Resin composition particles, dispersion, resin composition, varnish, cured product of resin composition, film or sheet, laminate, prepreg, printed wiring board, electronic device, and method for producing resin composition particles

Abstract

To provide resin composition particles of a cyclic olefin copolymer having curability.SOLUTION: Resin composition particles include: a thermosetting cyclic olefin copolymer (A) having a crosslinkable group; and a radical initiator (B), the radical initiator (B) being contained within the resin composition particles.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to resin composition particles, a dispersion, a resin composition, a varnish, a cured product of a resin composition, a film or sheet, a laminate, a prepreg, a printed wiring board, an electronic device, and a method for producing resin composition particles. [Background technology]

[0002] Resin compositions are used as materials for high-frequency printed wiring boards, etc. Patent Document 1 describes a technique for such resin compositions.

[0003] Patent Document 1 describes a cyclic olefin copolymer having a crosslinkable group from which a crosslinked product having excellent stability over time of dielectric properties and heat resistance, as well as excellent transparency, mechanical properties, dielectric properties, and gas barrier properties can be obtained, and further describes a cyclic olefin copolymer having a crosslinkable group, which comprises (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), and in which the repeating units (B) derived from a 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 %. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2012 / 046443 Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention provides curable cyclic olefin copolymer resin composition particles. [Means for solving the problem]

[0006] [1] Resin composition particles, a thermosetting cyclic olefin copolymer (A) having a crosslinkable group; a radical initiator (B), Resin composition particles, wherein the radical initiator (B) is present within the resin composition particles. [2] The resin composition particles are spherical, Number-based average particle diameter D based on scanning electron microscope observation image 50 The resin composition particles according to [1] above, wherein the particle size is 0.01 μm or more and 30 μm or less. [3] The resin composition particles according to the above [1] or [2], wherein the radical initiator (B) includes a non-peroxide radical initiator. [4] The resin composition particles according to any one of the above [1] to [3], further comprising an inorganic filler (C). [5] The resin composition particles according to [4], wherein the content of the inorganic filler (C) is 10 parts by mass or more and 1000 parts by mass or less when the content of the thermosetting cyclic olefin copolymer (A) is 100 parts by mass. [6] The resin composition particles according to [4] or [5] above, wherein the inorganic filler (C) contains silica. [7] The thermosetting cyclic olefin copolymer (A) is One or more olefin-derived repeating units (a) represented by the following formula (I); one or more repeating units (b) derived from a cyclic non-conjugated diene represented by the following formula (III); The resin composition particles according to any one of the above [1] to [6], which contain one or more repeating units (c) derived from cyclic olefins and represented by the following formula (V): [ka] [In the formula (I), R 300 represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms. [ka] [In the 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. [ka] [In the formula (V), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, and R 61 ~R 78 , 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. [8] The resin composition particles according to [7] above, wherein the olefin constituting the olefin-derived repeating unit (a) contains ethylene. [9] The resin composition particles according to [7] or [8], wherein the cyclic non-conjugated diene constituting the repeating unit (b) derived from the cyclic non-conjugated diene includes 5-vinyl-2-norbornene.

[10] The cyclic olefin constituting the cyclic olefin-derived repeating unit (c) is a tetracyclo[4.4.0.1 2,5 .1 7,10 The resin composition particles according to any one of [7] to [9] above, which contain one or two members selected from the group consisting of cyclo[2.2.1]-3-dodecene and bicyclo[2.2.1]-2-heptene.

[11] The resin composition particles according to any one of [7] to

[10] above, wherein, when the total number of moles of repeating units in the thermosetting cyclic olefin copolymer (A) is taken as 100 mol %, the content of the olefin-derived repeating units (a) is 10 mol % or more and 80 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 60 mol % or less.

[12] The resin composition particles according to any one of [1] to

[11] , wherein the content of the radical initiator (B) is 0.1 parts by mass or more and 25.0 parts by mass or less, relative to 100 parts by mass of the thermosetting cyclic olefin copolymer (A).

[13] The resin composition particles according to any one of [1] to

[12] , wherein the total content of the thermosetting cyclic olefin copolymer (A) and the radical initiator (B) in the resin composition particles is 5 parts by mass or more and 100 parts by mass or less, when the total amount of the resin composition particles is 100 parts by mass.

[14] The resin composition particles according to any one of [1] to

[13] above, which are in an uncured or semi-cured state.

[15] A dispersion comprising particles of the resin composition according to any one of the above [1] to

[14] and a polar solvent.

[16] A resin composition comprising the resin composition particles according to any one of the above [1] to

[14] and a matrix resin.

[17] A varnish comprising the resin composition according to

[16] above and a solvent.

[18] A cured product of the resin composition according to

[16] or

[17] above.

[19] A film or sheet comprising the resin composition according to

[16] or

[17] above, or the cured product according to

[18] above.

[20] A laminate comprising the film or sheet according to

[19] above. [twenty one] The laminate according to

[20] , further comprising a metal foil on at least one surface. [twenty two] A prepreg comprising the resin composition according to

[16] or

[17] above and a sheet-like fiber base material. [twenty three] A printed wiring board comprising an insulating layer containing the cured product according to

[18] above or the cured product of the prepreg according to

[22] above, and a conductor layer on the insulating layer. [twenty four] An electronic device comprising the printed wiring board according to

[23] . [twenty five] A method for producing the resin composition particles according to any one of [1] to

[14] above, A method for producing resin composition particles, comprising the step of spray-drying a mixture containing a thermosetting cyclic olefin copolymer (A) having a crosslinkable group and a radical initiator (B), or by crystallizing the mixture, to produce resin composition particles.

[26] The method for producing resin composition particles according to

[25] above, wherein the mixture further contains an organic solvent.

[27] The method for producing resin composition particles according to

[26] above, wherein the organic solvent includes a low-polarity solvent.

[28] The method for producing resin composition particles according to

[27] above, wherein the low-polarity solvent contains toluene. [Effects of the Invention]

[0007] According to the present invention, it is possible to provide curable cyclic olefin copolymer resin composition particles. DETAILED DESCRIPTION OF THE INVENTION

[0008] The present invention will be described below based on the embodiments. In this embodiment, "A to B" indicating a numerical range means A or more and B or less unless otherwise specified. Furthermore, when a numerical range is described in stages, the upper and lower limits of each numerical range can be combined arbitrarily. Furthermore, the description "A and / or B" is a concept that includes the case of A, the case of B, and the case of both A and B. In the description of groups (atomic groups) in this specification, when a notation does not specify whether the group is substituted or unsubstituted, it encompasses both groups that do not contain a substituent and groups that contain a substituent. For example, the term "alkyl group" encompasses not only alkyl groups that do not contain a substituent (unsubstituted alkyl groups) but also alkyl groups that contain a substituent (substituted alkyl groups). In this specification, the term "(meth)acrylic" represents a concept that encompasses both acrylic and methacrylic. Furthermore, each monomer constituting the "thermosetting cyclic olefin copolymer (A) having a crosslinkable group" in this specification may be a monomer obtained from a fossil raw material, or may be a monomer obtained from an animal or plant raw material.

[0009] The resin composition particles of this embodiment contain a thermosetting cyclic olefin copolymer (A) having a crosslinkable group and a radical initiator (B). The radical initiator (B) is present within the resin composition particles. The resin composition particles of this embodiment have such a structure and therefore can be cured.

[0010] Resin compositions used in printed wiring boards are required to have improved heat resistance as a basic property of the cured product obtained by curing the resin composition. Furthermore, when used in high-frequency printed wiring boards, the cured resin is required to have improved low dielectric properties in order to reduce transmission loss.

[0011] By blending the resin composition particles of this embodiment with a resin composition of a matrix resin, a cured product having an improved balance of low dielectric properties and heat resistance can be obtained. Furthermore, the resin composition particles of this embodiment can provide a film or sheet, a laminate, a prepreg, a printed wiring board, and an electronic device having an improved balance of low dielectric properties and heat resistance.

[0012] The reasons for this are thought to be as follows. Since it is possible to disperse the thermosetting cyclic olefin copolymer (A) with improved low dielectric properties and heat resistance in a matrix resin, it is believed that the performance balance of low dielectric properties and heat resistance can be improved compared to when the matrix resin is used alone.

[0013] <Thermosetting cyclic olefin copolymer (A)> The resin composition particles of this embodiment contain a thermosetting cyclic olefin copolymer (A) having a crosslinkable group (hereinafter also simply referred to as "copolymer (A)"). The thermosetting cyclic olefin copolymer (A) can be any copolymer that has thermosetting properties and contains repeating units derived from a cyclic olefin, without any particular limitations. The thermosetting cyclic olefin copolymer (A) also has a crosslinkable group, from the viewpoint of improving the heat resistance of the resulting cured product. The crosslinkable group includes one or more crosslinkable functional groups selected from the group consisting of 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 includes a vinyl group. The thermosetting cyclic olefin copolymer (A) will be described in detail below, but the thermosetting cyclic olefin copolymer (A) of this embodiment is not limited to the following aspects.

[0014] From the viewpoint of further improving the performance balance between low dielectric properties and heat resistance of the resulting cured product, the thermosetting cyclic olefin copolymer (A) preferably contains one or more olefin-derived repeating units (a) represented by formula (I), one or more cyclic non-conjugated diene-derived repeating units (b) represented by formula (III), and one or more cyclic olefin-derived repeating units (c) represented by formula (V).

[0015] [ka]

[0016] In formula (I), R 300 represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms.

[0017] [ka]

[0018] In 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.

[0019] [ka]

[0020] In 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 , 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.

[0021] In the thermosetting cyclic olefin copolymer (A), when the total number of moles of repeating units in the thermosetting cyclic olefin copolymer (A) is taken as 100 mol %, the content of each repeating unit can be as follows.

[0022] The content of the olefin-derived repeating unit (a) in the thermosetting cyclic olefin copolymer (A) of this embodiment is preferably 10 mol% or more and 80 mol% or less, more preferably 15 mol% or more and 77 mol% or less, even more preferably 20 mol% or more and 75 mol% or less, even more preferably 30 mol% or more and 73 mol% or less, even more preferably 40 mol% or more and 71 mol% or less, even more preferably 45 mol% or more and 69 mol% or less, even more preferably 50 mol% or more and 67 mol% or less, and even more preferably 55 mol% or more and 65 mol% or less.

[0023] Furthermore, the content of the repeating unit (b) derived from a cyclic non-conjugated diene in the thermosetting cyclic olefin copolymer (A) of this embodiment is preferably 1 mol% or more and 20 mol% or less, more preferably 3 mol% or more and 25 mol% or less, even more preferably 5 mol% or more and 30 mol% or less, even more preferably 8 mol% or more and 32 mol% or less, even more preferably 10 mol% or more and 34 mol% or less, even more preferably 15 mol% or more and 36 mol% or less, even more preferably 20 mol% or more and 38 mol% or less, and even more preferably 25 mol% or more and 40 mol% or less.

[0024] Furthermore, the content of the repeating unit (c) derived from a cyclic olefin in the thermosetting cyclic olefin copolymer (A) of this embodiment is preferably 1 mol% or more and 40 mol% or less, more preferably 3 mol% or more and 30 mol% or less, even more preferably 5 mol% or more and 25 mol% or less, even more preferably 8 mol% or more and 20 mol% or less, and even more preferably 10 mol% or more and 15 mol% or less.

[0025] When the content of each repeating unit in the thermosetting cyclic olefin copolymer (A) is within the above range, the performance balance of low dielectric properties and heat resistance can be further improved when the copolymer is made into a film. Furthermore, the performance balance of the film's mechanical properties, transparency, and gas barrier properties can be further improved. In other words, a film with an improved balance of these physical properties can be obtained.

[0026] The olefin, which is one of the copolymerization raw materials for the thermosetting cyclic olefin copolymer (A), is a monomer that undergoes addition copolymerization to give the skeleton represented by formula (I), and is an olefin represented by formula (Ia).

[0027] [ka]

[0028] In the above formula (Ia), R 300represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms. The olefin represented by formula (Ia), i.e., the olefin constituting the olefin-derived repeating unit (a), includes, for example, one or more olefins selected from 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, 1-eicosene, and the like. From the viewpoint of further improving the balance of low dielectric properties and heat resistance when formed into a film, the olefin represented by formula (Ia), i.e., the olefin constituting the olefin-derived repeating unit (a), preferably contains one or more olefins selected from the group consisting of ethylene and propylene, and more preferably contains ethylene. Two or more olefins represented by formula (Ia) may be used. Furthermore, the olefin may contain at least one biomass-derived monomer (biomass-derived ethylene, biomass-derived propylene, etc.).

[0029] The cyclic non-conjugated diene monomer, which is one of the copolymerization raw materials for the thermosetting cyclic olefin copolymer (A), undergoes addition copolymerization to form a repeating unit represented by formula (III). For example, a cyclic non-conjugated diene represented by formula (IIIa) corresponding to formula (III) is used. The cyclic non-conjugated diene may contain a structural unit derived from a biomass-derived monomer (cyclic non-conjugated diene).

[0030] [ka]

[0031] In 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 ~R76 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.

[0032] The cyclic non-conjugated diene represented by formula (IIIa), i.e., the cyclic non-conjugated diene constituting the repeating unit (b) derived from a cyclic non-conjugated diene, is not particularly limited, and includes, for example, one or more cyclic non-conjugated dienes selected from the cyclic non-conjugated dienes represented by the following chemical formulas. Among these, the cyclic non-conjugated diene represented by formula (IIIa), i.e., the cyclic non-conjugated diene constituting the repeating unit (b) derived from a cyclic non-conjugated diene, is preferably 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.

[0033] [ka]

[0034] [ka]

[0035] The cyclic non-conjugated diene represented by formula (IIIa) can also be represented by, for example, formula (IIIb).

[0036] [ka]

[0037] In formula (IIIb), n is an integer of 0 to 10, R1 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R2 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

[0038] The thermosetting cyclic olefin copolymer (A) contains a repeating unit derived from a cyclic non-conjugated diene represented by formula (III), and thus can contain double bonds in the side chain portion, i.e., in the portion other than the main chain of the copolymer.

[0039] The cyclic olefin, which is one of the copolymerization raw materials for the thermosetting cyclic olefin copolymer (A), undergoes addition copolymerization to form a repeating unit represented by formula (V). For example, a cyclic olefin represented by formula (Va) corresponding to formula (V) is used.

[0040] [ka]

[0041] In 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.

[0042] Specific examples of the cyclic olefin represented by formula (Va) include the compounds described in WO 2006 / 118261. The cyclic olefin represented by formula (Va), i.e., the cyclic olefin constituting the cyclic olefin-derived structural unit (c), is bicyclo[2.2.1]-2-heptene (also called "norbornene") and tetracyclo[4.4.0.1 2,5 .1 7,10 Preferably, the cyclic olefin contains one or more selected from the group consisting of cyclo[2.2.1]-3-dodecene (also known as "tetracyclododecene"), and more preferably bicyclo[2.2.1]-2-heptene. These cyclic olefins have the advantage that the modulus of elasticity of the copolymer (A) and the cured product is easily maintained because they contain a rigid ring structure, and that crosslinking is easily controlled because they do not contain heterogeneous double bond structures. The cyclic olefin represented by formula (Va) may contain a structural unit derived from a biomass-derived monomer (cyclic olefin).

[0043] By using the olefin represented by formula (Ia) and the cyclic olefin represented by formula (Va) as copolymerization components, the solubility of the thermosetting cyclic olefin copolymer (A) in solvents is further improved, resulting in good moldability and improved product yield.

[0044] The thermosetting cyclic olefin copolymer (A) may further contain, in addition to the repeating units (a) derived from one or more olefins represented by formula (I), the repeating units (b) derived from a cyclic non-conjugated diene represented by formula (III), and the repeating units (c) derived from one or more cyclic olefins represented by formula (V), one or more repeating units selected from the group consisting of repeating units derived from cyclic olefins other than the cyclic non-conjugated diene represented by formula (III) and the cyclic olefin represented by formula (V), and repeating units derived from chain polyenes. In this case, as copolymerization raw materials for the thermosetting cyclic olefin copolymer (A), in addition to the olefin represented by formula (Ia), the cyclic non-conjugated diene represented by formula (IIIa), and the cyclic olefin represented by formula (Va), a cyclic olefin other than the cyclic non-conjugated diene represented by formula (IIIa) and the cyclic olefin represented by formula (Va), and / or a chain polyene can be used. Examples of such cyclic olefins and chain polyenes include cyclic olefins represented by formula (VIa), cyclic olefins represented by formula (VIIa), chain polyenes represented by formula (VIIIa), etc. Two or more different types of these cyclic olefins and chain polyenes may be used.

[0045] [ka]

[0046] In formula (VIa), x and d are 0 or an integer of 1 or more, preferably an integer of 0 or more and 2 or less, more preferably 0 or 1, y and z are 0, 1, or 2, and R 81 ~R 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 the carbon atom to which R is bonded. 93 or the carbon atom to which R is attached 91 may be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and when y and z are both 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.

[0047] [ka]

[0048] In 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 an integer of 1 or more and 18 or less.

[0049] [ka]

[0050] In 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.

[0051] Specific examples of the cyclic olefins represented by formula (VIa) and formula (VIIa) that can be used include the compounds described in paragraphs 0037 to 0063 of WO 2006 / 118261.

[0052] Examples of the linear polyene represented by 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.

[0053] When the thermosetting cyclic olefin copolymer (A) contains a repeating unit derived from a chain polyene represented by formula (VIIIa), or a repeating unit derived from a cyclic non-conjugated diene represented by formula (IIIa) and a cyclic olefin other than the cyclic olefin represented by formula (Va) (e.g., formula (VIa) or formula (VIIa)), the content of the repeating units is, for example, 0.1 mol % or more and 100 mol % or less, preferably 0.1 mol % or more and 50 mol % or less, based on the total number of moles of the repeating units derived from one or more olefins represented by formula (I), the repeating units derived from one or more cyclic non-conjugated dienes represented by formula (III), and the repeating units derived from one or more cyclic olefins represented by formula (V).

[0054] By using the olefin represented by formula (Ia), the cyclic olefin represented by formula (VIa) or (VIIa), and the linear polyene represented by formula (VIIIa) as copolymerization components, the effects of this embodiment can be achieved, and the solubility of the thermosetting cyclic olefin copolymer (A) in solvents is further improved, resulting in good moldability and improved product yield. Among these, the cyclic olefin represented by formula (VIa) or (VIIa) is preferred. These cyclic olefins have the advantage that the elastic modulus of the thermosetting cyclic olefin copolymer (A) and film is easily maintained because they contain a rigid ring structure, and the absence of heterogeneous double bond structures makes it easier to control crosslinking.

[0055] The number average molecular weight (Mn) of the thermosetting cyclic olefin copolymer (A) measured by gel permeation chromatography (GPC) in terms of polystyrene is preferably 1,000 or more and 100,000 or less, more preferably 2,000 or more and 80,000 or less, even more preferably 3,000 or more and 60,000 or less, even more preferably 3,500 or more and 50,000 or less, even more preferably 4,000 or more and 40,000 or less, and even more preferably 4,500 or more and 30,000 or less, from the viewpoint of further improving the performance balance between low dielectric properties and heat resistance. The number average molecular weight (Mn) of the thermosetting cyclic olefin copolymer (A) can be controlled by the polymerization conditions such as the polymerization catalyst, co-catalyst, amount of H2 added, and polymerization temperature.

[0056] The comonomer content and glass transition temperature (Tg) of the thermosetting cyclic olefin copolymer (A) can be controlled by adjusting the monomer charging ratio depending on the intended application. The Tg of the thermosetting cyclic olefin copolymer (A) is preferably 110° C. or higher and 300° C. or lower, more preferably 110° C. or higher and 280° C. or lower, even more preferably 110° C. or higher and 260° C. or lower, even more preferably 110° C. or higher and 240° C. or lower, even more preferably 110° C. or higher and 220° C. or lower, even more preferably 110° C. or higher and 200° C. or lower, even more preferably 110° C. or higher and 180° C. or lower, and even more preferably 110° C. or higher and 160° C. When the Tg is within the above range, the melt moldability of the thermosetting cyclic olefin copolymer (A) and its solubility in solvents when made into a varnish are improved.

[0057] The intrinsic viscosity [η] of the thermosetting cyclic olefin copolymer (A) measured in decalin at 135°C is preferably 0.10 dL / g to 15 dL / g, more preferably 0.12 dL / g to 5 dL / g, and even more preferably 0.15 dL / g to 3 dL / g. When the intrinsic viscosity [η] is equal to or less than the upper limit, moldability can be further improved. On the other hand, when the intrinsic viscosity [η] is equal to or greater than the lower limit, the heat resistance and mechanical properties of the cured product can be further improved. The intrinsic viscosity [η] of the thermosetting cyclic olefin copolymer (A) can be controlled by the polymerization conditions such as the polymerization catalyst, co-catalyst, amount of H2 added, and polymerization temperature.

[0058] The content of the thermosetting cyclic olefin copolymer (A) in the resin composition particles of this embodiment, when the total amount of solids in the resin composition particles (the total amount of components remaining as solids when cured) is taken as 100 parts by mass, is preferably 10 parts by mass or more and 99 parts by mass or less, more preferably 12 parts by mass or more and 98 parts by mass or less, even more preferably 13 parts by mass or more and 80 parts by mass or less, even more preferably 14 parts by mass or more and 70 parts by mass or less, even more preferably 15 parts by mass or more and 60 parts by mass or less, even more preferably 16 parts by mass or more and 50 parts by mass or less, and even more preferably 17 parts by mass or more and 50 parts by mass or less, from the viewpoint of further improving the performance balance of the heat resistance, mechanical properties, and low dielectric properties of the resulting cured product.

[0059] <Method for producing thermosetting cyclic olefin copolymer (A)> The thermosetting cyclic olefin copolymer (A) 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.

[0060] <Radical initiator (B)> The resin composition particles of the present embodiment contain a radical initiator (B).

[0061] Crosslinking with the radical initiator (B) can be performed using the same crosslinking method using a normal radical initiator as used for polyolefins, etc. That is, the thermosetting cyclic olefin copolymer (A) is mixed with a radical initiator such as 2,3-dimethyl-2,3-diphenylbutane, and then heated to crosslink.

[0062] The radical initiator (B) may be a known thermal radical initiator, a known photoradical initiator, or a combination of these.

[0063] Examples of such thermal radical initiators include dialkyl peroxides such as dicumyl peroxide, t-butylcumyl peroxide, 2,5-bis(t-butylperoxy)2,5-dimethylhexane, 2,5-bis(t-butylperoxy)2,5-dimethylhexyne-3, di-t-butyl peroxide, isopropylcumyl-t-butyl peroxide, and bis(α-t-butylperoxyisopropyl)benzene; 1,1-bis(t-butylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclododecane, n-butyl-4,4-bis(t-butylperoxy)valerate, and ethyl-3,3-bis(t-butylperoxy). peroxyketals 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 2,3-dimethyl-2,3-diphenylbutane; and 3,3,5,7,7-pentamethyl-1,2,4-trioxepane.

[0064] Among the radical initiators (B), 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 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.

[0065] From the viewpoint of improving the performance balance of the dispersibility of the resin composition particles in polar solvents, heat resistance, and low dielectric properties, the radical initiator (B) preferably contains a non-peroxide radical initiator, more preferably contains a thermal radical initiator of a bibenzyl compound, and even more preferably contains 2,3-dimethyl-2,3-diphenylbutane (DMDPB).

[0066] The content of the radical initiator (B) in the resin composition particles of this embodiment is preferably 0.1 parts by mass or more and 25.0 parts by mass or less, more preferably 0.5 parts by mass or more and 20.0 parts by mass or less, more preferably 1.0 parts by mass or more and 15.0 parts by mass or less, even more preferably 1.5 parts by mass or more and 14.0 parts by mass or less, even more preferably 1.8 parts by mass or more and 13.0 parts by mass or less, even more preferably 2.0 parts by mass or more and 12.0 parts by mass or less, even more preferably 2.4 parts by mass or more and 11.0 parts by mass or less, even more preferably 2.7 parts by mass or more and 10.0 parts by mass or less, and even more preferably 3.0 parts by mass or more and 9.0 parts by mass or less, relative to 100 parts by mass of the thermosetting cyclic olefin copolymer (A), from the viewpoint of further improving the performance balance of low dielectric properties and heat resistance of the obtained cured product.

[0067] The total content of the thermosetting cyclic olefin copolymer (A) and the radical initiator (B) in the resin composition particles of this embodiment is preferably 5 parts by mass or more and 100 parts by mass or less, more preferably 8 parts by mass or more and 97 parts by mass or less, even more preferably 11 parts by mass or more and 94 parts by mass or less, even more preferably 14 parts by mass or more and 91 parts by mass or less, and even more preferably 17 parts by mass or more and 88 parts by mass or less, when the total amount of solids in the resin composition particles (the total amount of components that remain as solids when cured) is taken as 100 parts by mass.

[0068] The resin composition particles of this embodiment may further contain a crosslinking aid. There are no limitations on the crosslinking aid, but examples include oximes such as p-quinone dioxime and p,p'-dibenzoylquinone dioxime; acrylates or methacrylates such as ethylene dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, cyclohexyl methacrylate, acrylic acid / zinc oxide mixtures, and allyl methacrylate; vinyl monomers such as divinylbenzene, vinyltoluene, and vinylpyridine; allyl compounds such as hexamethylenediallylnadiimide, diaryl itaconate, diallyl phthalate, diallyl isophthalate, diallyl monoglycidyl isocyanurate, triallyl cyanurate, and triallyl 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.

[0069] <Inorganic filler (C)> The resin composition particles of this embodiment may further contain an inorganic filler (C).

[0070] The inorganic filler (C) includes, for example, one or more selected from the group consisting of silica, alumina, diatomaceous earth, titanium oxide, magnesium oxide, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, dolomite, calcium sulfate, potassium titanate, barium sulfate, calcium sulfite, asbestos, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, molybdenum sulfide, boron fiber, silicon carbide fiber, polyethylene fiber, polypropylene fiber, polyester fiber, polyamide fiber, boron nitride, talc, mica, clay, glass flake, calcium carbonate, alumina, wollastonite, sericite, hydrotalcite, montmorillonite, and graphite, and more preferably includes silica.

[0071] The true density ρ of the inorganic filler (C) is preferably 1.3 g / cm 3 More than 7.0g / cm3 or less, more preferably 1.5 g / cm 3 More than 6.0g / cm 3 or less, more preferably 1.8 g / cm 3 More than 5.0g / cm 3 or less, more preferably 1.8 g / cm 3 More than 4.0g / cm 3 or less, more preferably 1.8 g / cm 3 More than 3.0g / cm 3 The following is the result. Here, the true density ρ of the inorganic filler (C) is measured by the pycnometer method in accordance with JIS R1620:1995.

[0072] Average particle size D of inorganic filler (C) 50 is preferably 0.1 μm or more and 30.0 μm or less, more preferably 0.3 μm or more and 25.0 μm or less, and even more preferably 0.5 μm or more and 20.0 μm or less. Here, the average particle diameter D of the inorganic filler (C) 50 represents the particle size at which the cumulative frequency is 50% on a volume-based cumulative frequency distribution curve measured by a laser diffraction particle size distribution measurement method in accordance with JIS Z8825:2013. Average particle size D of inorganic filler (C) 50 When the average particle diameter D of the inorganic filler (C) is equal to or less than the upper limit, the characteristic error when dispersed in a resin composite can be improved. 50 When the content of the resin composition is equal to or greater than the lower limit, the resin composition can be more uniformly dispersed in a solvent when a varnish is prepared.

[0073] The content of the inorganic filler (C) in the resin composition particles of this embodiment, relative to 100 parts by mass of the thermosetting cyclic olefin copolymer (A), is preferably 0 parts by mass or more and 1,000 parts by mass or less, more preferably 10 parts by mass or more and 1,000 parts by mass or less, even more preferably 10 parts by mass or more and 800 parts by mass or less, even more preferably 50 parts by mass or more and 600 parts by mass or less, even more preferably 100 parts by mass or more and 550 parts by mass or less, and even more preferably 200 parts by mass or more and 500 parts by mass or less.

[0074] The content of the inorganic filler (C) in the resin composition particles of this embodiment, when the entire resin composition particles are taken as 100% by mass, is preferably 0% by mass or more and less than 100% by mass, preferably 10% by mass or more and 95% by mass or less, more preferably 20% by mass or more and 90% by mass or less, even more preferably 30% by mass or more and 85% by mass or less, and even more preferably 40% by mass or more and 80% by mass or less.

[0075] <Antioxidant (D)> The resin composition particles of this embodiment may further contain an antioxidant (D). The antioxidant (D) is not limited, and known antioxidants can be used, such as phenol-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, thioether-based antioxidants, and hindered amine-based antioxidants. These may be used alone or in combination. The antioxidant (D) preferably includes a phenolic antioxidant, such as Irganox 1010 manufactured by BASF.

[0076] Examples of phenolic antioxidants 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-methylphenyl acrylate, and the like. -(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-tetrahydrofuran Alkyl-substituted phenols such as xaspiro[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, 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 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.Among these, acrylate-based phenol compounds and alkyl-substituted phenol-based compounds are preferred, alkyl-substituted phenol-based compounds are more preferred, and pentaerythritol tetrakis[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate is even more preferred.

[0077] 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 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-butylphenanthren-10-oxide); 4,4'-Isopropylidene-bis(phenyl-di-alkyl(C12-C15) phosphite), 4,4'-Isopropylidene-bis(diphenyl monoalkyl(C12-C15) phosphite), 1,1,3-tris(2-methyl-4-di-tridecylphosphite-5-t-butylphenyl)butane, tetrakis(2,4-di-t-butylphenyl)-4,4'-biphenylene diphosphite, cyclic neo Examples of the diphosphite compounds include pentanetetraylbis(isodecylphosphite), cyclic neopentanetetraylbis(nonylphenylphosphite), cyclic neopentanetetraylbis(2,4-di-t-butylphenylphosphite), cyclic neopentanetetraylbis(2,4-dimethylphenylphosphite), and cyclic neopentanetetraylbis(2,6-di-t-butylphenylphosphite). Among these, monophosphite compounds are preferred, and tris(nonylphenyl)phosphite, tris(dinonylphenyl)phosphite, and tris(2,4-di-t-butylphenyl)phosphite are more preferred.

[0078] Examples of sulfur-based antioxidants include 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.

[0079] Examples of thioether antioxidants include 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.

[0080] The content of the antioxidant (D) in the resin composition particles of this embodiment is preferably 0.01 to 5.0 parts by mass, more preferably 0.02 to 3.0 parts by mass, even more preferably 0.03 to 2.0 parts by mass, even more preferably 0.04 to 1.0 parts by mass, even more preferably 0.04 to 0.5 parts by mass, and even more preferably 0.04 to 0.1 parts by mass, relative to 100 parts by mass of the thermosetting cyclic olefin copolymer (A), from the viewpoint of further improving the performance balance between low dielectric properties and heat resistance of the resulting cured product.

[0081] <Other ingredients> The resin composition particles of this embodiment may contain other components as long as the effects of the invention of this embodiment are not impaired. Examples of other components include one or more additives selected from the group consisting of organic fillers, heat stabilizers, weather stabilizers, 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 wettability improvers, hydrochloric acid absorbers, and metal deactivators; and resins other than the thermosetting cyclic olefin copolymer (A), such as epoxy resins and polystyrene resins.

[0082] <Method of manufacturing resin composition particles> The resin composition particles of this embodiment can be produced by the following procedure. The thermosetting cyclic olefin copolymer (A) is dissolved in a suitable solvent to prepare an intermediate solution. Alternatively, the solution obtained after the polymerization step of the thermosetting cyclic olefin copolymer (A) may be used as is without crystallization. The solvent may be, for example, a saturated hydrocarbon such as heptane, hexane, decane, or cyclohexane, or a low-polarity aromatic hydrocarbon such as toluene, benzene, or xylene. Here, the solvent is preferably an organic solvent from the viewpoint of ease of dissolving the thermosetting cyclic olefin copolymer (A). From the viewpoint of ease of dissolving the thermosetting cyclic olefin copolymer (A), the solvent is more preferably a low-polarity solvent. From the viewpoint of ease of dissolving the thermosetting cyclic olefin copolymer (A), the solvent is even more preferably toluene.

[0083] Next, the radical initiator (B) is added to the intermediate solution. At this time, other components such as the inorganic filler (D) are mixed in as needed. At this time, the radical initiator (B) and other components may be dissolved or dispersed in the intermediate solution.

[0084] Next, resin composition particles are produced from the intermediate solution. A known powder production method can be used to produce the resin composition particles. Known powder production methods can be used, including a breakdown method and a build-up method. Examples of breakdown methods that can be used include wet pulverization, dry pulverization, high-pressure emulsification, and laser ablation. Examples of built-up methods that can be used include spray drying and crystallization. A combination of the breakdown and build-up methods can also be used. From the viewpoint of reducing the particle size of the resin composition particles, it is preferable to use the build-up method. When using the build-up method, it is preferable to use the spray drying method, from the viewpoint of reducing the coarse particles of the resin composition particles.

[0085] The method for producing resin composition particles of this embodiment preferably includes a step of producing resin composition particles by spray-drying or crystallizing an intermediate solution that is a mixture containing the thermosetting cyclic olefin copolymer (A) and the radical initiator (B).The method for producing resin composition particles of this embodiment more preferably includes a step of producing resin composition particles by spray-drying an intermediate solution that contains the thermosetting cyclic olefin copolymer (A) and the radical initiator (B). The intermediate solution may further contain an organic solvent. The organic solvent preferably contains a low-polarity solvent. The low-polarity solvent preferably contains toluene.

[0086] <Physical properties of resin composition particles> Hereinafter, preferred properties of the resin composition particles of this embodiment will be described.

[0087] The resin composition particles of this embodiment are, for example, in an uncured state or a semi-cured state.

[0088] The resin composition particles of this embodiment are preferably spherical in shape from the viewpoint of improving dispersibility in polar solvents.

[0089] Average particle diameter D of the resin composition particles of this embodiment 50 From the viewpoint of improving dispersibility in polar solvents, the average particle size may be preferably 0.01 μm or more and 30.0 μm or less, more preferably 0.03 μm or more and 25.0 μm or less, even more preferably 0.05 μm or more and 20.0 μm or less, even more preferably 0.08 μm or more and 15.0 μm or less, even more preferably 0.10 μm or more and 10.0 μm or less, even more preferably 0.15 μm or more and 8.0 μm or less, even more preferably 0.20 μm or more and 6 μm or less, even more preferably 0.25 μm or more and 4 μm or less, and even more preferably 0.30 μm or more and 2.0 μm or less. Here, the average particle size D of the resin composition particles 50 is the average particle diameter D based on the number of particles observed in a scanning electron microscope (SEM) image. 50 Average particle diameter D 50 can be measured, for example, by the method described in the Examples.

[0090] The true density ρ of the resin composition particles of this embodiment is preferably 0.9 g / cm from the viewpoint of improving dispersibility in polar solvents. 3 More than 3.0g / cm 3 or less, more preferably 1.0 g / cm 3 More than 2.9g / cm 3 More preferably, 1.1 g / cm or less 3 More than 2.8g / cm 3 or less, more preferably 1.2 g / cm 3 More than 2.7g / cm 3 or less, more preferably 1.3 g / cm 3 More than 2.6g / cm 3 or less, more preferably 1.4 g / cm 3 More than 2.5g / cm 3 The following is the result. Here, the true density ρ of the resin composition particles of the present embodiment is measured by the pycnometer method in accordance with JIS R1620:1995.

[0091] [Uses of resin composition particles] The cured product of the resin composition particles of this embodiment has a good balance of low dielectric properties and heat resistance.Therefore, the cured product of the resin composition obtained by mixing the resin composition particles of this embodiment with a matrix resin can be used in applications such as optical fibers, optical waveguides, optical disk substrates, optical filters, lenses, optical adhesives, optical filters for PDPs, organic EL coating materials, 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 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, liquid crystal display and solar cell substrates, medical instruments, automotive components, resin modifiers, transparent substrates for displays, gas barrier coating materials, electric wire coating materials, automotive components, 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, hard coating materials, and the like. In particular, a cured product obtained by curing a resin composition in which the resin composition particles of this embodiment are mixed with a matrix resin has an improved balance of low dielectric properties and heat resistance, and is therefore suitable for use in printed wiring boards, and more suitable for use in high-frequency applications such as high-frequency printed wiring boards.

[0092] [Dispersion] The dispersion of this embodiment includes resin composition particles and a polar solvent. The dispersion is produced by dispersing the resin composition particles in the polar solvent. The dispersion may also be produced by mixing the resin composition particles in the polar solvent. Examples of polar solvents that may be used include alcohols such as methanol, ethanol, isopropyl alcohol, butanol, pentanol, hexanol, propanediol, and phenol; ketone-based 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; and halogenated hydrocarbons such as trichloroethylene, dichloroethylene, and chlorobenzene. These solvents may be used alone or in combination of two or more in any ratio. The polar solvent may preferably be a ketone-based solvent, from the viewpoint of being able to dissolve other resin compositions in the dispersion. For example, methyl ethyl ketone (MEK) may be used as the ketone-based solvent.

[0093] [Resin composition] The resin composition of the present embodiment includes resin composition particles and a matrix resin. The resin composition is produced by mixing the resin composition particles into the matrix resin. The resin composition may also be produced by dispersing the resin composition particles in the matrix resin.

[0094] <Matrix resin> The matrix resin may be a synthetic resin or a natural resin. The matrix resin may be a thermosetting resin or a thermoplastic resin. The thermoplastic resin may be an ABS resin (acrylonitrile-butadiene-styrene copolymer resin), a polyamide resin, a polyimide resin, a polyarylate resin, a polybutylene terephthalate resin, a polycarbonate resin, a polyethylene resin, a polyetherimide resin, a polyether ether ketone resin, a polytetrafluoroethylene resin, a polyethersulfone resin, a polyethylene terephthalate resin, a polymethacrylic resin, a polyacetal resin, a polypropylene resin, a polystyrene resin, a polyvinyl chloride resin, a polyvinylidene fluoride resin, a polyamide-imide resin, a polychlorotrifluoroethylene resin, a polyphenylene ether resin, a polyphenylene sulfide resin, a polyphenylene oxide resin, a polybenzimidazole resin, or a polyparaphenylene resin. The thermosetting resin may be a phenolic resin, an epoxy resin, a silicone resin, a polyurethane resin, a melamine resin, a urea resin, an alkyd resin, or an unsaturated polyester resin, a modified polyphenylene ether resin, a modified oligophenylene ether resin, a maleimide resin, a triazine resin, a bismaleimide-triazine resin, a cyanate resin, a benzoxazine resin, etc. The matrix resin may be one of these resins or a mixture of two or more of them in any ratio.

[0095] The total content of the resin composition particles in the resin composition is preferably 0.0010 parts by mass or more, more preferably 0.010 parts by mass or more, even more preferably 0.10 parts by mass or more, and even more preferably 1.0 part by mass or more, and is preferably 90 parts by mass or less, more preferably 80 parts by mass or less, even more preferably 70 parts by mass or less, even more preferably 60 parts by mass or less, and even more preferably 50 parts by mass or less, based on 100 parts by mass of the matrix resin.

[0096] <Other ingredients> The resin composition of this embodiment may contain other components as long as the effects of the invention of this embodiment are not impaired. Examples of other components include one or more additives selected from the group consisting of crosslinking aids, antioxidants, heat stabilizers, weather stabilizers, 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, organic fillers, inorganic fillers, hydrochloric acid absorbers, and metal deactivators.

[0097] The resin composition of this embodiment may further contain a crosslinking aid. There are no limitations on the crosslinking aid, but examples include oximes such as p-quinone dioxime and p,p'-dibenzoylquinone dioxime; acrylates or methacrylates such as ethylene dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, cyclohexyl methacrylate, acrylic acid / zinc oxide mixtures, and allyl methacrylate; vinyl monomers such as divinylbenzene, vinyltoluene, and vinylpyridine; allyl compounds such as hexamethylenediallylnadimide, diaryl itaconate, diallyl phthalate, diallyl isophthalate, diallyl monoglycidyl isocyanurate, triallyl cyanurate, and triallyl 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.

[0098] [varnish] The resin composition of the present embodiment can be mixed with a solvent to form a varnish, that is, the varnish of the present embodiment contains the resin composition and a solvent. The solvent for preparing the varnish is not limited as long as it does not impair the solubility or affinity of the resin composition (resin composition particles, matrix resin). 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; and halogenated hydrocarbons such as trichloroethylene, dichloroethylene, and chlorobenzene. These solvents can be used alone or in combination in any proportion. The polar solvent may be preferably a ketone solvent, from the viewpoint of being able to dissolve other resin compositions in the dispersion. As the ketone solvent, for example, methyl ethyl ketone (MEK) may be used.

[0099] The amount of solvent added to the resin composition is preferably 60 parts by mass or more and 400 parts by mass or less, more preferably 65 parts by mass or more and 300 parts by mass or less, and even more preferably 70 parts by mass or more and 230 parts by mass or less, based on 100 parts by mass of the entire resin composition, from the viewpoint of further improving the handling and coating properties of the varnish.

[0100] The total content of the resin composition in the varnish is preferably 15 parts by mass or more and 70 parts by mass or less, more preferably 30 parts by mass or more and 67 parts by mass or less, even more preferably 40 parts by mass or more and 64 parts by mass or less, and even more preferably 50 parts by mass or more and 60 parts by mass or less, when the entire varnish is 100 parts by mass.

[0101] Furthermore, the total content of the resin composition particles in the varnish is preferably 0.0010 parts by mass or more and 45 parts by mass or less, more preferably 0.010 parts by mass or more and 40 parts by mass or less, even more preferably 0.10 parts by mass or more and 35 parts by mass or less, and even more preferably 1.0 parts by mass or more and 30 parts by mass or less, when the matrix resin is taken as 100 parts by mass.

[0102] 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 in which the components are mixed is not limited, and the components may be mixed in any manner, such as all at once or in portions. The apparatus for preparing the varnish is also not limited, and any apparatus capable of stirring and mixing, such as a batch type or a continuous type, may be used. The temperature at which the varnish is prepared can be selected arbitrarily from room temperature to the boiling point of the solvent.

[0103] [Cured product] The cured product of this embodiment is a cured product of the resin composition of this embodiment. The cured product of this embodiment can be obtained by curing one or more resins selected from the group consisting of resin composition particles and matrix resins in the resin composition of this embodiment. The resin composition particles and matrix resin can be cured by crosslinking the resin composition particles and matrix resin. The crosslinking can be performed by a crosslinking step appropriate for the type of resin. The temperature, time, degree of vacuum, etc. of the crosslinking step can be appropriately selected depending on the resin and the crosslinking aid contained in the resin.

[0104] The crosslinking step can be carried out with the resin composition of the present embodiment in a molten state, or with the resin composition in a solution state where it is dissolved or dispersed in a solvent. Alternatively, the crosslinking step can be carried out by volatilizing the solvent from a solution state where the resin composition is dissolved in a solvent, forming the resin composition into any shape such as a film or coating, and then further promoting the crosslinking reaction. When the reaction is carried out in a molten state, the mixture of raw materials is melt-kneaded and reacted using a kneading device such as a mixing roll, a Banbury mixer, an extruder, a kneader, a continuous mixer, etc. Alternatively, the crosslinking reaction can be further 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 above solution blending method can be used as the solvent.

[0105] [Film or Sheet] The film or sheet of this embodiment contains the resin composition of this embodiment or the cured product of this embodiment. The resin composition of this embodiment or the cured product of this embodiment can be formed into a film or sheet (hereinafter referred to as a film or the like) and used in various applications. Various known methods can be used to form the resin composition of this embodiment or the cured product of this embodiment into a film or the like. 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, if necessary, heat-treated to crosslink the resin composition to obtain a cured product, and a film or the like made of the resin composition of this embodiment is formed. Examples of thermoplastic resin films include PET films and polyimide resin films. 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 is a method in which the resin composition of the present embodiment is melt-molded to obtain a film or the like, and then, if necessary, the resin composition is crosslinked by a heat treatment or the like to form a cured product, thereby forming a film or the like made of the resin composition of the present embodiment.

[0106] [Laminate] The laminate of this embodiment includes the film or sheet of this embodiment. For example, by laminating the film of the present embodiment on a substrate, it can be used as a laminate for various purposes. That is, by laminating the film of the present embodiment on a substrate, it can be used as a laminate for various purposes. For example, it can be used as an organic insulating film that requires low dielectric properties or a curable adhesive sheet for a device that includes 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 or the like produced by the above-mentioned method onto a substrate, and, if necessary, heat-curing the laminate using a press or the like. Alternatively, a laminate can be produced by laminating an electrical insulating layer containing the above-mentioned cured product onto a conductor layer.

[0107] [Multi-layer molded body or multi-layer laminated film] The cured product obtained by curing the resin composition of the present 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 laminated films include a multilayer molded article for an optical lens in which the film of this embodiment is formed on the surface of a resin optical lens, and a multilayer gas barrier film in which the cured product 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.

[0108] [Prepreg] The prepreg of the present embodiment is formed by combining the resin composition of the present embodiment with a sheet-like fiber base material. That is, the prepreg of the present embodiment includes the resin composition and the sheet-like fiber base material. The method for producing the prepreg is not particularly limited, and various known methods can be applied. For example, there is a method including a step of impregnating a sheet-like fiber substrate with the above-mentioned varnish to obtain an impregnated body, and a step of heating the obtained impregnated body to dry the solvent contained in the varnish. The impregnation of the sheet-like fiber substrate with the varnish can be carried out, for example, by applying a predetermined amount of varnish to the sheet-like fiber substrate by a known method such as spray coating, dip coating, roll coating, curtain coating, die coating, or slit coating, and if necessary, placing a protective film on top of it and pressing it from above with a roller or the like. The process of heating the impregnated body and drying the solvent contained in the varnish is not particularly limited, but examples thereof include a batch method of drying in air or nitrogen using a blower dryer, or a continuous method of drying by passing through a heating furnace. 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.

[0109] The fibers constituting the sheet-like fiber substrate can be inorganic or organic, and are not particularly limited. Examples include organic fibers such as PET (polyethylene terephthalate) fibers, polystyrene fibers, aramid fibers, ultra-high molecular weight polyethylene fibers, polyamide (nylon) fibers, and liquid crystal polyester fibers; and inorganic fibers such as glass fibers, carbon fibers, alumina fibers, tungsten fibers, molybdenum fibers, titanium fibers, steel fibers, boron fibers, silicon carbide fibers, and silica fibers. Among these, preferred are one or more types selected from the group consisting of organic fibers and glass fibers, and more preferred are one or more types selected from the group consisting of aramid fibers, liquid crystal polyester fibers, and glass fibers. Examples of glass fibers include E-glass, NE-glass, S-glass, D-glass, H-glass, and T-glass. The impregnation of the sheet-like fiber substrate with the varnish is carried out, for example, by immersion and coating. The impregnation may be repeated multiple times as necessary.

[0110] The thickness of the prepreg is appropriately selected depending on the intended use, but is, for example, 0.001 mm to 1.0 mm, preferably 0.005 mm to 0.5 mm, and more preferably 0.01 mm to 0.3 mm. This range is suitable because it allows for sufficient shaping during lamination and the mechanical strength and toughness of the laminate obtained by curing.

[0111] [Metal-clad laminate] 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 by a lamination press or the like. That is, the laminate of this embodiment may further include a metal foil on at least one surface. The metal foil may be attached to both surfaces of the laminate. Examples of metal foils include copper foil, aluminum foil, nickel foil, gold foil, silver foil, stainless steel foil, etc. From the viewpoints of economy, processability, thermal conductivity, and electrical conductivity, electrolytic copper foil is preferred. As a method for producing the metal clad laminate of this embodiment, various known methods can be applied. 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 it by pressing or the like.

[0112] The metal clad laminate of this embodiment contains a cured product of the resin composition of this embodiment, and therefore has an improved balance of low dielectric properties and heat resistance. Therefore, the metal clad laminate of this embodiment can be suitably used as an insulating layer material for printed wiring boards.

[0113] [Printed wiring board] The cured product obtained by curing the resin composition of this embodiment has an improved balance of low dielectric properties and heat resistance, and is therefore suitable for use in printed wiring boards. The printed wiring board of this embodiment includes an insulating layer containing the cured product of this embodiment or a cured product of the prepreg of this embodiment, and a conductor layer on the insulating layer. A commonly known method can be used to manufacture a printed wiring board, and is not particularly limited. For example, a film or laminate manufactured by the above-described method is heat-cured using a lamination press or the like to form an electrical insulating layer. Next, a conductor layer is laminated on the obtained electrical insulating layer using a known method to produce a laminate. Thereafter, the conductor layer in the laminate is subjected to circuit processing or the like to obtain a printed wiring board.

[0114] 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.

[0115] Such a printed wiring board can be used as an electronic device by mounting electronic components such as semiconductor elements on it. That is, the electronic device of this embodiment includes the printed wiring board of this embodiment. The electronic device can be manufactured based on publicly known information. Examples of such electronic devices include ICT infrastructure equipment such as servers, routers, supercomputers, mainframes, and workstations; antennas such as GPS antennas, antennas for wireless base stations, millimeter-wave antennas, and RFID antennas; communication devices such as mobile phones, smartphones, PHS, PDAs, and tablet terminals; digital devices such as personal computers, televisions, digital cameras, digital video cameras, POS terminals, wearable terminals, and digital media players; in-vehicle electronic devices such as electronic control system devices, in-vehicle communication devices, car navigation devices, millimeter-wave radars, and in-vehicle camera modules; semiconductor testing equipment, high-frequency measuring equipment, and the like.

[0116] [Uses of the cured product] The cured product of the resin composition of the present embodiment has a good balance of low dielectric properties and heat resistance, 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 electroluminescence (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, wire coating materials, automotive components, aerospace components, semiconductor processing materials, wire coating materials, lithium-ion battery components, fuel cell components, capacitor films, flexible display components, anchor coating materials, transparent adhesives, and hard coating materials. In particular, the cured product obtained by curing the resin composition of the present embodiment has an improved balance of low dielectric properties and heat resistance, and therefore can be suitably used for printed wiring boards, and more suitably used for high-frequency applications such as high-frequency printed wiring boards.

[0117] Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various other configurations can also be adopted. Furthermore, the present invention is not limited to the above-described embodiment, and modifications and improvements within the scope that do not impair the effects of the present invention are included in the present invention. [Example]

[0118] 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.

[0119] (Materials used in Examples and Comparative Examples) The materials used in each example are listed. Thermosetting cyclic olefin copolymer 1: Synthesis Example 1 described below Radical initiator: 2,3-dimethyl-2,3-diphenylbutane (manufactured by Thermo Scientific Chemicals) (hereinafter referred to as DMDPB) Inorganic filler: amorphous silica (product name: ADMAFINE SC2300-SVJ, manufactured by Admatechs Co., Ltd.)

[0120] The following raw materials were used to synthesize thermosetting cyclic olefin copolymer 1.

[0121] ·Transition metal compounds (1): It was synthesized by the method described in Synthesis Example 1 of JP-A No. 2004-331965.

[0122] Modified methylaluminoxane (MMAO, manufactured by Tosoh Finechem Co., Ltd.) Toluene (Fujifilm Wako Pure Chemical Industries, Ltd.: Wako Special Grade) Tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene (hereinafter also referred to as TD) (manufactured by Mitsui Chemicals, Inc.) 5-vinyl-2-norbornene (hereinafter referred to as VNB) (Tokyo Chemical Industry Co., Ltd.) Acetone (Fujifilm Wako Pure Chemical Industries, Ltd.: Wako Special Grade) Methanol (Fujifilm Wako Pure Chemical Industries, Ltd.: Wako Special Grade)

[0123] [Synthesis Example 1: Thermosetting Cyclic Olefin Copolymer 1] A 1 L stainless steel autoclave was thoroughly purged with nitrogen and charged with 455 ml of toluene, 29 ml of VNB, 16 ml of TD, a hexane solution of MMAO (0.8 mmol in terms of aluminum atom), and 446 ml of hydrogen. 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 50 minutes. The polymerization was then terminated by injecting 1 ml of methanol. After the polymerization was completed, ion-exchanged water was added to the resulting polymer solution and stirred for 1 hour, after which the organic layer was filtered through filter paper. This organic layer was poured into a mixed solvent of acetone and methanol to precipitate the 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 the thermosetting cyclic olefin copolymer (A), an ethylene / TD / VNB copolymer.

[0124] After synthesis, the thermosetting cyclic olefin copolymer 1 was subjected to measurement of the content of each repeating unit and the number average molecular weight (Mn).

[0125] [Measurement of the content of each repeating unit in thermosetting cyclic olefin copolymer 1] The contents of repeating units (a), (b) and (c) in the thermosetting cyclic olefin copolymer 1 were measured using a nuclear magnetic resonance spectrometer "EXcalibur270" manufactured by JEOL Ltd. under the following conditions. Number of times: 16 to 64 ·Measurement temperature: Room temperature (25℃) The results obtained from the above measurements 1 From the H-NMR spectrum, the contents of repeating unit (a), repeating unit (b), and repeating unit (c) were calculated based on the intensities of the peaks derived from hydrogen directly bonded to the double bond carbon and the peaks derived from other hydrogen.

[0126] The content of each repeating unit in the thermosetting cyclic olefin copolymer 1 was measured using a nuclear magnetic resonance spectrometer. 1 The content of repeating units (c) derived from TD in copolymer (A) determined by 1 H-NMR was 11 mol %, and the content of repeating units (b) derived from VNB was 26 mol %.

[0127] [Measurement of number average molecular weight (Mn) of thermosetting cyclic olefin copolymer 1] The number average molecular weight (Mn) of the thermosetting cyclic olefin copolymer 1 dissolved in o-dichlorobenzene was measured using gel permeation chromatography (GPC) under the following conditions, calibrating the molecular weight with monodisperse polystyrene standards (manufactured by Tosoh Corporation). Measurement equipment: Tosoh gel permeation chromatograph HLC-8321 GPC / HT type Data processing software: Waters Empower3 Detector: Tosoh Bryce type double-path, dual-flow RI detector (built-in) Column: Tosoh TSKgel GMH6-HT, TSKgel GMH6-HTL Column temperature: 140℃ Sample concentration: 0.1% (w / v) ·Injection volume: 400μL Sampling interval: 0.5 seconds ·Flow rate: 1.0ml / min The number average molecular weight (Mn) of the thermosetting cyclic olefin copolymer 1 determined by GPC measurement was 25,000.

[0128] [Example 1] (Preparation of Varnish) A toluene solution (10% by mass) of thermosetting cyclic olefin copolymer 1 (Synthesis Example 1) was prepared. To the toluene solution of thermosetting cyclic olefin copolymer 1, an inorganic filler was added as needed, and a radical initiator was dissolved. The blending composition of each component was in accordance with the blending composition in Table 1. A varnish was prepared by stirring the toluene solution of thermosetting cyclic olefin copolymer 1 containing the radical initiator and the like. Note that the blending composition of each raw material in Table 1 is expressed in parts by mass.

[0129] (Preparation of Resin Composition Particles) The resulting varnish was converted into a fine powder using a spray dryer under the following spray drying conditions. Equipment: Spray dryer (product name: B-290, manufactured by Nippon Buchi), dehumidifier, collector, and inert loop included Atmosphere: Nitrogen flow Air flow rate: approx. 30L / min Nozzle inlet temperature: 180℃ The fine powder obtained by the spray dryer was collected by a collector to obtain resin composition particles.

[0130] [Examples 2-3 and Comparative Examples 1-2] For Example 2 and Comparative Example 1, varnish and resin composition particles were prepared in the same manner as in Example 1, except that the formulation of thermosetting cyclic olefin copolymer 1 and other materials was changed to the formulation in Table 1. In Example 3 and Comparative Example 2, the varnish and resin composition particles were prepared in the same manner as in Example 1, except that the formulation of the thermosetting cyclic olefin copolymer 1 and other materials was changed to the formulation shown in Table 1 and the manufacturing method of the resin composition particles was changed.

[0131] In Example 3 and Comparative Example 2, resin composition particles were produced by a crystallization method instead of a spray-drying method. Details of the crystallization method are as follows. At 23°C, 5.6 g of the varnish obtained in each Example and Comparative Example was added dropwise to 100 mL of acetone at approximately 0.3 mL / s. After the addition was completed, the mixture was decanted and filtered to obtain a powder. The obtained powder was dried at 100°C for 4 minutes in a nitrogen atmosphere to obtain resin composition particles.

[0132] The varnishes and resin composition particles obtained in Examples 1 to 3 and Comparative Examples 1 and 2 were measured according to the following methods. Specifically, the average particle diameter D 50 The results are shown in Table 1.

[0133] [Average particle diameter D 50 Measurement of Number-based average particle diameter D from an image observed using a scanning electron microscope (SEM) 50 The average particle diameter D 50 was calculated using SEM images of resin composition particles taken under the following conditions, where one SEM image contained 20 or more resin composition particles. Equipment: Electron beam microscope (product name: S-4800, manufactured by Hitachi High-Technologies Corporation) Magnification: ×10,000 Acceleration voltage: 3.0 kV Number of shots: 1 Twenty resin composition particles (recognizable as spherical particles) were randomly extracted from the SEM image. Their diameters were measured to obtain the number-based average particle diameter D 50 was calculated. In Comparative Example 2, the particles were aggregated and formed into clumps, so the number-based average particle diameter D 50 could not be calculated.

[0134] Next, the properties of the resulting resin composition particles were evaluated according to the following criteria: curability at 200°C, presence or absence of coarse particles, solvent resistance, and particle dispersibility. The results are shown in Table 1.

[0135] [Curability] The resulting resin composition particles were cured under the following conditions. If the resin composition particles remained solid after curing, they were rated as "A", if some solid remained, they were rated as "B", and if most of them were not maintained as solid, they were rated as "C". (Curing conditions) ·Temperature: 200℃ ·Curing time: 30 minutes Atmosphere: atmospheric pressure

[0136] [Presence or absence of coarse particles] 0.1 g of the obtained resin composition particles was weighed out. If no coarse particles with a diameter of 2.0 mm or more were present among the weighed resin composition particles, it was rated as "A", and if coarse particles with a diameter of 2.0 mm or more were present, it was rated as "B". Note that if coarse particles with a diameter of 2.0 mm or more were present, the resin composition particles could not be used effectively. The presence or absence of coarse particles was determined by observing 0.1 g of the resin composition particles with an optical microscope.

[0137] [Solvent resistance] The cured resin composition particles were mixed with a solvent in a vial. After the solvent was completely evaporated in a nitrogen stream, the case where the particle shape was maintained and no dissolved resin was attached to the bottom of the vial was rated "A", the case where the particle shape was not maintained or the dissolved resin was attached to most of the bottom of the vial was rated "B", and the case where the particle shape was not maintained and the dissolved resin was attached to most of the bottom of the vial was rated "C". The dissolution conditions were as follows. (Dissolution conditions) Low polarity solvent: Toluene (Fujifilm Wako Pure Chemical Industries, Ltd.: Wako special grade) ·Temperature: 23℃ Amount of resin composition particles: 1 mg ·Mixing method: Stir for 10 seconds How to judge dissolution: After 10 seconds of stopping stirring, completely evaporate the solvent in a nitrogen stream, and then visually check the degree of dissolution.

[0138] [Dispersibility] The resulting resin composition particles were mixed with a polar solvent. 10 seconds after mixing, the case where the particles were dispersed in the polar solvent without generating coarse particles was rated "A", the case where the particles were dispersed in the polar solvent with generating coarse particles was rated "B", and the case where clumps were generated in the polar solvent was rated "C". The dispersion conditions were as follows: (Dissolution conditions) Polar solvent: Methyl ethyl ketone (Fujifilm Wako Pure Chemical Industries, Ltd.: Wako special grade) Amount of polar solvent: 3g ·Temperature: 23℃ Amount of resin composition particles: 1 mg ·Mixing method: Stir for 30 seconds How to judge dissolution: Visually check dispersion 5 seconds after stirring has stopped

[0139] Although not shown as a comparative example, the varnish of Example 1 (a mixture before preparing resin composition particles) was mixed with a polar solvent according to the above (dissolution conditions). In this case, the weight of the varnish of Example 1 was set to 1 mg. When the varnish of Example 1 was added dropwise to a polar solvent, the varnish of Example 1 separated from the polar solvent, and therefore could not be dispersed in the polar solvent. In other words, the above evaluation of [Dispersibility] was "C."

[0140] [Table 1]

Claims

1. Resin composition particles, a thermosetting cyclic olefin copolymer (A) having a crosslinkable group; a radical initiator (B); Resin composition particles, wherein the radical initiator (B) is present within the resin composition particles.

2. The resin composition particles are spherical, Number-based average particle diameter D in an image observed by a scanning electron microscope ５０ The resin composition particles according to claim 1, wherein the particle size is 0.01 μm or more and 30 μm or less.

3. The resin composition particles according to claim 1 , wherein the radical initiator (B) comprises a non-peroxide radical initiator.

4. The resin composition particles according to claim 1 , further comprising an inorganic filler (C).

5. 5. The resin composition particles according to claim 4, wherein the content of the inorganic filler (C) is 10 parts by mass or more and 1,000 parts by mass or less when the content of the thermosetting cyclic olefin copolymer (A) is 100 parts by mass.

6. The resin composition particles according to claim 4 , wherein the inorganic filler (C) comprises silica.

7. The thermosetting cyclic olefin copolymer (A) is one or more olefin-derived repeating units (a) represented by the following formula (I); One or more repeating units (b) derived from a cyclic non-conjugated diene represented by the following formula (III); The resin composition particles according to claim 1, further comprising one or more repeating units (c) derived from cyclic olefins represented by the following formula (V): 【Chemical 1】 [In the formula (I), R ３００ represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms. 【Chemistry 2】 [In the 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. 【Chemistry 3】 [In the formula (V), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, and R ６１ ~R ７８ , 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.

8. The resin composition particles according to claim 7 , wherein the olefin constituting the olefin-derived repeating unit (a) contains ethylene.

9. The resin composition particles according to claim 7, wherein the cyclic non-conjugated diene constituting the repeating unit (b) derived from the cyclic non-conjugated diene includes 5-vinyl-2-norbornene.

10. The cyclic olefin constituting the cyclic olefin-derived repeating unit (c) is tetracyclo[4.4.0.1 ２，５ .1 ７，１０ 8. The resin composition particles according to claim 7, comprising one or two members selected from the group consisting of cyclo[2.2.1]-3-dodecene and bicyclo[2.2.1]-2-heptene.

11. 8. The resin composition particles according to claim 7, wherein, when the total number of moles of repeating units in the thermosetting cyclic olefin copolymer (A) is taken as 100 mol%, the content of the olefin-derived repeating unit (a) is 10 mol% or more and 80 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 60 mol% or less.

12. 2. The resin composition particles according to claim 1, wherein the content of the radical initiator (B) is 0.1 parts by mass or more and 25.0 parts by mass or less when the content of the thermosetting cyclic olefin copolymer (A) is 100 parts by mass.

13. 2. The resin composition particles according to claim 1, wherein the total content of the thermosetting cyclic olefin copolymer (A) and the radical initiator (B) in the resin composition particles is 5 parts by mass or more and 100 parts by mass or less, when the total amount of the resin composition particles is 100 parts by mass.

14. The resin composition particles according to claim 1 , which are in an uncured or semi-cured state.

15. A dispersion comprising the resin composition particles according to claim 1 and a polar solvent.

16. A resin composition comprising the resin composition particles according to claim 1 and a matrix resin.

17. A varnish comprising the resin composition according to claim 16 and a solvent.

18. A cured product of the resin composition according to claim 16.

19. A film or sheet comprising the resin composition according to claim 16 or the cured product according to claim 18.

20. A laminate comprising the film or sheet of claim 19.

21. 21. The laminate of claim 20 further comprising a metal foil on at least one side.

22. A prepreg comprising the resin composition according to claim 16 and a sheet-like fiber base material.

23. A printed wiring board comprising an insulating layer comprising the cured product according to claim 18 or the cured product of the prepreg according to claim 22, and a conductor layer on the insulating layer.

24. An electronic device comprising the printed wiring board according to claim 23.

25. A manufacturing method for manufacturing the resin composition particles according to any one of claims 1 to 14, comprising: A method for producing resin composition particles, comprising the step of spray-drying a mixture containing a thermosetting cyclic olefin copolymer (A) having a crosslinkable group and a radical initiator (B), or by crystallizing the mixture, to produce resin composition particles.

26. The method for producing resin composition particles according to claim 25 , wherein the mixture further contains an organic solvent.

27. The method for producing resin composition particles according to claim 26, wherein the organic solvent comprises a low-polarity solvent.

28. The method for producing resin composition particles according to claim 27, wherein the low-polarity solvent comprises toluene.

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