Resin compositions, varnishes, prepregs, films, laminates, metal-clad laminates, and printed circuit boards

Abstract

To provide a resin composition capable of giving a cured product improved in performance balance of low dielectric properties in a high frequency region, crosslinkability, and heat resistance.SOLUTION: The resin composition contains: a thermosetting cyclic olefinic (co)polymer (m) having a crosslinkable group (α); and a crosslinking aid (A). The crosslinking aid (A) contains a crosslinkable compound (a) having three or more crosslinkable groups (β). The crosslinkable groups (β) include at least one functional group selected from the group consisting of a vinyl group and an allyl group. The content of the crosslinking aid (A) is 6 pts.mass or more based on 100 pts.mass of the thermosetting cyclic olefinic (co)polymer (m).SELECTED DRAWING: None

Description

Technical Field

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

Background Art

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

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

[0004] In Patent Document 2, as a material for a circuit board, an interlayer insulating film for a circuit board for a highly integrated arithmetic unit (also referred to as an interlayer insulating layer in the circuit board) and a resin composition capable of obtaining a crosslinked product excellent in dielectric properties, heat resistance, and mechanical properties in a high-frequency region suitable for a circuit board and the like are provided as an issue. A cyclic olefin copolymer resin composition containing a cyclic olefin copolymer (M) and a maleimide compound (L), wherein the cyclic olefin copolymer (M) is composed of one or more repeating units derived from olefins represented by a specific chemical formula (I), one or more repeating units derived from cyclic non-conjugated dienes represented by a specific chemical formula (III), and one or more repeating units derived from cyclic olefins represented by a specific chemical formula (V). The cyclic olefin copolymer (m) is included, and the maleimide compound (L) includes a bismaleimide compound (l) having at least two maleimide groups in the molecule and having a solubility parameter (SP value) of 19 J 1 / 2 / cm 3 / 2 or more and 26 J 1 / 2 / cm 3 / 2 or less, and a cyclic olefin copolymer resin composition in which the content of the maleimide compound (L) is 1 part by mass or more and 50 parts by mass or less when the total of the cyclic olefin copolymer (M) and the maleimide compound (L) is 100 parts by mass is described.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0006] The present invention provides a resin composition capable of obtaining a cured product with an improved balance of low dielectric properties, crosslinkability, and heat resistance in a high-frequency region. [Means for Solving the Problems]

[0007] As a result of intensive studies to solve the above problems, the present inventors have found that by using a resin composition in which a specific crosslinking aid is combined with a thermosetting cyclic olefin-based (co)polymer, it is possible to obtain a cured product having an improved performance balance of low dielectric properties and heat resistance even at high frequencies even with thermosetting at a lower temperature, and have completed the present invention.

[0008] The present invention is as follows.

[0009] [1] A resin composition comprising a thermosetting cyclic olefin-based (co)polymer (m) having a crosslinkable group (α) and a crosslinking aid (A), The crosslinking aid (A) contains a crosslinkable compound (a) having three or more crosslinkable groups (β), and the crosslinkable group (β) contains at least one functional group selected from the group consisting of a vinyl group and an allyl group, The resin composition wherein the content of the crosslinking aid (A) with respect to 100 parts by mass of the thermosetting cyclic olefin-based (co)polymer (m) is 6 parts by mass or more. [2] The resin composition according to [1], wherein the crosslinkable compound (a) further has a heterocyclic structure. [3] The thermosetting cyclic olefin-based (co)polymer (m) is (A) a repeating unit derived from one or more olefins represented by the following general formula (I), (B) a repeating unit derived from one or more cyclic non-conjugated dienes represented by the following general formula (III), (C) a repeating unit derived from one or more cyclic olefins represented by the following general formula (V), and the resin composition according to [1] or [2]. [Chemical Formula] [In the above general formula (I), R 300represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms.〕 [Chemical formula] 〔In the above general formula (III), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, and R 61 ~R 76 as well as R a1 and R b1 may be the same as or different from each other, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, R 104 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, t is a positive integer from 0 to 10, and R 75 and R 76 may be bonded to each other to form a monocyclic or polycyclic ring.〕 [Chemical formula] 〔In the above general formula (V), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, and R 61 ~R 78 as well as R a1 and R b1 may be the same as or different from each other, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, R 75 ~R 78 may be bonded to each other to form a monocyclic or polycyclic ring.〕 [4] When the total number of moles of the repeating units in the thermosetting cyclic olefin copolymer (m) is 100 mol%, the content of the repeating unit (A) derived from the olefin is 10 mol% or more and 90 mol% or less, the content of the repeating unit (B) derived from the cyclic non-conjugated diene is 1 mol% or more and 40 mol% or less, and The resin composition according to [3] above, wherein the content of the repeating unit (C) derived from the cyclic olefin is 1 mol% or more and 50 mol% or less. [5] The resin composition according to [3] or [4] above, wherein the cyclic non-conjugated diene constituting the repeating unit (B) derived from the cyclic non-conjugated diene contains 5-vinyl-2-norbornene. [6] The cyclic olefin constituting the structural unit (C) derived from the cyclic olefin is tetracyclo[4.4.0.1 2,5 .1 7,10 -3-dodecene and at least one selected from the group consisting of bicyclo[2.2.1]-2-heptene, and the resin composition according to any one of [3] to [5] above. [7] The resin composition according to any one of [1] to [6] above, further comprising a radical initiator. [8] The resin composition according to any one of [1] to [7] above, further comprising an antioxidant (B). [9] The resin composition according to any one of [1] to [8] above, wherein the dielectric tangent of the cured product obtained by heating the resin composition at 220°C is less than 0.0010 at 10 GHz.

[10] The resin composition according to any one of [1] to [9] above, wherein the glass transition temperature of the cured product obtained by heating the resin composition at 220°C is 141°C or higher.

[11] A varnish comprising the resin composition according to any one of [1] to

[10] above and a solvent.

[12] A prepreg obtained by impregnating a fiber substrate with the resin composition according to any one of [1] to

[10] above or the varnish according to

[11] above.

[13] A film comprising a cured product of the resin composition according to any one of [1] to

[12] above.

[14] A laminate comprising the prepreg according to

[12] above or the film according to

[13] above.

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

[14] .

[16] A printed wiring board manufactured using the prepreg described in

[12] or the metal-clad laminate described in

[15] .

[17] An electronic device including the film described in

[13] or the printed wiring board described in

[16] .

[18] The electronic device according to

[17] , wherein the electronic device includes a high-speed communication compatible module.

Advantages of the Invention

[0010] According to the present invention, it is possible to provide a resin composition capable of obtaining a cured product having an improved balance of low dielectric properties, crosslinkability, and heat resistance in the high-frequency region.

Embodiments for Carrying Out the Invention

[0011] Hereinafter, the present invention will be described based on embodiments. In this embodiment, "A to B" indicating a numerical range represents A or more and B or less unless otherwise specified. In addition, in the present specification, the "cyclic olefin-based (co)polymer" means at least one polymer selected from the group consisting of a homopolymer of a cyclic olefin and a copolymer of a cyclic olefin and a monomer component other than the cyclic olefin. Each monomer constituting the cyclic olefin-based (co)polymer (m) according to the present invention may be a monomer obtained from a fossil raw material or a monomer obtained from an animal or plant-based raw material. In addition, in this embodiment, -CH=CH2 in the (meth)acrylic group is not included in the vinyl group. In addition, in this embodiment, crosslinkability means the property that crosslinkable groups of a compound react with each other by a curing reaction to form a crosslinked bond, giving a cured product, and is an index of the small amount of thermal energy required to obtain a desired cured product in the curing reaction. The better the crosslinkability, the more it means that a cured product can be obtained with lower thermal energy.

[0012] [Resin composition] The resin composition of this embodiment is a resin composition containing a thermosetting cyclic olefin-based (co)polymer (m) having a crosslinkable group (α) and a crosslinking aid (A), wherein the crosslinking aid (A) contains a crosslinkable compound (a) having three or more crosslinkable groups (β) (hereinafter, also simply referred to as "crosslinkable compound (a)"), the crosslinkable group (β) contains at least one functional group selected from the group consisting of a vinyl group and an allyl group, and the content of the crosslinking aid (A) with respect to 100 parts by mass of the thermosetting cyclic olefin-based (co)polymer (m) is 6 parts by mass or more. According to the resin composition of this embodiment, a cured product with an improved performance balance of low dielectric properties, crosslinkability, and heat resistance in the high-frequency region can be obtained. Hereinafter, each component will be specifically described.

[0013] [Thermosetting cyclic olefin-based (co)polymer (m) having a crosslinkable group (α)] The resin composition of this embodiment contains a thermosetting cyclic olefin-based (co)polymer (m) having a crosslinkable group (α) (hereinafter, also simply referred to as "cyclic olefin-based (co)polymer (m)"). The cyclic olefin-based (co)polymer (m) can be used without particular limitation as long as it is a cyclic olefin-based (co)polymer having thermosetting properties and containing repeating units derived from cyclic olefins. For example, it may be a ring-opening polymer of a cyclic olefin or an addition polymer of a monomer such as an α-olefin and a cyclic olefin. In addition, the cyclic olefin-based (co)polymer (m) has a crosslinkable group (α) which is a functional group that can be used in a crosslinking reaction, from the viewpoint of improving the heat resistance of the cured product obtained by forming a crosslinked structure. Examples of the crosslinkable group (α) include 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; a crosslinkable functional group such as a carboxyl group, and preferably a vinyl group. Since the cyclic olefin-based (co)polymer (m) has the crosslinkable group (α), a crosslinked structure can be formed with the crosslinking aid (A) described later, and the low thermal expansibility can be further improved. In one molecule of the cyclic olefin-based (co)polymer (m), the number of crosslinkable groups (α) may be one or more. When there are a plurality of crosslinkable groups (α) in one molecule, they may be of a single kind or two or more kinds.

[0014] The cyclic olefin-based (co)polymer (m) of this embodiment is preferably (A) one or more repeating units derived from an olefin represented by the following general formula (I), and (B) one or more repeating units derived from a cyclic non-conjugated diene represented by the following general formula (III), and (C) one or more repeating units derived from a cyclic olefin represented by the following general formula (V).

[0015]

Chemical formula

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

[0017]

Chemical formula

[0018] In the general formula (III) above, 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 as well as R a1 and R b1 may be the same as or different from each other, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and R 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]

Chemical formula

[0020] In the general formula (V) above, 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 as well as R a1 and R b1 may be the same as or different from each other, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and R 75 ~R 78 may be bonded to each other to form a monocyclic or polycyclic ring.

[0021] When the cyclic olefin-based (co)polymer (m) is a copolymer (m) containing the repeating units (A) to (C) above, when the total number of moles of the repeating units in the thermosetting cyclic olefin-based copolymer (m) is 100 mol%, The content of the repeating unit (A) derived from olefin is preferably 10 mol% or more and 90 mol% or less, more preferably 20 mol% or more and 85 mol% or less, still more preferably 30 mol% or more and 80 mol% or less, still more preferably 40 mol% or more and 70 mol% or less, still more preferably 50 mol% or more and 70 mol% or less, still more preferably 55 mol% or more and 65 mol% or less. The content of the repeating unit (B) derived from cyclic non-conjugated diene is preferably 1 mol% or more and 40 mol% or less, more preferably 5 mol% or more and 40 mol% or less, still more preferably 5 mol% or more and 35 mol% or less, still more preferably 7 mol% or more and 30 mol% or less, still more preferably 10 mol% or more and 30 mol% or less, still more preferably 15 mol% or more and 30 mol% or less, still more preferably 20 mol% or more and 30 mol% or less. The content of the repeating unit (C) derived from cyclic olefin is preferably 1 mol% or more and 50 mol% or less, more preferably 3 mol% or more and 40 mol% or less, still more preferably 10 mol% or more and 35 mol% or less, still more preferably 10 mol% or more and 30 mol% or less, still more preferably 10 mol% or more and 25 mol% or less, still more preferably 10 mol% or more and 20 mol% or less, still more preferably 10 mol% or more and 15 mol% or less. When each content of the repeating units in the cyclic olefin copolymer (m) is within the above range, the cured product obtained from the above resin composition can further improve the dielectric properties and heat resistance. Furthermore, a cured product with an improved performance balance of mechanical properties, dielectric properties, transparency, and gas barrier properties can be obtained.

[0022] The olefin monomer that can be one of the copolymerization raw materials of the cyclic olefin copolymer (m) is a monomer that undergoes addition copolymerization to give the skeleton represented by the above formula (I), and can be an olefin represented by the following general formula (Ia).

[0023]

Chemical formula

[0024] In the above general formula (Ia), R 300represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms. Examples of the olefin represented by the general formula (Ia) include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, and the like. From the viewpoint of obtaining a cured product having more excellent heat resistance, mechanical properties, dielectric properties, transparency, and gas barrier properties, among these, one or two selected from the group consisting of ethylene and propylene are preferable, and ethylene is more preferable. Two or more kinds of the olefin monomer represented by the above formula (Ia) may be used.

[0025] The cyclic non-conjugated diene monomer, which can be one of the copolymerization raw materials of the cyclic olefin copolymer (m), can be addition-copolymerized to form a structural unit represented by the above formula (III). Specifically, a cyclic non-conjugated diene represented by the following general formula (IIIa) corresponding to the above general formula (III) can be used.

[0026] [Chemical formula]

[0027] In the above general formula (IIIa), u is 0 or 1, v is 0 or a positive integer, preferably an integer of 0 or more and 2 or less, more preferably 0 or 1, w is 0 or 1, and R 61 ~R 76 as well as R a1 and R b1 may be the same as or different from each other, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and R 104is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, t is a positive integer of 0 to 10, and R 75 and R 76 may be bonded to each other to form a monocyclic or polycyclic ring.

[0028] Examples of the cyclic non-conjugated diene represented by the general formula (IIIa) include, but are not limited to, cyclic non-conjugated dienes represented by the following chemical formulas. Among these, the cyclic non-conjugated diene represented by the general formula (IIIa), that is, the cyclic non-conjugated diene constituting the repeating unit (B) derived from the cyclic non-conjugated diene, is 5-vinyl-2-norbornene and 8-vinyl-9-methyltetracyclo[4.4.0.1 2,5 .1 7,10 -3-dodecene, and preferably contains at least one selected from the group consisting of them, and more preferably contains 5-vinyl-2-norbornene.

[0029]

Chemical formula

[0030]

Chemical formula

[0031] The cyclic non-conjugated diene represented by the general formula (IIIa) can specifically be represented by the following general formula (IIIb).

[0032]

Chemical formula

[0033] n in the general formula (IIIb) 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.

[0034] When the cyclic olefin copolymer (m) of the present embodiment contains a structural unit derived from a cyclic non-conjugated diene represented by the general formula (III), it has a double bond in the side chain portion, that is, a portion other than the main chain of the copolymerization. The functional group containing the double bond can be one of the crosslinkable groups (α).

[0035] The cyclic olefin monomer that can be one of the copolymerization raw materials of the cyclic olefin copolymer (m) can be addition copolymerized to form a structural unit represented by the above formula (V). Specifically, a cyclic olefin monomer represented by the following general formula (Va) corresponding to the above general formula (V) can be used.

[0036]

Chemical formula

[0037] In the above general formula (Va), u is 0 or 1, v is 0 or a positive integer, preferably an integer of 0 or more and 2 or less, more preferably 0 or 1, w is 0 or 1, and R 61 ~R 78 as well as R a1 and R b1 may be the same as or different from each other, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms. R 75 ~R 78 may be bonded to each other to form a monocyclic or polycyclic ring.

[0038] As specific examples of the cyclic olefin represented by the above general formula (Va), the compounds described in International Publication No. 2006 / 118261 can be used. The cyclic olefin that forms the cyclic olefin represented by the above general formula (Va), that is, the structural unit (C) derived from the cyclic olefin, is bicyclo[2.2.1]-2-heptene (also called norbornene.) and tetracyclo[4.4.0.1 2,5 .1 7,10It is preferable to contain at least one selected from the group consisting of -3-dodecene (also referred to as tetracyclododecene). Since these cyclic olefins have a rigid ring structure, the elastic modulus of the cured product composed of the cyclic olefin-based copolymer (m) and the resin composition is easily retained, and since they do not contain a hetero double bond structure, there is an advantage that crosslinking is easily controlled.

[0039] By using the olefin monomer represented by the general formula (Ia) and the cyclic olefin represented by the general formula (Va) as the copolymerization components, the solubility of the cyclic olefin-based copolymer (m) in a solvent is further improved, so the moldability becomes good and the yield of the product is improved.

[0040] In addition to the repeating unit derived from one or more olefins represented by the general formula (I), the repeating unit derived from the cyclic non-conjugated diene represented by the general formula (III), and the repeating unit derived from one or more cyclic olefins represented by the general formula (V), the cyclic olefin-based copolymer (m) may be composed of a cyclic non-conjugated diene represented by the general formula (III) and a cyclic olefin other than the cyclic olefin represented by the general formula (V), and / or a repeating unit derived from a chain polyene. In this case, as the copolymerization raw materials of the cyclic olefin-based copolymer (m), in addition to the olefin monomer represented by the general formula (Ia), the cyclic non-conjugated diene monomer represented by the general formula (IIIa), and the cyclic olefin monomer represented by the general formula (Va), a cyclic non-conjugated diene monomer represented by the general formula (IIIa) and a cyclic olefin monomer other than the cyclic olefin monomer represented by the general formula (Va), and / or a chain polyene monomer can be used. As such a cyclic olefin monomer and a chain polyene monomer, a cyclic olefin represented by the following general formula (VIa) or (VIIa) or a chain polyene represented by the following general formula (VIIIa) can be used. Two or more different kinds of these cyclic olefins and chain polyenes may be used.

[0041]

Chemical formula

[0042] In general formula (VIa), x and d are integers of 0 or 1 or more, preferably integers 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 as or different from each other, and is a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group which is an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms or an alkoxy group, and R 89 and R 90 the carbon atom to which is bonded, the carbon atom to which R 93 is bonded or the carbon atom to which R 91 is bonded may be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and when y = z = 0, R 95 and R 92 or R 95 and R 99 may be bonded to each other to form a monocyclic or polycyclic aromatic ring.

[0043]

Chemical formula

[0044] In general formula (VIIa), R 100 and R 101 may be the same as or different from each other, represent a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and f satisfies 1 ≦ f ≦ 18.

[0045]

Chemical formula

[0046] In general formula (VIIIa), from R 201 to R 206may be the same as or different from each other, and is 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.

[0047] As specific examples of the cyclic olefins represented by the general formula (VIa) and the general formula (VIIa), the compounds described in paragraphs 0037 to 0063 of International Publication No. 2006 / 118261 can be used.

[0048] As the chain polyene represented by the general formula (VIIIa), specifically, 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. can be mentioned. Also, a cyclic polyene cyclized from polyenes such as 1,3 - butadiene and 1,5 - hexadiene may be used.

[0049] When the cyclic olefin - based copolymer (m) contains a structural unit derived from the chain polyene represented by the above general formula (VIIIa), or a cyclic olefin other than the cyclic non - conjugated diene represented by the general formula (III) and the cyclic olefin represented by the general formula (V) [for example, the general formula (VIa), the general formula (VIIa)], the content of the structural unit is preferably 0.1 to 100 mol%, more preferably 0.1 to 50 mol% with respect to the total number of moles of the repeating units derived from one or more olefins represented by the above general formula (I), the repeating units derived from one or more cyclic non - conjugated dienes represented by the above general formula (III), and the repeating units derived from one or more cyclic olefins represented by the above general formula (V).

[0050] As the copolymerized components, by using the olefin monomer represented by the general formula (I) described above, the cyclic olefin represented by the general formula (VIa) or (VIIa), and the chain polyene represented by the general formula (VIIIa), the solubility of the cyclic olefin-based copolymer (m) in a solvent is further improved, so that the moldability becomes good and the yield of the product is improved. Among these, the cyclic olefin represented by the general formula (VIa) or (VIIa) is preferable. Since these cyclic olefins have a rigid ring structure, the elastic modulus of the cured product composed of the cyclic olefin-based copolymer (m) and the resin composition is easily retained, and since they do not contain a hetero double bond structure, there is an advantage that crosslinking is easily controlled.

[0051] The cyclic olefin-based (co)polymer (m) can control its comonomer content and glass transition temperature (Tg) according to the intended use by the charging ratio of the monomers. The Tg of the cyclic olefin-based (co)polymer (m) is, for example, 300 °C or lower, preferably 250 °C or lower, more preferably 200 °C or lower, still more preferably 170 °C or lower, still more preferably 150 °C or lower, still more preferably 120 °C or lower, still more preferably 110 °C or lower. When the Tg is below the above upper limit value, the melt moldability of the cyclic olefin-based (co)polymer (m) and the solubility in a solvent when it is varnished are improved. The lower limit value of the Tg of the cyclic olefin-based (co)polymer (m) is not particularly limited, but is, for example, 50 °C or higher, and may be 70 °C or higher, or may be 90 °C or higher.

[0052] The number average molecular weight (Mn) in terms of polystyrene measured by gel permeation chromatography of the cyclic olefin-based (co)polymer (m) is preferably 5,000 or more, more preferably 10,000 or more, still more preferably 15,000 or more, and still more preferably 20,000 or more from the viewpoint of further improving the performance balance of dielectric properties, low thermal expansion properties, and mechanical properties. Also, from the viewpoint of further improving moldability such as impregnation property into a fiber base material and wiring embedding property during the production of a printed wiring board, it is preferably 100,000 or less, more preferably 80,000 or less, still more preferably 60,000 or less, still more preferably 40,000 or less, still more preferably 30,000 or less, and still more preferably 25,000 or less. The number average molecular weight (Mn) of the cyclic olefin-based (co)polymer (m) can be controlled by polymerization conditions such as a polymerization catalyst, a cocatalyst, an H2 addition amount, and a polymerization temperature.

[0053] [Production method of cyclic olefin-based (co)polymer (m)] The cyclic olefin-based (co)polymer (m) of the present embodiment can be produced, for example, according to the production method of the cyclic olefin copolymer described in paragraphs 0075 to 0219 of International Publication No. 2012 / 046443. Details are omitted here.

[0054] [Crosslinking aid (A)] The crosslinking aid (A) of the present embodiment contains a crosslinkable compound (a) having 3 or more crosslinkable groups (β). The crosslinkable group (β) contains at least one functional group selected from the group consisting of a vinyl group and an allyl group.

[0055] The crosslinkable compound (a) preferably has 3 or more and 10 or less crosslinkable groups (β), more preferably 3 or more and 8 or less crosslinkable groups (β), still more preferably 3 or more and 6 or less crosslinkable groups (β), and still more preferably 3 or more and 4 or less crosslinkable groups (β) from the viewpoint of further improving the performance balance of low dielectric properties, crosslinkability, and heat resistance in the high-frequency region.

[0056] In addition, from the viewpoint of further improving the performance balance of low dielectric properties, crosslinkability, and heat resistance in the high-frequency region, the crosslinkable compound (a) preferably further has a heterocyclic structure, more preferably has a nitrogen-containing heterocyclic ring, and even more preferably has one or more selected from the group consisting of an isocyanuric ring structure and a glycoluril ring structure.

[0057] The crosslinkable compound (a) contains one or more selected from the group consisting of a glycoluril-based crosslinkable compound, a bisisocyanurate-based crosslinkable compound, and an isocyanurate-based crosslinkable compound from the viewpoint of further improving the performance balance of low dielectric properties, crosslinkability, and heat resistance in the high-frequency region.

[0058] The glycoluril-based crosslinkable compound of the present embodiment preferably contains a compound represented by the following formula (1). The bisisocyanurate-based crosslinkable compound and the isocyanurate-based crosslinkable compound of the present embodiment preferably contain a compound represented by the following formula (2-a).

[0059] [Chemical formula] In formula (1), at least 3 of R 1 ~R 4 are organic groups having 1 to 10 carbon atoms containing a vinyl group or organic groups having 1 to 10 carbon atoms containing an allyl group. Preferably, at least 3 of R 1 ~R 4 are organic groups having 1 to 5 carbon atoms containing a vinyl group or organic groups having 1 to 5 carbon atoms containing an allyl group. More preferably, at least 3 of R 1 ~R 4 are a vinyl group or an allyl group. Even more preferably, all of R 1 ~R 4 are a vinyl group or an allyl group. Even more preferably, all of R 1 ~R 4 are an allyl group. Also, R 1 ~R 4may be, for example, a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group. Each X is independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group, preferably a hydrogen atom.

[0060]

Chemical formula

[0061]

Chemical formula

[0062] Examples of glycoluril-based crosslinkable compounds include 1,3,4,6-tetraallylglycoluril (e.g., TA-G manufactured by Shikoku Chemicals Corporation), 1,3,4,6-tetraallyl-3a-methylglycoluril, 1,3,4,6-tetraallyl-3a,6a-dimethylglycoluril, 1,3,4,6-tetraallyl-3a,6a-diphenylglycoluril, and the like. Examples of bisisocyanurate-based crosslinkable compounds include bis(diallylisocyanurate) compounds (e.g., DD-1 manufactured by Shikoku Chemicals Corporation), and the like. Examples of isocyanurate-based crosslinkable compounds include triallylisocyanurate (e.g., TAIC manufactured by Mitsubishi Chemical Corporation), and the like.

[0063] From the viewpoint of further improving the performance balance of low dielectric properties, crosslinkability, and heat resistance in the high-frequency region, the content of the crosslinking aid (A) in the resin composition of the present embodiment is 6 parts by mass or more, preferably 7 parts by mass or more, more preferably 8 parts by mass or more, and still more preferably 9 parts by mass or more with respect to 100 parts by mass of the cyclic olefin-based (co)polymer (m). The upper limit of the content of the crosslinking aid (A) in the resin composition of the present embodiment is not particularly limited, but is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and still more preferably 13 parts by mass or less.

[0064] The crosslinking aid (A) of the present embodiment may further contain a crosslinking aid other than the crosslinkable compound (a). The crosslinking aid is not particularly limited, and examples thereof include oximes such as p - quinonedioxime and p,p'-dibenzoylquinonedioxime; (meth)acrylates such as ethylenedi(meth)acrylate, polyethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, cyclohexyl (meth)acrylate, acrylic acid / zinc oxide mixture, allyl (meth)acrylate; vinyl monomers such as divinylbenzene, vinyltoluene, vinylpyridine; allyl compounds such as hexamethylenediallylnadiimide, diallyl itaconate, diallyl phthalate, diallyl isophthalate, diallyl monoglycidyl isocyanurate; maleimide compounds such as N,N'-m-phenylenebismaleimide, N,N'-(4,4'-methylenediphenylene)dimaleimide, and the like. These crosslinking aids may be used alone or in combination.

[0065] The content of the crosslinkable compound (a) in the crosslinking aid (A) of the present embodiment is preferably 50 parts by mass or more, more preferably 70 parts by mass or more, still more preferably 80 parts by mass or more, still more preferably 90 parts by mass or more, still more preferably 95 parts by mass or more, still more preferably 98 parts by mass or more, still more preferably 100 parts by mass or more, and preferably 100 parts by mass or less, based on 100 parts by mass of the crosslinking aid (A).

[0066] [Radical initiator] The resin composition of the present embodiment preferably further contains a radical initiator. By including a radical initiator in the resin composition, it becomes easier to form a cured product described later. The crosslinking by the radical initiator can directly apply the usual crosslinking method by a radical initiator applied to polyolefins. That is, a radical initiator is blended into the resin composition, and then heated and crosslinked.

[0067] From the perspective of further improving the performance balance between the heat resistance and mechanical properties of the cured product, the content of the radical initiator in the resin composition of the present embodiment is preferably 0.02 parts by mass or more, more preferably 0.05 parts by mass or more, still more preferably 0.1 parts by mass or more, still more preferably 0.5 parts by mass or more, still more preferably 1.0 parts by mass or more, still more preferably 1.5 parts by mass or more, still more preferably 2.0 parts by mass or more, still more preferably 2.5 parts by mass or more, still more preferably 3.0 parts by mass or more, still more preferably 3.5 parts by mass or more, based on 100 parts by mass of the cyclic olefin-based (co)polymer (m). From the perspective of further improving the dielectric properties of the cured product, it is preferably 20.0 parts by mass or less, more preferably 10.0 parts by mass or less, still more preferably 5.0 parts by mass or less.

[0068] As radical initiators, known thermal radical initiators, photo radical initiators, and combinations thereof can be used. When using a thermal radical initiator among these radical initiators, from the viewpoint of storage stability, the half-life temperature for 10 hours is, for example, 80°C or higher, preferably 120°C or higher. Examples of such initiators include dialkyl peroxides such as dicumyl peroxide, t-butyl cumyl peroxide, 2,5-bis(t-butylperoxy)2,5-dimethylhexane, 2,5-bis(t-butylperoxy)2,5-dimethylhexine-3, di-t-butyl peroxide, isopropyl cumyl-t-butyl peroxide, bis(α-t-butylperoxyisopropyl)benzene; peroxyketals such as 1,1-bis(t-butylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclododecane, n-butyl-4,4-bis(t-butylperoxy)valerate, ethyl-3,3-bis(t-butylperoxy)butyrate, 3,3,6,6,9,9-hexamethyl-1,2,4,5-tetraoxacyclononane; peroxy esters such as bis(t-butylperoxy)isophthalate, t-butyl peroxybenzoate, t-butyl peroxyacetate; hydroperoxides such as t-butyl hydroperoxide, t-hexyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide; bibenzyl compounds such as hexaphenylethane, 1-t-butyl-3-[2-(4-t-butylphenyl)-1,1,2-trimethylpropyl]benzene, 2,3-dimethyl-2,3-diphenylbutane; 3,3,5,7,7-pentamethyl-1,2,4-trioxepane, and the like.

[0069] Among radical initiators, photo radical initiators include, for example, benzoin alkyl ethers, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzophenone, methyl benzoyl formate, isopropyl thioxanthone, and mixtures of two or more of these. Further, a sensitizer can also be used together with these photo radical initiators. Examples of sensitizers include carbonyl compounds such as anthraquinone, 1,2-naphthoquinone, 1,4-naphthoquinone, benzanthrone, p,p'-tetramethyldiaminobenzophenone, chloranil, nitro compounds such as nitrobenzene, p-dinitrobenzene, 2-nitrofluorene, aromatic hydrocarbons such as anthracene, chrysene, sulfur compounds such as diphenyl disulfide, and nitrogen compounds such as nitroaniline, 2-chloro-4-nitroaniline, 5-nitro-2-aminotoluene, tetracyanoethylene, etc.

[0070] As the radical initiator, it is more preferable to include a thermal radical initiator, and it is even more preferable to include bibenzyl compounds. Thereby, the storage stability can be further improved, and the dielectric properties, heat resistance, and mechanical properties can be further improved.

[0071] [Antioxidant (B)] The resin composition of this embodiment preferably further includes an antioxidant (B). The antioxidant (B) preferably includes one or more selected from the group consisting of, for example, phenolic antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, and thioether-based antioxidants, and more preferably includes a phenolic antioxidant. Thereby, the storage stability during storage of the resin composition and after forming into a film can be further improved.

[0072] 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-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,2'-methylenebis(4-methyl-6-t-butylphenol), 4,4'-butylidenebis(6-t-butyl-m-cresol), 4,4'-thiobis(3-methyl-6-t-butylphenol), bis(3-cyclohexyl-2-hydroxy-5-methylphenyl)methane, 3,9-bis(2-(3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy)-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5] Undecane, 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, tetrakis(methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenylpropionate)methane [i.e., pentaerythrityl-tetrakis(3-(3,5-di-t-butyl-4-hydroxyphenylpropionate)], pentaerythritol-tetrakis[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, triethylene glycol bis(3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate), alkyl-substituted phenolic compounds such as tocopherol; 6-(4-hydroxy-3,5-di-t-butylanilino)-2,4-bis(octylthio)-1,3,5-triazine, 6-(4-hydroxy-3,5-dimethylanilino)-2,4-bis(octylthio)-1,3,5-triazine, 6-(4-hydroxy-3-methyl-5-t-butylanilino)-2,4-bis(octylthio)-1,3,5-triazine, 2-octylthio-4,6-bis-(3,5-di-t-butyl-4-oxyani lino)-1,3,5-triazine and other triazine group-containing phenolic compounds; and at least one selected from the group consisting of the like. Among these, at least one selected from the group consisting of acrylate-based phenolic compounds and alkyl-substituted phenolic compounds is preferable, and alkyl-substituted phenolic compounds are more preferable.

[0073] Examples of phosphorus-based antioxidants include at least one selected from the group consisting of monophosphite compounds such as 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) octyl phosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(3,5-di-t-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene; diphosphite compounds such as 4,4'-butylidene-bis(3-methyl-6-t-butylphenyl-di-tridecyl phosphite), 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-tridecyl phosphite-5-t-butylphenyl) butane, tetrakis(2,4-di-t-butylphenyl)-4,4'-biphenylenediphosphite, cyclic neopentanetetrayl bis(isodecyl phosphite), cyclic neopentanetetrayl bis(nonylphenyl phosphite), cyclic neopentanetetrayl bis(2,4-di-t-butylphenyl phosphite), cyclic neopentanetetrayl bis(2,4-dimethylphenyl phosphite), cyclic neopentanetetrayl bis(2,6-di-t-butylphenyl phosphite). Among these, monophosphite compounds are preferred, and at least one selected from the group consisting of tris(nonylphenyl) phosphite, tris(dinonylphenyl) phosphite, and tris(2,4-di-t-butylphenyl) phosphite is more preferred.

[0074] Examples of the sulfur-based antioxidant include at least one selected from the group consisting of dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, lauryl stearyl 3,3'-thiodipropionate, pentaerythritol - tetrakis-(β-lauryl-thio-propionate), and 3,9-bis(2-dodecylthioethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane. Examples of the thioether-based antioxidant include at least one selected from the group consisting of tetrakis{methylene-3-(laurylthio)propionate}methane, bis〔methyl-4-{3-n-alkyl(C12orC14)thiopropioniodyl}-5-t-butylphenyl〕sulfide, and ditridecyl 3,3'-thiodipropionate.

[0075] From the viewpoint of further improving the storage stability, the content of the antioxidant (B) in the resin composition of the present embodiment is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, still more preferably 0.01% by mass or more, still more preferably 0.02% by mass or more, and preferably 1.0% by mass or less, more preferably 0.50% by mass or less, still more preferably 0.30% by mass or less, still more preferably 0.20% by mass or less, still more preferably 0.10% by mass or less, based on the whole resin composition excluding the solvent.

[0076] [Additives] Various additives may be further added to the resin composition of the present embodiment according to the purpose. The addition amount of the additive is appropriately selected according to the use within the range that does not impair the object of the present invention. The above additives include one or more additives selected from the group consisting of heat stabilizers, weather stabilizers, radiation-resistant agents, plasticizers, lubricants, mold release agents, nucleating agents, friction and wear resistance improvers, flame retardants, foaming agents, antistatic agents, colorants, antifogging agents, antiblocking agents, impact-resistant agents, surface wettability improvers, fillers, hydrochloric acid absorbers, and metal deactivators. For example, heat stabilizers, light stabilizers, ultraviolet absorbers, radiation-resistant agents, plasticizers, lubricants, mold release agents, nucleating agents, friction and abrasion resistance improvers, flame retardants, foaming agents, antistatic agents, colorants, antifogging agents, antiblocking agents, impact-resistant agents, surface wetting improvers, fillers, hydrochloric acid absorbers, metal deactivators, etc. described in paragraphs 0085 to 0120 of International Publication No. 2017 / 150218 can be used.

[0077] <Method for preparing resin composition> The resin composition of the present embodiment can be prepared by mixing a cyclic olefin-based (co)polymer (m) and a crosslinking aid (A), and other components as required. As the mixing method, a method of melt blending with an extruder or the like, or a solution blending method in which it is dissolved and dispersed in a suitable solvent, for example, saturated hydrocarbons such as heptane, hexane, decane, and cyclohexane; aromatic hydrocarbons such as toluene, benzene, and xylene, etc. can be adopted.

[0078] From the viewpoint of further improving the performance balance of low dielectric properties, crosslinkability, and heat resistance in the high-frequency region, the dielectric loss tangent Df of the cured product obtained by heating the resin composition of the present embodiment at 220 °C is preferably less than 0.0010 at a frequency of 10 GHz. There is no limitation on the lower limit of the dielectric loss tangent Df, but it may be, for example, 0.0001 or more, 0.0003 or more, or 0.0005 or more. The dielectric loss tangent Df of the cured product obtained by heating the resin composition of the present embodiment at 220 °C can be measured by the method described in the examples below.

[0079] From the viewpoint of further improving the performance balance of low dielectric properties, crosslinkability, and heat resistance in the high-frequency region, the glass transition temperature Tg of the cured product obtained by heating the resin composition of the present embodiment at 220 °C is preferably 141 °C or higher, more preferably 143 °C or higher, still more preferably 145 °C or higher, and even more preferably 148 °C or higher. The upper limit of the glass transition temperature of the cured product obtained by heating the resin composition of the present embodiment at 220°C is not particularly limited, and may be, for example, 200°C or lower, 180°C or lower, 170°C or lower, or 160°C or lower. The glass transition temperature Tg of the cured product obtained by heating the resin composition of the present embodiment at 220°C can be measured by the method described in the examples below.

[0080] [Varnish] The resin composition of the present embodiment can be made into a varnish by mixing with a solvent. That is, the varnish of the present embodiment contains the resin composition of the present embodiment and a solvent. The solvent for preparing the varnish is not limited as long as it does not impair the solubility or affinity for the cyclic olefin copolymer (m) and the crosslinking aid (A). Preferably, the solvent is a saturated hydrocarbon such as heptane, hexane, octane, decane; an alicyclic hydrocarbon such as cyclohexane, methylcyclohexane, decahydronaphthalene; an aromatic hydrocarbon such as toluene, benzene, xylene, mesitylene, pseudocumene; an alcohol such as methanol, ethanol, isopropyl alcohol, butanol, pentanol, hexanol, propanediol, phenol; a ketone solvent such as acetone, methyl isobutyl ketone, methyl ethyl ketone, pentanone, hexanone, cyclohexanone, isophorone, acetophenone; a cellosolve such as methyl cellosolve, ethyl cellosolve; an ester such as methyl acetate, ethyl acetate, butyl acetate, methyl propionate, butyl formate; a halogenated hydrocarbon such as trichloroethylene, dichloroethylene, chlorobenzene, etc. are used. From the viewpoint of further improving the solubility and availability of the resin composition, heptane, decane, cyclohexane, methylcyclohexane, decahydronaphthalene, toluene, benzene, xylene, mesitylene, pseudocumene are more preferably used. These solvents can be used alone or in combination of two or more in any ratio. As the amount of the solvent added to the resin composition, from the viewpoint of further improving the handleability and coatability of the varnish, when the total amount of the resin composition is 100 parts by mass, it is preferably 100 parts by mass or more, more preferably 120 parts by mass or more, and preferably 500 parts by mass or less, more preferably 450 parts by mass or less, still more preferably 400 parts by mass or less. In addition, the total content of the cyclic olefin copolymer (m) and the crosslinking aid (A) in the varnish is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, and preferably less than 100% by mass, more preferably 50% by mass or less.

[0081] In this embodiment, as a method for producing the varnish, any method may be used. For example, it includes a step of mixing the resin composition and the solvent. There is no limitation on the order of mixing of each component, and it can be carried out in any manner such as batchwise or divided. There is also no limitation on the apparatus for preparing the varnish, and it may be carried out using any batch-type or continuous-type apparatus capable of stirring and mixing. The temperature during the preparation of the varnish can be arbitrarily selected within the range from room temperature to the boiling point of the solvent. Note that the varnish may be prepared by directly using the reaction solution obtained when the thermosetting cyclic olefin copolymer (m) is obtained as the solvent.

[0082] [Cured product] The cured product of this embodiment can be obtained by crosslinking the thermosetting cyclic olefin copolymer (A) in the resin composition of this embodiment. The crosslinking can be carried out, for example, by a crosslinking step of crosslinking the resin composition at a temperature of 150°C or higher and a press pressure of 0.2 MPa or higher under a vacuum of 20 kPa or lower. In the crosslinking process, the crosslinking temperature is preferably 150 °C or higher, more preferably 160 °C or higher, still more preferably 170 °C or higher, from the viewpoint of further improving the heat resistance of the resulting cured product, and preferably 280 °C or lower, more preferably 260 °C or lower, still more preferably 250 °C or lower, still more preferably 240 °C or lower, from the viewpoint of suppressing thermal decomposition of the thermosetting cyclic olefin copolymer (A) and the cured product. The press pressure in the crosslinking process is 0.2 MPa or higher, preferably 1 MPa or higher, more preferably 2 MPa or higher, still more preferably 3 MPa or higher, from the viewpoint of ensuring the uniformity of the resulting cured product. The degree of vacuum in the crosslinking process is under a vacuum of 20 kPa or lower, preferably under a vacuum of 10 kPa or lower, more preferably under a vacuum of 5 kPa or lower, still more preferably under a vacuum of 2 kPa or lower, from the viewpoint of maintaining the dielectric properties of the resulting cured product.

[0083] The crosslinking process can be carried out in a molten state of the resin composition of the present embodiment, or can also be carried out in a solution state in which the resin composition is dissolved or dispersed in a solvent. Further, the crosslinking process can also be carried out by volatilizing the solvent from a solution state in which the resin composition is dissolved in a solvent, forming it into an arbitrary form such as a film or a coating, and then further proceeding with the crosslinking reaction. When carrying out the reaction in a molten state, a kneading device such as a mixing roll, a Banbury mixer, an extruder, a kneader, or a continuous mixer is used to melt-knead and react the mixture of raw materials. Further, the crosslinking reaction can also be proceeded after molding by an arbitrary method. As the solvent used when carrying out the reaction in a solution state, the same solvent as the solvent used in the above solution blending method can be used.

[0084] [Prepreg] The prepreg of the present embodiment is obtained by impregnating a fiber base material with the resin composition or the varnish of the present embodiment, and is preferably formed by laminating the resin composition of the present embodiment and a sheet-like fiber base material. The method for manufacturing the prepreg is not particularly limited, and various known methods are applicable. For example, a method including a step of impregnating the varnish described above into a sheet-like fiber base material to obtain an impregnated body, and a step of heating the obtained impregnated body to dry the solvent contained in the varnish can be mentioned. The impregnation of the varnish into the sheet-like fiber base material can be carried out, for example, by applying a predetermined amount of the varnish to the sheet-like fiber base material by a known method such as a spray coating method, a dip coating method, a roll coating method, a curtain coating method, a die coating method, a slit coating method, etc., and if necessary, overlaying a protective film thereon and pressing it from above with a roller or the like. Moreover, the step of heating the impregnated body to dry the solvent contained in the varnish is not particularly limited, but for example, drying in air or nitrogen by a batch-type air dryer, or drying by passing through a heating furnace in a continuous process, etc. can be mentioned. After impregnating the varnish into the sheet-like fiber base material, by heating the obtained impregnated body to a predetermined temperature, the solvent contained in the varnish evaporates, and a prepreg is obtained.

[0085] As the fibers constituting the sheet-like fiber base material, inorganic or organic fibers can be used and are not particularly limited. For example, organic fibers such as PET (polyethylene terephthalate) fibers, polystyrene fibers, aramid fibers, ultra-high molecular polyethylene fibers, polyamide (nylon) fibers, liquid crystal polyester fibers, etc.; inorganic fibers such as glass fibers, carbon fibers, alumina fibers, tungsten fibers, molybdenum fibers, titanium fibers, steel fibers, boron fibers, silicon carbide fibers, silica fibers, etc. can be mentioned. Among these, preferably, it is at least one selected from the group consisting of organic fibers and glass fibers, and more preferably, it is at least one selected from the group consisting of aramid fibers, liquid crystal polyester fibers, and glass fibers. Examples of glass fibers include E glass, NE glass, S glass, D glass, H glass, T glass, etc. The impregnation of the varnish into the sheet-like fiber base material is carried out, for example, by immersion and coating. The impregnation may be repeated a plurality of times as necessary. These sheet-like fiber base materials can be used individually or in combination of two or more, and the amount used is appropriately selected as desired. However, in the prepreg or laminate, for example, it is 10% by mass or more, preferably 20% by mass or more, more preferably 30% by mass or more, and also, for example, in the range of 90% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less. Within this range, the dielectric properties and mechanical strength of the resulting laminate are highly balanced, which is preferable.

[0086] The thickness of the prepreg is appropriately selected according to the intended use. For example, it is 0.001 mm or more, preferably 0.005 mm or more, more preferably 0.01 mm or more, and also, for example, 10 mm or less, preferably 1 mm or less, more preferably 0.5 mm or less. Within this range, the formability during lamination and the properties such as the mechanical strength and toughness of the cured laminate are fully exhibited, which is preferable.

[0087] [Film] The film of this embodiment contains a cured product of the resin composition of this embodiment. The cured product obtained by curing the resin composition of this embodiment can be formed into a film and used for various applications. In this embodiment, the "film" is a general term for planar molded articles and includes concepts such as sheets, membranes, and tapes. As a method of curing the resin composition of this embodiment to obtain a cured product and forming it into a film, various known methods are applicable. For example, a method of forming a film made of the resin composition of this embodiment can be mentioned, in which the varnish described above is applied onto a support substrate such as a thermoplastic resin film, dried, and then heat-treated or the like to crosslink the resin composition to obtain a cured product. As the thermoplastic resin film, a PET film, a polyimide resin film, etc. can be used. The method of 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. Further, after obtaining a film by melt-molding the resin composition of the present embodiment, the resin composition may be crosslinked by heat treatment or the like to form a cured product, and a method of forming a film made of the resin composition of the present embodiment can also be mentioned.

[0088] [Laminate] The laminate of the present embodiment includes the film of the present embodiment or the prepreg of the present embodiment. The film of the present embodiment or the prepreg of the present embodiment can be laminated on a base material and used for various applications as a laminate. For example, it can also be used as an organic insulating film that requires low dielectric properties or a curable adhesive sheet for a device having an adhesive layer. Various known methods can be applied to the method of forming the laminate of the present embodiment. For example, a laminate can be produced by laminating the film produced by the above-described method on a base material and heat-curing it by pressing or the like as necessary. Further, a laminate can also be produced by laminating an electrical insulating layer containing the above-described cured product on a conductor layer.

[0089] [Multilayer molded body or multilayer 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 bodies or multilayer laminated films. Examples of various multilayer molded bodies or multilayer laminated films include a multilayer molded body for an optical lens in which the film of the present embodiment is formed on the surface of a resin optical lens, and a multilayer gas barrier film in which the film of the present embodiment is formed on the surface of a resin film such as a PET film or a PE film for imparting gas barrier properties.

[0090] [Metal-clad laminate] The metal-clad laminate of the present embodiment includes a metal foil on at least one side of the laminate of the present embodiment. The laminate of the present embodiment may be formed into a metal-clad laminate by laminating a metal foil on at least one surface of the laminate of the present embodiment and heat-curing it by laminate pressing or the like. Further, the metal foil may be bonded to both surfaces of the laminate. Examples of the metal foil 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 preferably used. Various known methods can be applied to the method for producing the metal-clad laminate of the present embodiment. For example, a metal-clad laminate can be produced by laminating a metal foil on the laminate of the present embodiment and, if necessary, heating and curing it by pressing or the like.

[0091] Since the metal-clad laminate of the present embodiment uses a cured product obtained by curing the resin composition of the present embodiment, the balance between low dielectric properties and heat resistance in the high-frequency region, which is suitable for printed wiring boards, is improved. Therefore, the metal-clad laminate of the present embodiment can be suitably used as a material for the insulating layer of a printed wiring board.

[0092] [Printed Wiring Board] The printed wiring board of the present embodiment is manufactured using the prepreg of the present embodiment or the metal-clad laminate of the present embodiment. Since the cured product obtained by curing the resin composition of the present embodiment has an improved balance between low dielectric properties and heat resistance in the high-frequency region, it can be suitably used for printed wiring boards. As a method for manufacturing a printed wiring board, generally known methods can be adopted and are not particularly limited. For example, a film or laminate manufactured by the above-described method is heat-cured by lamination pressing or the like to form an electrical insulating layer. Next, a conductor layer is laminated on the obtained electrical insulating layer by a known method to produce a laminate. Thereafter, a printed wiring board can be obtained by circuit processing or the like of the conductor layer in the laminate.

[0093] As the metal for the conductor layer, for example, copper, aluminum, nickel, gold, silver, stainless steel, etc. can be used. As the method for forming the conductor layer, for example, a method of thermally fusing the above metals in the form of foil, etc. onto the electrical insulation layer, a method of bonding the above metals in the form of foil, etc. onto the electrical insulation layer using an adhesive, or a method of forming a conductor layer made of the above metals onto the electrical insulation layer by means of sputtering, vapor deposition, plating, etc. can be mentioned. As the aspect of the printed wiring board, either a single-sided board or a double-sided board may be used.

[0094] Such a printed wiring board can be used as an electronic device, for example, by mounting electronic components such as semiconductor elements. Also, the electronic device of the present embodiment includes the film or the printed wiring board of the present embodiment. The electronic device of the present embodiment can be manufactured based on known information. Examples of such electronic devices include ICT infrastructure devices such as servers, routers, supercomputers, mainframes, workstations, etc.; antennas such as GPS antennas, wireless base station antennas, millimeter wave antennas, RFID antennas, etc.; communication devices such as mobile phones, smartphones, PHS, PDAs, tablet terminals, etc.; digital devices such as personal computers, TVs, digital cameras, digital video cameras, POS terminals, wearable terminals, digital media players, etc.; in-vehicle electronic devices such as electronic control system devices, in-vehicle communication devices, car navigation devices, millimeter wave radars, in-vehicle camera modules, etc.; semiconductor test devices, high-frequency measurement devices, etc.; high-speed communication compatible modules; and the like.

[0095] [High-speed communication compatible module] The electronic device of the present embodiment includes a high-speed communication compatible module. The high-speed communication compatible module of the present embodiment is a high-speed communication compatible module manufactured using the film or the printed wiring board of the present embodiment. The high-speed communication compatible module of this embodiment is, for example, a communication module formed by mounting a semiconductor chip or the like on the printed wiring board of this embodiment, and particularly uses signals in the high-frequency range such as wireless communication devices and network infrastructure devices, and is suitable for applications with a large amount of information communication and high speed.

[0096] [Applications of the cured product] Since the cured product obtained by curing the resin composition of this embodiment has a good balance of low dielectric properties and heat resistance in the high-frequency region, for example, optical fibers, optical waveguides, optical disk substrates, optical filters, lenses, optical adhesives, optical filters for PDPs, coating materials for organic ELs, base film substrates for solar cells in the aerospace field, coating materials for solar cells and thermal control systems, semiconductor elements, light-emitting diodes, electronic elements such as various memories, hybrid ICs, MCMs, printed wiring boards, prepregs and laminates used to form the insulating layer of printed wiring boards, overcoat materials or interlayer insulating materials for display components, substrates for liquid crystal displays and solar cells, medical instruments, automotive members, resin modifiers, transparent substrates for displays, gas barrier coating materials, wire sheathing materials, automotive members, aerospace members, process materials for semiconductors, wire coating materials, members for lithium-ion batteries, members for fuel cells, capacitor films, flexible display members, anchor coating materials, transparent adhesives, hard coating materials, etc. It can be used in applications such as. In particular, the cured product obtained by curing the resin composition of this embodiment has an improved balance of low dielectric properties and heat resistance in the high-frequency region, and also has a good performance balance such as insulating properties and mechanical properties. Therefore, it can be suitably used for printed wiring boards, and can be more suitably used for high-frequency applications such as high-frequency printed wiring boards.

[0097] The embodiments of the present invention have been described above, but these are examples of the present invention, and various configurations other than the above can also be adopted. Further, the present invention is not limited to the above-described embodiments, and modifications, improvements, etc. within the range that does not impair the effects of the present invention are included in the present invention.

Examples

[0098] Hereinafter, this embodiment will be described in detail with reference to examples and the like. Note that this embodiment is not limited to the descriptions of these examples at all.

[0099] (Raw materials) Crosslinking aid 1: Glycoluril-based crosslinkable compound (1,3,4,6-tetraallylglycoluril, TA-G manufactured by Shikoku Kasei Co., Ltd.)

[0100]

Chem.

[0101] Crosslinking aid 2: Bis isocyanurate-based crosslinkable compound (bis(diallyl isocyanurate) compound, product name: DD-1, manufactured by Shikoku Kasei Co., Ltd.)

[0102]

Chem.

[0103] Crosslinking aid 3: Isocyanurate-based crosslinkable compound (triallyl isocyanurate, manufactured by Tokyo Chemical Industry Co., Ltd.)

[0104]

Chem.

[0105] Crosslinking aid 4: Isocyanurate-based crosslinkable compound (tris(2-acryloyloxyethyl) isocyanurate, manufactured by Tokyo Chemical Industry Co., Ltd.)

[0106]

Chem.

[0107] Crosslinking aid 5: Divinylbenzene (manufactured by Fujifilm Wako Pure Chemical Corporation) Since the number of crosslinkable groups (β) is two, it does not correspond to the crosslinkable compound (a).

[0108] Thermosetting cyclic olefin copolymer (m-1): The synthesis method will be described later. Radical polymerization initiator 1: 2,3-dimethyl-2,3-diphenylbutane (manufactured by Acros Organics) Antioxidant 1: Phenolic antioxidant (pentaerythritol tetrakis[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate), product name: Irganox 1010, manufactured by BASF)

[0109] The following raw materials were used for the synthesis of the thermosetting cyclic olefin copolymer (m-1). Transition metal compound (1): Synthesized by the method described in JP-A-2004-331965.

[0110]

Chemical formula

[0111] Modified methylaluminoxane (MMAO, manufactured by Tosoh Finechem Corporation) Toluene (manufactured by Fujifilm Wako Pure Chemical Corporation: Wako special grade) 5-Vinyl-2-norbornene (hereinafter, VNB) (manufactured by Tokyo Chemical Industry Co., Ltd.) Tetracyclo[4.4.0.1 2,5 .1 7,10 -3-dodecene (hereinafter, TD) (manufactured by Mitsui Chemicals, Inc.) Methanol (manufactured by Fujifilm Wako Pure Chemical Corporation: Wako special grade)

[0112] [Method for measuring the content of each structural unit constituting the cyclic olefin copolymer] The contents of the structural unit (A), the structural unit (B), and the structural unit (C) were measured under the following conditions using a "EXcalibur270" nuclear magnetic resonance apparatus manufactured by JEOL Ltd. Number of integrations: 16 to 64 times Measurement temperature: Room temperature (25 °C) From the 1 1H-NMR spectrum obtained in the above measurement, they were calculated respectively from the intensities of the peaks derived from the hydrogen directly bonded to the double bond carbon and the peaks of the other hydrogens.

[0113] Also, the number average molecular weight (Mn) of the thermosetting cyclic olefin copolymer (m) used in the synthesis examples, examples, and comparative examples was measured by GPC measurement and determined as a standard polystyrene conversion value. The GPC measurement was carried out under the following conditions. Apparatus: GPC HLC-8321 (manufactured by Tosoh Corporation) Solvent: o-dichlorobenzene Columns: TSKgel GMH6-HT×2, TSKgel GMH6-HTL×2 (both manufactured by Tosoh Corporation) Flow rate: 1.0 ml / min Sample: 1 mg / mL o-dichlorobenzene solution Temperature: 140 °C

[0114] [Glass transition temperature Tg (°C)] Using DSC-6220 manufactured by Shimadzu Science Corporation, the glass transition temperature Tg of the cyclic olefin copolymer was measured under a N2 (nitrogen) atmosphere. The cyclic olefin copolymer was heated from 25 °C to 200 °C at a heating rate of 10 °C / min and then held for 5 minutes, and then cooled to -20 °C at a cooling rate of 10 °C / min and then held for 5 minutes. Then, the glass transition temperature (Tg) of the cyclic olefin copolymer was determined from the endothermic curve when heating to 200 °C at a heating rate of 10 °C / min.

[0115] [Synthesis Example 1 (Thermosetting Cyclic Olefin Copolymer (m))] Into a 1 L SUS autoclave with sufficient nitrogen substitution, 450 ml of toluene, 30 ml of VNB, 16 ml of TD, a hexane solution of MMAO with 0.9 mmol in terms of Al, and 360 ml of hydrogen were charged, and then ethylene was introduced into the system until the total pressure reached 0.6 MPa. A toluene solution of 0.028 mmol of the transition metal compound (1) was added, and polymerization was carried out at 35 °C for 180 minutes. Then, the polymerization was stopped by injecting 1 ml of methanol under pressure. After the coincidence ended, ion-exchanged water was added to the obtained polymer solution and stirred for 1 hour. Then, the organic layer was filtered through filter paper and concentrated until the solid content reached 20% to obtain a toluene varnish containing 20% by mass of the cyclic olefin copolymer (m-1). The composition ratio of the TD-derived structure in the polymer determined by NMR for the cyclic olefin copolymer (m-1) contained in the varnish was 12 mol%, the composition ratio of the VNB-derived structure was 26 mol%, the number average molecular weight (Mn) determined by GPC measurement was 21,000, and the glass transition temperature Tg was 99°C.

[0116] [Example 1] (Preparation of varnish) To the toluene varnish containing 20% by mass of the thermosetting cyclic olefin copolymer (m-1) obtained in Synthesis Example 1, a crosslinking assistant, a radical initiator, and an antioxidant weighed according to the composition shown in Table 1 were added and stirred until completely dissolved to obtain the target varnish-like cyclic olefin copolymer composition. The unit of the blending ratio of each raw material in Table 1 is parts by mass.

[0117] (Production of laminated film) The obtained varnish-like cyclic olefin copolymer resin composition was coated on a release-treated PET film at a speed of 10 mm / second, and then dried in a hot air dryer under a nitrogen stream at 150°C for 4 minutes to obtain a laminated film of the PET film and the composition. Two obtained laminated films were overlapped so that the resin compositions were in contact with each other, and under a vacuum controlled to 20 kPa or less by a vacuum press, a press pressure of 3.5 MPa was applied, the temperature was raised from room temperature (25°C) at a constant speed, and held at 180°C for 60 minutes. After holding, it was taken out once, the PET film was peeled off, and then under a vacuum controlled to 20 kPa or less by a vacuum press with a polyimide film sandwiched, a press pressure of 3.5 MPa was applied, the temperature was raised from room temperature (25°C) at a constant speed, and held at 220°C for 120 minutes to obtain a polyimide / cured product / polyimide laminated film. Dielectric tangent measurement and heat resistance evaluation were performed on the obtained laminated film based on the following procedure. The results obtained are shown in Table 1.

[0118] Dielectric tangent evaluation: For the laminated films obtained in the examples and comparative examples, the dielectric tangent Df at 10 GHz was measured by the cylindrical cavity resonator method and evaluated as follows. Those with a dielectric tangent less than 0.0010 were designated as "A" as having excellent low dielectric characteristics in the high-frequency region, and those with a dielectric tangent of 0.0010 or more were designated as "B" as having inferior low dielectric characteristics in the high-frequency region.

[0119] Heat resistance evaluation: The solid viscoelastic temperature dispersion of the laminate obtained under the following conditions was measured, and the glass transition temperature Tg of the composition was evaluated. The glass transition temperature Tg of the composition was taken as the peak temperature of the loss tangent (tanδ). The results obtained are shown in Table 1. Apparatus: RSA-III (manufactured by TA Instruments) Deformation mode: Tension Temperature range: 25°C to 300°C Heating rate: 3°C / min Frequency: 1 Hz Set strain: 0.1% Environment: Under a nitrogen atmosphere

[0120] [Examples 2 to 3, Reference Example 1, and Comparative Examples 1 to 3] Except for changing to the compounding compositions shown in Table 1, varnish and laminated films were prepared in the same manner as in Example 1, and evaluation was carried out. The results obtained are shown in Table 1.

[0121]

Table 1

Claims

1. A resin composition comprising a thermosetting cyclic olefin (co)polymer (m) having a crosslinkable group (α), and a crosslinking aid (A), The crosslinking aid (A) comprises a crosslinkable compound (a) having three or more crosslinkable groups (β), wherein each crosslinkable group (β) comprises at least one functional group selected from the group consisting of vinyl groups and allyl groups. A resin composition in which the amount of the crosslinking aid (A) per 100 parts by mass of the thermosetting cyclic olefin (co)polymer (m) is 6 parts by mass or more.

2. The resin composition according to claim 1, wherein the crosslinkable compound (a) further has a heterocyclic structure.

3. The aforementioned thermosetting cyclic olefin-based (co)polymer (m) (A) One or more repeating units derived from olefins represented by the following general formula (I), (B) A repeating unit derived from one or more cyclic non-conjugated dienes represented by the following general formula (III), (C) The resin composition according to claim 1, comprising one or more repeating units derived from a cyclic olefin represented by the following general formula (V). 【Chemistry 1】 [In the above general formula (I), R ３００ This represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms. 【Chemistry 2】 [In the above general formula (III), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, R ６１ ~R ７６ R ａ１ and R ｂ１ These may be the same or different from each other, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, R １０４ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, t is a positive integer from 0 to 10, and R ７５ and R ７６ These may be bonded to each other to form a monocycle or polycycle. 【Transformation 3】 〔In the above general formula (V), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, R ６１ ~R ７８ as well as R ａ１ and R ｂ１ may be the same as or different from each other, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and R ７５ ~R ７８ may be bonded to each other to form a monocyclic or polycyclic ring.〕

4. When the total number of moles of repeating units in the thermosetting cyclic olefin copolymer (m) is set to 100 mol%, The content of the repeating units (A) derived from the olefin is 10 mol% or more and 90 mol% or less. The content of the repeating units (B) derived from the cyclic non-conjugated diene is 1 mol% or more and 40 mol% or less, The resin composition according to claim 3, wherein the content of repeating units (C) derived from the cyclic olefin is 1 mol% or more and 50 mol% or less.

5. The resin composition according to claim 3, wherein the cyclic non-conjugated diene constituting the repeating unit (B) derived from the cyclic non-conjugated diene contains 5-vinyl-2-norbornene.

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

7. The resin composition according to claim 1, wherein the cured product obtained by heating the resin composition at 220°C has a dielectric loss tangent at 10 GHz of less than 0.0010.

8. The resin composition according to claim 1, wherein the glass transition temperature of the cured product obtained by heating the resin composition at 220°C is 141°C or higher.

9. A varnish comprising the resin composition according to claim 1 and a solvent.

10. A prepreg comprising a fibrous substrate impregnated with the resin composition described in claim 1 or the varnish described in claim 9.

11. A film comprising a cured product of the resin composition described in claim 1.

12. A laminate comprising the prepreg described in claim 10.

13. A laminate comprising the film described in Claim 11.

14. A metal-clad laminate comprising a metal foil on at least one side of the laminate according to claim 12.

15. A printed circuit board manufactured using the metal-clad laminate described in claim 14.

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