for 60 minutes. The film was then peeled off from the PET film to obtain a pre-cured laminated film. The obtained uncured laminate film was sandwiched between polyimide films, and a pressure of 3.5 MPa was applied using a vacuum press under a vacuum controlled to 20 kPa or less. The temperature was raised from room temperature (25°C) at a constant rate, and the film was held at 200°C for 120 minutes. Thereafter, the film was peeled off from the polyimide films to obtain a cured laminate film. The dielectric loss tangent and heat resistance of the obtained cured laminate film were measured using the following procedures.

[0142] [Evaluation of Dielectric Loss Tangent] The dielectric loss tangent Df at 10 GHz of the cured laminate films obtained in the Examples and Comparative Examples was measured by a cylindrical cavity resonator method. The results are shown in Table 1.

[0143] [Evaluation of Heat Resistance] The solid viscoelastic temperature dispersion of the cured laminated films obtained in the Examples and Comparative Examples was measured under the following conditions, and the peak temperature of the loss tangent (tan δ) was determined as the glass transition temperature Tg of the cured product obtained by heating the resin composition of this Example at 200°C. １ Apparatus: RSA-III (manufactured by TA Instruments) Deformation mode: Tensile Temperature range: 25°C to 300°C Heating rate: 3°C / min Frequency: 1 Hz Set strain: 0.1% Environment: Nitrogen atmosphere The glass transition temperature Tg of the cured product obtained by heating the resin composition of this example obtained by the above method at 200°C was １ and the Tg of the thermosetting cyclic olefin copolymer (m-1) ０ From this, ΔTg was calculated by the following formula (10): ΔTg=Tg １ -Tg０ (10) The results are shown in Table 1. In this evaluation, it was determined that the larger the ΔTg, the more improved the heat resistance.

[0144] [Example 2 and Comparative Examples 1 to 3] Varnishes and laminated films were prepared and evaluated under the same conditions as in Example 1, except that the blending compositions and pressing temperatures were changed as shown in Table 1. The pressing temperatures shown in Table 1 are those of the laminated films before curing. The results obtained are shown in Table 1.

[0145]

[0146] With the resin compositions of the examples, it was possible to obtain cured products with an improved balance of low dielectric properties and heat resistance in the high frequency range at a crosslinking temperature of 200° C. or less. This shows that with the resin composition of the present embodiment, it is possible to obtain cured products with an improved balance of low dielectric properties and heat resistance in the high frequency range at a crosslinking temperature of 200° C. or less.

[0147] This application claims priority based on Japanese Patent Application No. 2024-035037, filed March 7, 2024, the disclosure of which is incorporated herein by reference in its entirety.

Claims

1. A resin composition comprising a thermosetting cyclic olefin (co)polymer (m) having a crosslinkable group (α) and a radical initiator (A), wherein the radical initiator (A) comprises a compound represented by the following general formula (1): [In general formula (1), R １ From R １０ are each independently a hydrogen atom, a halogen atom, an alkyl group having from 1 to 20 carbon atoms, a cycloalkyl group having from 3 to 20 carbon atoms, an aromatic hydrocarbon group having from 6 to 20 carbon atoms, or a halogenated alkyl group having from 1 to 20 carbon atoms; R １１ From R １４ are each 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; R １１ From R １４ at least one of which 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.

2. In the general formula (1), R １ From R １０ and each independently represent 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.

3. In the general formula (1), R １ From R １０ The resin composition according to claim 2 , wherein is a hydrogen atom.

4. In the general formula (1), R １１ From R １４ and each independently represent 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.

5. In the general formula (1), R １１ From R １４ The resin composition according to claim 4 , wherein each of the groups independently represents an alkyl group having 2 to 20 carbon atoms.

6. In the general formula (1), R １１ From R １４ The resin composition according to claim 5 , wherein is an ethyl group.

7. A resin composition according to claim 1 or 2, wherein the content of the radical initiator (A) in the resin composition is 0.02 parts by mass or more and 20.0 parts by mass or less per 100 parts by mass of the thermosetting cyclic olefin (co)polymer (m).

8. The resin composition according to claim 1 or 2, wherein the thermosetting cyclic olefin (co)polymer (m) comprises: (A) one or more olefin-derived repeating units represented by the following general formula (I); (B) one or more cyclic non-conjugated diene-derived repeating units represented by the following general formula (III); and (C) one or more cyclic olefin-derived repeating units represented by the following general formula (V). [In the above general formula (I), R ３００ represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms. [In the above general formula (III), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, and R ６１ ~R ７６ and R ａ１ and R ｂ１ may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms; R １０４ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, t is a positive integer of 0 to 10, and R ７５ and R ７６ may be bonded to each other to form a monocyclic or polycyclic ring. [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 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 may be bonded to each other to form a monocyclic or polycyclic ring.

9. The resin composition according to claim 8, wherein, when the total number of moles of repeating units in the thermosetting cyclic olefin (co)polymer (m) is taken as 100 mol%, the content of the olefin-derived repeating units (A) is 10 mol% or more and 90 mol% or less, the content of the cyclic non-conjugated diene-derived repeating units (B) is 1 mol% or more and 40 mol% or less, and the content of the cyclic olefin-derived repeating units (C) is 1 mol% or more and 50 mol% or less.

10. The resin composition according to claim 8, wherein the cyclic non-conjugated diene constituting the repeating unit (B) derived from the cyclic non-conjugated diene includes 5-vinyl-2-norbornene.

11. The cyclic olefin constituting the cyclic olefin-derived repeating unit (C) is tetracyclo[4.4.0.1 ２，５ .1 ７，１０ 9. The resin composition according to claim 8, comprising at least one member selected from the group consisting of cyclo[2.2.1]-3-dodecene and bicyclo[2.2.1]-2-heptene.

12. The resin composition according to claim 1 or 2, further comprising an antioxidant (B).

13. The resin composition according to claim 1 or 2, wherein the cured product obtained by heating the resin composition at 200°C has a dielectric loss tangent at 10 GHz of less than 0.0020.

14. The resin composition according to claim 1 or 2, wherein ΔTg represented by the following formula (10) is 30°C or higher. ΔTg = Tg １ -Tg ０ (10) [In formula (10), Tg ０ is the glass transition temperature of the thermosetting cyclic olefin (co)polymer (m), and Tg １ is the glass transition temperature of the cured product obtained by heating the resin composition at 200°C.

15. A varnish comprising the resin composition according to claim 1 or 2 and a solvent.

16. A prepreg obtained by impregnating a fiber substrate with the resin composition according to claim 1 or 2 or the varnish according to claim 15.

17. A film comprising a cured product of the resin composition according to claim 1 or 2.

18. A laminate comprising the prepreg of claim 16 or the film of claim 17.

19. A metal clad laminate comprising a metal foil on at least one side of the laminate of claim 18.

20. A printed wiring board manufactured using the prepreg according to claim 16 or the metal clad laminate according to claim 19.

21. An electronic device comprising the film of claim 17 or the printed wiring board of claim 20.

22. The electronic device of claim 21, wherein the electronic device includes a high-speed communications-enabled module.