Method for producing cyclic olefin copolymer, cyclic olefin copolymer, and resin composition

Abstract

To provide a method for producing a cyclic olefin copolymer that allows control of increase in number-average molecular weight (Mn).SOLUTION: Provided is a method for producing a cyclic olefin copolymer that includes structural units derived from an α-olefin (A), structural units derived from a cyclic non-conjugated diene (B), and structural units derived from a cyclic olefin (C), the method comprising a step of polymerizing the cyclic olefin copolymer in the presence of a transition metal compound (D), an organoaluminum compound (E), a hindered phenol compound (F), and hydrogen.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a method for producing a cyclic olefin copolymer, a cyclic olefin copolymer, and a resin composition.

Background Art

[0002] Recently, in addition to the increase in wireless communication devices using high-frequency bands, due to the increase in communication speed, inevitably, a higher-frequency band is often used. Along with this, a circuit board with a small dielectric tangent is required to reduce transmission loss at high frequencies to the limit.

[0003] Patent Document 1 discloses a cyclic olefin copolymer (m) containing (A) repeating units derived from one or more olefins represented by a specific general formula, (B) repeating units derived from one or more cyclic non-conjugated dienes represented by a specific general formula, and (C) repeating units derived from one or more cyclic olefins represented by a specific general formula. When the total number of moles of the repeating units in the cyclic olefin copolymer is 100 mol%, the content of the repeating units (B) derived from the cyclic non-conjugated diene is 19 mol% or more and 36 mol% or less, and the number average molecular weight Mn of the cyclic olefin copolymer is in the range of 3,000 or more and 16,000 or less, and a cyclic olefin copolymer having a crosslinkable group is disclosed. The invention described in Patent Document 1 is described in Patent Document 1 as being capable of obtaining a crosslinked product having excellent dielectric properties in a high-frequency region suitable for circuit boards and the like and also having excellent moldability, a cyclic olefin copolymer, and a cyclic olefin copolymer composition.

[0004] Patent Document 2 discloses an α-olefin·cyclic olefin·polyene copolymer containing a structural unit (A) represented by a specific general formula, a structural unit (B) represented by a specific general formula, and a structural unit (C) represented by a specific general formula, which is amorphous or has a heat of fusion of less than 90 kJ / kg. The invention described in Patent Document 2 aims to provide a cyclic olefin copolymer containing highly reactive double bonds and an efficient method for producing the copolymer. Specifically, it aims to provide a copolymer of an α-olefin, a cyclic olefin, and a polyene, which retains a large number of double bonds not involved in the copolymerization derived from the polyene, and a method for producing the same, as described in Patent Document 2.

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 method for producing a cyclic olefin copolymer capable of suppressing an increase in the number average molecular weight Mn.

Means for Solving the Problems

[0007] According to the present invention, there are provided a method for producing a cyclic olefin copolymer, a cyclic olefin copolymer, and a resin composition as shown below.

[0008] 1. A method for producing a cyclic olefin copolymer containing a structural unit derived from an α-olefin (A), a structural unit derived from a cyclic non-conjugated diene (B), and a structural unit derived from a cyclic olefin (C), comprising a step of polymerizing the cyclic olefin copolymer in the presence of a transition metal compound (D), an organoaluminum compound (E), a hindered phenol compound (F), and hydrogen. 2. The production method of the cyclic olefin copolymer according to 1., wherein the number of moles of the phenolic hydroxyl group in the hindered phenol compound (F) relative to 1 mole of the aluminum atom in the organoaluminum compound (E) is 0.020 mol or more and less than 0.50 mol. 3. The production method of the cyclic olefin copolymer according to 1. or 2., wherein the hindered phenol compound (F) contains a structure represented by the following formula (1).

Chemical formula

Chemical formula

Chemical formula

Advantages of the Invention

[0009] According to the present invention, a method for producing a cyclic olefin copolymer capable of suppressing an increase in the number average molecular weight Mn can be provided.

Embodiments for Carrying Out the Invention

[0010] Hereinafter, the present invention will be described based on embodiments.

[0011] In this embodiment, the description of "XX or more and YY or less" and "XX to YY" representing a numerical range means a numerical range including the lower limit and the upper limit which are endpoints, unless otherwise specified. When numerical ranges are described stepwise, the upper and lower limits of each numerical range can be arbitrarily combined.

[0012] In this embodiment, each monomer constituting the cyclic olefin copolymer of this embodiment may be a monomer obtained from a fossil raw material or a monomer obtained from an animal or plant raw material.

[0013] 1. Method for producing cyclic olefin copolymer Hereinafter, the method for producing the cyclic olefin copolymer of this embodiment will be described.

[0014] The method for producing the cyclic olefin copolymer of this embodiment is a method for producing a cyclic olefin copolymer containing a structural unit derived from α-olefin (A), a structural unit derived from cyclic non-conjugated diene (B), and a structural unit derived from cyclic olefin (C), and includes a step of polymerizing the cyclic olefin copolymer of this embodiment in the presence of a transition metal compound (D), an organoaluminum compound (E), a hindered phenol compound (F), and hydrogen. According to the method for producing the cyclic olefin copolymer of this embodiment, an increase in the number average molecular weight Mn can be suppressed.

[0015] Although the mechanism by which an increase in the number average molecular weight Mn can be suppressed by the method for producing the cyclic olefin copolymer of this embodiment is not clear, a mechanism is presumed in which the polymerization reaction is controlled by the interaction between the organoaluminum compound (E) and the hindered phenol compound (F), and an increase in Mn is suppressed.

[0016] <Hindered phenol compound (F)> As the hindered phenol compound (F), known hindered phenol compounds can be used without particular limitation. The hindered phenol compound (F) of the present embodiment includes a phenol compound having a bulky substituent at at least one of two adjacent positions of the phenolic hydroxy group, and preferably includes a phenol compound having bulky substituents at both of the two adjacent positions of the phenolic hydroxy group. The bulky substituent of the present embodiment includes, for example, one or more selected from the group consisting of an alkyl group such as an isopropyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group; an alkenyl group; an alkynyl group; an aryl group; a heterocyclic group; an alkoxy group; an aryloxy group; a substituted amino group; an alkylthio group; and an arylthio group, and preferably includes tert-butyl.

[0017] Hindered phenol compounds (F) include, for example, 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butylphenol, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylmethyl), pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) (product name: Irganox 1010, manufactured by BASF), bis[3-[3,5-di(tert-butyl)-4-hydroxyphenyl]propionate] thiodiethylene (product name: Irganox 1035, manufactured by BASF), octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (product name: Irganox 1076, manufactured by BASF), N,N′-(1,6-hexanediyl)bis[3,5-bis(1,1-dimethylethyl)-4-hydroxybenzene propanamide] (product name: Irganox 1098, manufactured by BASF), octyl 3-(4-hydroxy-3,5-diisopropylphenyl)propionate (product name: Irganox 1135, manufactured by BASF), 4,4′,4′′-[(2,4,6-trimethylbenzene-1,3,5-triyl)tris(methylene)]tris(2,6-di-tert-butylphenol) (product name: Irganox 1330, manufactured by BASF), calcium bis[3,5-di(tert-butyl)-4-hydroxybenzyl(ethoxy)phosphinate] (product name: Irganox 1425WL, manufactured by BASF), 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (product name: Irganox 259, manufactured by BASF), 1,3,5-tris[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (product name: Irganox 3114, manufactured by BASF), 4-[[4,6-bis(octylthio)-1,3,5-triazin-2-yl]amino]-2,6-di-tert-butylphenol (product name: Irganox 565, manufactured by BASF), 2,4,6-trimethylbenzene, 2-tert-butylphenol, 2-tert-butyl-p-cresol, 3,3’,5,5’-tetra-tert-butyl-4,It contains one or more selected from the group consisting of 4'-dihydroxybiphenyl, 3,3',5,5'-tetra-tert-butyl-2,2'-dihydroxybiphenyl, 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 4,4',4''-(1-methylpropan-3-ylidene)tris(6-tert-butyl-m-cresol), triethylene glycol bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate (product name: SONGNOX 2450, manufactured by SONGWON), ethylene bis(oxyethylene)bis[3-(5-tert-butyl-hydroxy-m-tolyl)propionate] (product name: Irganox 245, manufactured by BASF), 1,1,3-tris-(2-methyl-4-hydroxy-5-tert-butylphenyl)butane (product name: Adekastab AO-30, manufactured by ADEKA), 4,4'-butylidenebis(3-methyl-6-tert-butyl)phenol (product name: Adekastab AO-40, manufactured by ADEKA), and 4,4'-thiobis(3-methyl-6-tert-butyl)phenol (product name: No Crack 300, manufactured by Ouchi Shinko Chemical Industry Co., Ltd).

[0018] From the viewpoint that the hindered phenol compound (F) can further suppress the increase in the number average molecular weight Mn, and from the viewpoint that the ratio (Mw / Mn) of the number average molecular weight Mn, which is an index indicating the sharpness of the molecular weight distribution, to the weight average molecular weight Mw can be reduced, it preferably contains a structure represented by the following formula (1).

[0019]

Chemical formula

[0020] The hindered phenol compound (F) containing the structure represented by formula (1) includes, for example, 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butylphenol, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylmethyl), pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) (product name: Irganox 1010, manufactured by BASF), bis[3-[3,5-di(tert-butyl)-4-hydroxyphenyl]propionate]thioethylene (product name: Irganox 1035, manufactured by BASF), octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (product name: Irganox 1076, manufactured by BASF), N,N′-(1,6-hexanediyl)bis[3,5-bis(1,1-dimethylethyl)-4-hydroxybenzene propanamide] (product name: Irganox 1098, manufactured by BASF), octyl 3-(4-hydroxy-3,5-diisopropylphenyl)propionate (product name: Irganox 1135, manufactured by BASF), 4,4′,4′′-[(2,4,6-trimethylbenzene-1,3,5-triyl)tris(methylene)]tris(2,6-di-tert-butylphenol) (product name: Irganox 1330, manufactured by BASF), calcium bis[3,5-di(tert-butyl)-4-hydroxybenzyl(ethoxy)phosphinate] (product name: Irganox 1425WL, manufactured by BASF), 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (product name: Irganox 259, manufactured by BASF), 1,3,5-tris[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (product name: Irganox 3114, manufactured by BASF) and 4-[[4,6-bis(octylthio)-1,3,5-triazin-2-yl]amino]-2,It contains one or more selected from the group consisting of 6-di-tert-butylphenol (product name: Irganox 565, manufactured by BASF). From the viewpoint of further suppressing the increase in the number average molecular weight Mn and the viewpoint of reducing Mw / Mn, it preferably contains one or more selected from the group consisting of 2,6-di-tert-butyl-4-methylphenol, pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) (product name: Irganox 1010, manufactured by BASF), octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (product name: Irganox 1076, manufactured by BASF), and 4,4′,4′′-[(2,4,6-trimethylbenzene-1,3,5-triyl)tris(methylene)]tris(2,6-di-tert-butylphenol) (product name: Irganox 1330, manufactured by BASF), more preferably contains one or two selected from the group consisting of 2,6-di-tert-butyl-4-methylphenol and pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) (product name: Irganox 1010, manufactured by BASF).

[0021] The number of moles of phenolic hydroxyl groups in the hindered phenol compound (F) relative to 1 mole of aluminum atoms in the organoaluminum compound (E) is preferably 0.020 mol or more, more preferably 0.022 mol or more, still more preferably 0.024 mol or more, from the viewpoint of further suppressing the increase in the number average molecular weight Mn and from the viewpoint of reducing Mw / Mn. And it is preferably less than 0.50 mol, more preferably less than 0.45 mol, still more preferably less than 0.40 mol, still more preferably less than 0.35 mol, still more preferably less than 0.30 mol, still more preferably less than 0.25 mol, still more preferably less than 0.20 mol. And it is preferably 0.020 mol or more and less than 0.50 mol, more preferably 0.020 mol or more and less than 0.45 mol, still more preferably 0.020 mol or more and less than 0.40 mol, still more preferably 0.020 mol or more and less than 0.35 mol, still more preferably 0.020 mol or more and less than 0.30 mol, still more preferably 0.020 mol or more and less than 0.25 mol, still more preferably 0.020 mol or more and less than 0.20 mol, still more preferably 0.022 mol or more and less than 0.20 mol, still more preferably 0.024 mol or more and less than 0.20 mol.

[0022] <Structural unit of cyclic olefin copolymer> The structural unit derived from the α-olefin (A) preferably contains a structural unit derived from an α-olefin represented by the following general formula (I).

[0023]

Chemical formula

[0024] In the general formula (I), R 300 is a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms.

[0025] The α-olefin (A) of the present embodiment is represented by the following general formula (Ia).

[0026]

Chemical formula

[0027] In general formula (Ia), R 300 is a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms.

[0028] The α-olefin (A) of the present embodiment includes, for example, one or more selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. From the viewpoint of improving heat resistance, mechanical properties, dielectric properties, transparency, and gas barrier properties, it preferably contains one or two selected from the group consisting of ethylene and propylene, and more preferably contains ethylene.

[0029] When the total content of all structural units in the cyclic olefin copolymer of the present embodiment is 100 mol%, the content of the structural unit derived from the α-olefin (A) is preferably 40 mol% or more and 80 mol% or less, more preferably 45 mol% or more and 75 mol% or less, still more preferably 50 mol% or more and 70 mol% or less, still more preferably 52 mol% or more and 67 mol% or less, still more preferably 55 mol% or more and 65 mol% or less, from the viewpoint of improving the solubility of the cyclic olefin copolymer in a solvent. And it is preferably 40 mol% or more, more preferably 45 mol% or more, still more preferably 50 mol% or more, still more preferably 52 mol% or more, still more preferably 55 mol% or more, and is preferably 80 mol% or less, more preferably 75 mol% or less, still more preferably 70 mol% or less, still more preferably 67 mol% or less, still more preferably 65 mol% or less. Note that the content of the structural unit derived from the α-olefin (A) of the present embodiment 1 can be measured by 1H-NMR.

[0030] The structural unit derived from the cyclic non-conjugated diene (B) preferably contains a structural unit derived from a non-conjugated diene represented by the following general formula (III).

[0031]

Chemical formula

[0032] In the general formula (III), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, 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 of 0 to 10, R 75 and R 76 may be bonded to each other to form a monocyclic or polycyclic ring.

[0033] The cyclic non-conjugated diene (B) of the present embodiment is represented by the following general formula (IIIa).

[0034]

Chemical formula

[0035] In the general formula (IIIa), u is 0 or 1, v is 0 or a positive integer, preferably an integer of 0 or more and 2 or less, more preferably 0 or 1, w is 0 or 1, R 61 ~R 76 as well as R a1 and R b1may be the same as or different from each other, and is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, R 104 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, t is a positive integer of 0 to 10, R 75 and R 76 may be bonded to each other to form a monocyclic or polycyclic ring.

[0036] The cyclic non-conjugated diene represented by the general formula (IIIa) is not particularly limited, and examples thereof include cyclic non-conjugated dienes represented by the following chemical formulas.

[0037]

Chemical formula

[0038]

Chemical formula

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

[0040]

Chemical formula

[0041] In the general formula (IIIb), n is an integer of 0 to 10, R1 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R2 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

[0042] The structural unit derived from the cyclic non-conjugated diene (B) preferably contains one or two selected from the group consisting of a structural unit derived from 5-vinyl-2-norbornene and a structural unit derived from 5-ethylidene-2-norbornene.

[0043] The cyclic olefin copolymer of the present embodiment is characterized in that, since it 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.

[0044] When the total content of all the structural units in the cyclic olefin copolymer of the present embodiment is 100 mol%, the content of the structural unit derived from the cyclic non-conjugated diene (B) is preferably 1 mol% or more and 40 mol% or less, more preferably 3 mol% or more and 35 mol% or less, still more preferably 5 mol% or more and 33 mol% or less, still more preferably 8 mol% or more and 30 mol% or less, still more preferably 10 mol% or more and 28 mol% or less, from the viewpoint of improving the solubility of the cyclic olefin copolymer in a solvent, and is preferably 1 mol% or more, more preferably 3 mol% or more, still more preferably 5 mol% or more, still more preferably 8 mol% or more, still more preferably 10 mol% or more, and is preferably 40 mol% or less, more preferably 35 mol% or less, still more preferably 33 mol% or less, still more preferably 30 mol% or less, still more preferably 28 mol% or less. Note that the content of the structural unit derived from the cyclic non-conjugated diene (B) of the present embodiment is 1 measurable by 1H-NMR.

[0045] The structural unit derived from the cyclic olefin (C) preferably contains a structural unit derived from a cyclic olefin represented by the following general formula (V).

[0046]

Chemical formula

[0047] In the 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 b1may be the same as or different from each other, and is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, R 75 ~R 78 may be bonded to each other to form a monocyclic or polycyclic ring.

[0048] The cyclic olefin (C) of the present embodiment is represented by the following general formula (Va).

[0049] [Chemical formula]

[0050] In the general formula (Va), u is 0 or 1, v is 0 or a positive integer, preferably an integer of 0 or more and 2 or less, more preferably 0 or 1, w is 0 or 1, R 61 ~R 78 as well as R a1 and R b1 may be the same as or different from each other, and is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, R 75 ~R 78 may be bonded to each other to form a monocyclic or polycyclic ring.

[0051] As specific examples of the cyclic olefin represented by the general formula (Va), the compounds described in International Publication No. 2006 / 118261 can be used.

[0052] The structural unit derived from the cyclic olefin (C) is preferably a structural unit derived from bicyclo[2.2.1]-2-heptene and tetracyclo[4.4.0.1 2,5 .1 7,10- It contains one or two selected from the group consisting of structural units derived from 3-dodecene. As a result, the cyclic olefin copolymer has a rigid ring structure, and it becomes easier to maintain the elastic modulus of the cyclic olefin copolymer.

[0053] When the total content of all structural units in the cyclic olefin copolymer of the present embodiment is 100 mol%, the content of the structural unit derived from cyclic olefin (C) is preferably 1 mol% or more and 40 mol% or less, more preferably 3 mol% or more and 35 mol% or less, still more preferably 5 mol% or more and 30 mol% or less, still more preferably 8 mol% or more and 25 mol% or less, still more preferably 10 mol% or more and 20 mol% or less, and preferably 1 mol% or more, more preferably 3 mol% or more, still more preferably 5 mol% or more, still more preferably 8 mol% or more, still more preferably 10 mol% or more, and preferably 40 mol% or less, more preferably 35 mol% or less, still more preferably 30 mol% or less, still more preferably 25 mol% or less, still more preferably 20 mol% or less. In addition, the content of the structural unit derived from cyclic olefin (C) of the present embodiment 1 can be measured by 1H-NMR.

[0054] From the viewpoint of improving the solubility of the cyclic olefin copolymer in a solvent, the cyclic olefin copolymer of the present embodiment may further contain one or more selected from the group consisting of a structural unit derived from a cyclic olefin represented by the following general formula (VIa), a structural unit derived from a cyclic olefin represented by the following general formula (VIIa), and a structural unit derived from a chain polyene represented by the following general formula (VIIIa). Further, the cyclic olefin copolymer of the present embodiment may further contain one or more selected from the group consisting of a structural unit derived from a cyclic olefin represented by the following general formula (VIa) and a structural unit derived from a chain polyene represented by the following general formula (VIIIa). As a result, the cyclic olefin copolymer has a rigid ring structure, and it becomes easier to maintain the elastic modulus of the cyclic olefin copolymer.

[0055] [Chemical formula]

[0056] In general formula (VIa), x and d may be 0 or an integer of 1 or more, for example, an integer of 0 or more and 2 or less, and may be, for example, 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, and 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.

[0057] When the total content of all structural units in the cyclic olefin copolymer of the present embodiment is 100 mol%, the content of the structural unit derived from the cyclic olefin represented by the general formula (VIa) is not particularly limited, and may be, for example, 0.1 mol% or more and 50 mol% or less.

[0058] As specific examples of the cyclic olefin represented by the general formula (VIa), the compounds described in paragraphs 0037 to 0063 of International Publication No. 2006 / 118261 can be used.

[0059] [Chemical formula]

[0060] In general formula (VIIa), R 100 and R101 may be the same as or different from each other, and represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and f satisfies 1 ≦ f ≦ 18.

[0061] When the total content of all structural units in the cyclic olefin copolymer of the present embodiment is 100 mol%, the content of the structural unit derived from the cyclic olefin represented by the general formula (VIIa) is not particularly limited, and may be, for example, 0.1 mol% or more and 50 mol% or less.

[0062] As specific examples of the cyclic olefin represented by the general formula (VIIa), the compounds described in paragraphs 0037 to 0063 of International Publication No. 2006 / 118261 can be used.

[0063]

Chemical formula

[0064] In the general formula (VIIIa), R 201 to R 206 may 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.

[0065] Specific examples of the chain polyene represented by the general formula (VIIIa) include 1,4 - hexadiene, 3 - methyl - 1,4 - hexadiene, 4 - methyl - 1,4 - hexadiene, 5 - methyl - 1,4 - hexadiene, 4,5 - dimethyl - 1,4 - hexadiene, 7 - methyl - 1,6 - octadiene, DMDT, 1,3 - butadiene, 1,5 - hexadiene, etc. Also, cyclizable polyenes cyclized from polyenes such as 1,3 - butadiene and 1,5 - hexadiene may be used.

[0066] When the total content of all structural units in the cyclic olefin copolymer of the present embodiment is 100 mol%, the content of the structural unit derived from the cyclic olefin represented by the general formula (VIIIa) is not particularly limited, and may be, for example, 0.1 mol% or more and 50 mol% or less.

[0067] <Transition metal compound (D)> The transition metal compound (D) may be a conventionally known transition metal compound. For example, it may be a transition metal compound exemplified in paragraphs 0095 to 0160 of International Publication No. 2006 / 118261, or may be a transition metal compound exemplified in paragraphs 0036 to 0177 of JP-A-2004-331965.

[0068] From the viewpoint of enhancing the copolymerizability of the cyclic olefin and the cyclic non-conjugated diene, the transition metal compound (D) preferably contains a transition metal compound represented by the following general formula (VIII).

[0069]

Chemical formula

[0070] In the general formula (VIII), M is a transition metal of Group 3 to Group 11, m is an integer of 1 to 4, and R 1 ~R 6 may be the same as or different from each other, and is a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group. R 1 ~R 6 may be bonded to each other to form a monocyclic or polycyclic ring. When m is 2 or more, one of the groups R 1 ~R 6 contained in one ligand and one of the groups R 1 ~R 6 contained in another ligand may be linked. R 1 with each other, R 2 with each other, R 3 with each other, R 4 with each other, R5 each other, R 6 each other may be the same or different, n is a number that satisfies the valence of M, and X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group. When n is 2 or more, the plurality of groups represented by X may be the same or different from each other, and X may be bonded to each other to form a monocyclic or polycyclic ring.

[0071] In general formula (VIII), M is a transition metal atom of Groups 3 to 11 of the periodic table (Group 3 includes lanthanoids), preferably a transition metal atom of Groups 3 to 6, and more preferably a transition metal atom of Group 4 or 5. M may be, for example, scandium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, cobalt, iron, or ruthenium, preferably titanium, zirconium, hafnium, or vanadium, and more preferably titanium.

[0072] In general formula (VIII), m is an integer of 1 to 4, preferably 1 or 2, and more preferably 2.

[0073] In general formula (VIII), R 1 ~R 6 are a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group.

[0074] R 1 ~R 6 When R 1 ~R 6 is a hydrocarbon group, R 1 ~R 6 may be substituted with a hydrogen atom by a halogen, and may be, for example, a halogenated hydrocarbon group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, such as a trifluoromethyl group, a pentafluorophenyl group, or a chlorophenyl group.

[0075] R 1 ~R 6 When ~R is a hydrocarbon group, R 1 ~R 6 may be substituted with another hydrocarbon group, and for example, may be an aryl group-substituted alkyl group such as a benzyl group or a cumyl group.

[0076] R 1 ~R 6 When ~R is a hydrocarbon group, R 1 ~R 6 is, for example, a heterocyclic compound residue; an oxygen-containing group such as an alkoxy group, an aryloxy group, an ester group, an ether group, an acyl group, a carboxyl group, a carbonate group, a hydroxy group, a peroxy group, a carboxylic anhydride group; a nitrogen-containing group such as an amino group, an imino group, an amide group, an imide group, a hydrazino group, a hydrazono group, a nitro group, a nitroso group, a cyano group, an isocyano group, a cyanate ester group, an amidino group, a diazo group, an ammonium salt of an amino group; a boron-containing group such as a borandiyl group, a borantriyl group, a diboranyl group; a sulfur-containing group such as a mercapto group, a thioester group, a dithioester group, an alkylthio group, an arylthio group, a thioacyl group, a thioether group, a thiocyanate ester group, an isothiocyanate ester group, a sulfone ester group, a sulfonamide group, a thiocarboxyl group, a dithiocarboxyl group, a sulfo group, a sulfonyl group, a sulfinyl group, a sulfenyl group; a phosphorus-containing group such as a phosphide group, a phosphoryl group, a thiophosphoryl group, a phosphato group; a silicon-containing group; a germanium-containing group; or a tin-containing group.

[0077] R 1 ~R 6 When ~R is a hydrocarbon group, R 1 ~R 6is preferably a linear or branched alkyl group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, neopentyl group, n-hexyl group; an aryl group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, such as phenyl group, naphthyl group, biphenyl group, terphenyl group, phenanthryl group, anthracenyl group; or a substituted aryl group in which 1 to 5 substituents such as a halogen atom, an alkyl group or an alkoxy group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, an aryl group or an aryloxy group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms are substituted on these aryl groups.

[0078] R 1 ~R 6 When R 1 ~R 6 is a heterocyclic compound residue, R

[0079] R 1 ~R 6 When R

[0080] R 1 ~R 6 is an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group or a phosphorus-containing group, examples of these groups include the same ones as those exemplified above. 1 ~R 6is, for example, a hydrocarbon-substituted silyl group such as a silyl group; a siloxy group; a methylsilyl group, dimethylsilyl group, trimethylsilyl group, ethylsilyl group, diethylsilyl group, triethylsilyl group, diphenylmethylsilyl group, triphenylsilyl group, dimethylphenylsilyl group, dimethyl-tert-butylsilyl group or dimethyl(pentafluorophenyl)silyl group; or a hydrocarbon-substituted siloxy group such as a trimethylsiloxy group.

[0081] R 1 ~R 6 When R and ~R are germanium-containing groups or tin-containing groups, examples of these groups include those in which silicon in the silicon-containing group is substituted with germanium or tin.

[0082] In general formula (VIII), n is a number that satisfies the valence of M, and is, for example, an integer of 0 to 5, preferably 1 to 4, more preferably 1 to 3.

[0083] In general formula (VIII), X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group or a tin-containing group.

[0084] When X is a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, a phosphorus-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group or a tin-containing group, examples of these groups include the same ones as those exemplified above.

[0085] When X is an aluminum-containing group, X may be, for example, AlR4 (where R represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, etc.).

[0086] When X is a halogen-containing group, X may be, for example, a fluorine-containing group such as PF6, BF4; a chlorine-containing group such as ClO4, SbCl6; or an iodine-containing group such as IO4.

[0087] The method for adding the transition metal compound (D) of the present embodiment into the reaction system is not particularly limited, and the entire amount of the transition metal compound (D) may be added into the reaction system at once, or the transition metal compound (D) may be added in multiple portions. From the viewpoint of uniformly controlling the heat generation amount during polymerization, it is preferable to add the transition metal compound (D) in multiple portions.

[0088] <Organic aluminum compound (E)> From the viewpoint of enhancing the polymerization activity, the organic aluminum compound (E) preferably contains an organic aluminum oxy compound.

[0089] The organic aluminum oxy compound of the present embodiment may be a conventionally known organic aluminum oxy compound, for example, the organic aluminum oxy compound exemplified in JP-A-2-78687.

[0090] Conventionally known organic aluminum oxy compounds can be produced, for example, by the following methods (1) to (3), and are usually obtained as a solution in a hydrocarbon solvent. (1) A method of adding an organic aluminum compound to a hydrocarbon medium suspension of a compound containing adsorbed water or a salt containing crystal water, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, cerium(I) chloride hydrate, etc., to react the adsorbed water or crystal water with the organic aluminum compound. (2) A method of directly reacting water, ice or steam with an organic aluminum compound in a medium such as benzene, toluene, ethyl ether, tetrahydrofuran, etc. (3) A method of reacting an organic aluminum compound with an organic tin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene, toluene, etc.

[0091] The organoaluminum compounds used in preparing organoaluminum oxy compounds include, for example, tri-n-alkylaluminums such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum; tri-branched chain alkylaluminums such as triisopropylaluminum, triisobutylaluminum, tri-sec-butylaluminum, tri-tert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylbutylaluminum, tri-2-methylpentylaluminum, tri-3-methylpentylaluminum, tri-4-methylpentylaluminum, tri-2-methylhexylaluminum, tri-3-methylhexylaluminum, tri-2-ethylhexylaluminum; tricycloalkylaluminums such as tricyclohexylaluminum, tricyclooctylaluminum; triarylaluminums such as triphenylaluminum, tritolylaluminum; dialkylaluminum hydrides such as diisobutylaluminum hydride; (i-C4H9) x Al y (C5H 10 ) z (wherein x, y, and z are positive numbers and z ≧ 2x.) trialkenylaluminums such as triisoprenylaluminum represented thereby; alkylaluminum alkoxides such as isobutylaluminum methoxide, isobutylaluminum ethoxide, isobutylaluminum isopropoxide; dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide, dibutylaluminum butoxide; alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide, butylaluminum sesquibutoxide; R a 2.5 Al(OR b ) 0.5Partially alkoxylated alkylaluminum having an average composition represented by etc.; dialkylaluminum aryloxides such as diethylaluminum phenoxide, diethylaluminum(2,6-di-t-butyl-4-methylphenoxide), ethylaluminum bis(2,6-di-t-butyl-4-methylphenoxide), diisobutylaluminum(2,6-di-t-butyl-4-methylphenoxide), isobutylaluminum bis(2,6-di-t-butyl-4-methylphenoxide); dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride; alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide; partially halogenated alkylaluminum such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide; dialkylaluminum hydrides such as diethylaluminum hydride, dibutylaluminum hydride; alkylaluminum dihydrides such as ethylaluminum dihydride, propylaluminum dihydride and other partially hydrogenated alkylaluminum; and partially alkoxylated and halogenated alkylaluminum such as ethylaluminum ethoxychloride, butylaluminum butoxychloride, ethylaluminum ethoxybromide, comprising one or more selected from the group consisting of, preferably comprising one or more selected from the group consisting of trimethylaluminum, triisobutylaluminum and tricycloalkylaluminum, more preferably comprising one or two selected from the group consisting of trimethylaluminum and triisobutylaluminum.

[0092] Examples of commercially available products of the organoaluminum compound (E) include polymethylaluminoxane (abbreviation: PMAO, TMAO-312 manufactured by Tosoh Finechem Corporation), and modified methylaluminoxane (abbreviation: MMAO, MMAO-3A, TMAO-341 manufactured by Tosoh Finechem Corporation).

[0093] <Polymerization method> The step of polymerizing the cyclic olefin copolymer of the present embodiment can be carried out by any of liquid phase polymerization methods such as solution polymerization and suspension polymerization or gas phase polymerization. The solvent used in the liquid phase polymerization method contains, for example, one or more selected from the group consisting of alicyclic hydrocarbons, linear aliphatic hydrocarbons, aromatic hydrocarbons, and halogenated hydrocarbons. The alicyclic hydrocarbon of the present embodiment contains, for example, one or more selected from the group consisting of cyclopentane, cyclohexane, methylcyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, and decahydronaphthalene. The linear hydrocarbon of the present embodiment contains, for example, one or more selected from the group consisting of hexane, heptane, octane, nonane, decane, undecane, and dodecane. The aromatic hydrocarbon of the present embodiment contains, for example, one or more selected from the group consisting of toluene, benzene, xylene, mesitylene, and pseudocumene. The halogenated hydrocarbon of the present embodiment contains, for example, one or two selected from the group consisting of chlorobenzene and dichlorobenzene.

[0094] The step of polymerizing the cyclic olefin copolymer of the present embodiment can be carried out by any of batch, semi-continuous, and continuous methods. Further, the polymerization can be carried out in two or more stages with different reaction conditions.

[0095] The temperature in the step of polymerizing the cyclic olefin copolymer of the present embodiment is not particularly limited, but may be, for example, -50°C or higher and 200°C or lower, preferably 0°C or higher and 100°C or lower, and more preferably 20°C or higher and 70°C or lower. The polymerization temperature may be kept constant or changed during the polymerization.

[0096] The pressure in the step of polymerizing the cyclic olefin copolymer of the present embodiment is not particularly limited, and may be, for example, normal pressure or higher and 10 MPa or lower, preferably 0.2 MPa or higher and 5 MPa or lower, more preferably 0.3 MPa or higher and 1 MPa or lower. The polymerization pressure may be kept constant or may be changed during the polymerization.

[0097] In the step of polymerizing the cyclic olefin copolymer of the present embodiment, the molecular weight can also be adjusted by polymerization conditions such as the structure of the transition metal compound (D), the addition amount of the organoaluminum compound (E), the hydrogen addition amount, or the polymerization temperature.

[0098] The number average molecular weight Mn of the cyclic olefin copolymer of the present embodiment is preferably 3,000 or more, more preferably 4,000 or more, still more preferably 5,000 or more, still more preferably 5,500 or more, still more preferably 6,000 or more, still more preferably 6,500 or more, still more preferably 7,000 or more, still more preferably 7,500 or more, and preferably 16,000 or less, more preferably 15,000 or less, still more preferably 14,000 or less, still more preferably 13,000 or less, still more preferably 12,500 or less, still more preferably 12,000 or less, still more preferably 11,500 or less, still more preferably 11,000 or less, still more preferably 10,500 or less, and preferably 3,000 or more and 16,000 or less, more preferably 4,000 or more and 15,000 or less, still more preferably 5,000 or more and 14,000 or less, still more preferably 5,500 or more and 13,000 or less, still more preferably 6,000 or more and 12,500 or less, still more preferably 6,500 or more and 12,000 or less, still more preferably 7,000 or more and 11,500 or less, still more preferably 7,500 or more and 11,000 or less, still more preferably 7,500 or more and 10,500 or less. Note that the number average molecular weight Mn of the cyclic olefin copolymer of the present embodiment can be adjusted by polymerization conditions such as the structure of the transition metal compound (D), the organoaluminum compound (E), the hydrogen addition amount, or the polymerization temperature.

[0099] The ratio Mw / Mn of the number average molecular weight Mn to the weight average molecular weight Mw of the cyclic olefin copolymer of the present embodiment is preferably 5.0 or less, more preferably 4.5 or less, still more preferably 4.0 or less, still more preferably 3.5 or less, still more preferably 3.0 or less, and may be, for example, 1.0 or more, 1.3 or more, or 1.5 or more.

[0100] The glass transition temperature (Tg) of the cyclic olefin copolymer of the present embodiment may be, for example, 300°C or less. From the viewpoint of improving the solubility of the cyclic olefin copolymer in a solvent, it is preferably 250°C or less, more preferably 200°C or less, still more preferably 170°C or less, still more preferably 150°C or less, still more preferably 120°C or less, still more preferably 100°C or less. Note that the Tg of the cyclic olefin copolymer of the present embodiment can be controlled by the monomer charge ratio and the like.

[0101] The intrinsic viscosity [η] measured in decalin at 135°C of the cyclic olefin copolymer of the present embodiment is preferably more than 0.01 dl / g, more preferably 0.02 dl / g or more, still more preferably 0.05 dl / g or more, from the viewpoint of improving heat resistance and mechanical properties. And from the viewpoint of improving moldability such as impregnation property into other materials such as fiber base materials and wiring embedding property, it is preferably less than 0.20 dl / g, more preferably 0.19 dl / g or less, still more preferably 0.18 dl / g or less. Note that the intrinsic viscosity [η] measured in decalin at 135°C of the cyclic olefin copolymer of the present embodiment can be controlled by polymerization conditions such as the structure of the transition metal compound (D), the amount of the organoaluminum compound (E), the hydrogenation amount, or the polymerization temperature.

[0102] 2. Cyclic olefin copolymer Hereinafter, the cyclic olefin copolymer of the present embodiment will be described. The cyclic olefin copolymer of the present embodiment is obtained by the method for producing the cyclic olefin copolymer of the present embodiment.

[0103] 3. Resin Composition Hereinafter, the resin composition of this embodiment will be described. The resin composition of this embodiment is a resin composition containing a cyclic olefin copolymer containing structural units derived from α-olefin (A), structural units derived from cyclic non-conjugated diene (B), and structural units derived from cyclic olefin (C), and a hindered phenol compound (F). The number average molecular weight Mn of the cyclic olefin copolymer of this embodiment is 3,000 or more and 16,000 or less. When the content of the cyclic olefin copolymer of this embodiment is 100 parts by mass, the content of the hindered phenol compound (F) is 0.010 parts by mass or more and 0.50 parts by mass or less.

[0104] In the resin composition of this embodiment, when the content of the cyclic olefin copolymer of this embodiment is 100 parts by mass, the content of the hindered phenol compound (F) is preferably 0.015 parts by mass or more, more preferably 0.020 parts by mass or more, still more preferably 0.025 parts by mass or more, and preferably 0.40 parts by mass or less, more preferably 0.30 parts by mass or less, still more preferably 0.20 parts by mass or less.

[0105] In the resin composition of the present embodiment, the number average molecular weight Mn of the cyclic olefin copolymer of the present embodiment is preferably 3,000 or more, more preferably 4,000 or more, still more preferably 5,000 or more, still more preferably 5,500 or more, still more preferably 6,000 or more, still more preferably 6,500 or more, still more preferably 7,000 or more, still more preferably 7,500 or more, and preferably 16,000 or less, more preferably 15,000 or less, still more preferably 14,000 or less, still more preferably 13,000 or less, still more preferably 12,500 or less, still more preferably 12,000 or less, still more preferably 11,500 or less, still more preferably 11,000 or less, still more preferably 10,500 or less, and preferably 3,000 or more and 16,000 or less, more preferably 4,000 or more and 15,000 or less, still more preferably 5,000 or more and 14,000 or less, still more preferably 5,500 or more and 13,000 or less, still more preferably 6,000 or more and 12,500 or less, still more preferably 6,500 or more and 12,000 or less, still more preferably 7,000 or more and 11,500 or less, still more preferably 7,500 or more and 11,000 or less, still more preferably 7,500 or more and 10,500 or less. The number average molecular weight Mn of the cyclic olefin copolymer of the present embodiment can be adjusted by polymerization conditions such as the structure of the transition metal compound (D), the organoaluminum compound (E), the hydrogenation amount, or the polymerization temperature.

[0106] In the resin composition of the present embodiment, Mw / Mn, which is the ratio of the weight average molecular weight Mw to the number average molecular weight Mn of the cyclic olefin copolymer of the present embodiment, is preferably 5.0 or less, more preferably 4.5 or less, still more preferably 4.0 or less, still more preferably 3.5 or less, still more preferably 3.0 or less, and may be, for example, 1.0 or more, 1.3 or more, or 1.5 or more.

[0107] The resin composition of the present embodiment preferably further contains an organic solvent.

[0108] When the resin composition of the present embodiment contains an organic solvent, the resin composition of the present embodiment is preferably in the form of a varnish.

[0109] The organic solvent of the present embodiment preferably contains one or more selected from the group consisting of alicyclic hydrocarbons, linear hydrocarbons, aromatic hydrocarbons, and halogenated hydrocarbons. The alicyclic hydrocarbon of the present embodiment contains, for example, one or more selected from the group consisting of cyclopentane, cyclohexane, methylcyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, and decahydronaphthalene. The linear aliphatic hydrocarbon of the present embodiment contains, for example, one or more selected from the group consisting of hexane, heptane, octane, nonane, decane, undecane, and dodecane. The aromatic hydrocarbon of the present embodiment contains, for example, one or more selected from the group consisting of toluene, benzene, xylene, mesitylene, and pseudocumene. The halogenated hydrocarbon of the present embodiment contains, for example, one or two selected from the group consisting of chlorobenzene and dichlorobenzene. From the viewpoint of improving solubility, the organic solvent of the present embodiment preferably contains one or more selected from the group consisting of toluene, xylene, cyclohexane, and methylcyclohexane.

[0110] When the resin composition of the present embodiment is in the form of a varnish, the content of the cyclic olefin copolymer of the present embodiment in the resin composition of the present embodiment is preferably 1 part by mass or more and 70 parts by mass or less, more preferably 10 parts by mass or more and 60 parts by mass or less, and still more preferably 20 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the resin composition of the present embodiment from the viewpoint of improving the fluidity of the resin composition.

[0111] The method for preparing the varnish-like resin composition of the present embodiment may be carried out by any method. For example, it may be prepared by mixing a cyclic olefin copolymer composition and an organic solvent, or the reaction solution when the cyclic olefin copolymer is polymerized may be used as it is or after purification. When using the reaction solution when the cyclic olefin copolymer is polymerized, the content ratio of the cyclic olefin copolymer may be adjusted by concentration or dilution using the above organic solvent, and a solvent different from the reaction solvent may be added.

[0112] Since the cyclic olefin copolymer and the resin composition of the present embodiment have improved heat resistance, mechanical strength, and transparency, 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, circuit boards, prepregs and laminates used for forming insulating layers of circuit boards, overcoat materials or interlayer insulating materials for display parts, substrates for liquid crystal displays and solar cells, medical instruments, automotive members, release agents, resin modifiers, transparent substrates for displays, members for lithium ion batteries, semiconductor process members, film capacitors, gas barrier coating materials, wire coating materials, automotive members, aerospace members, semiconductor process materials, wire coating materials, members for lithium ion batteries, members for fuel cells, capacitor films, flexible display members, anchor coating materials, transparent adhesives, modifiers, crosslinking aids, medical containers, medical catheter members, waterproof seal materials, release materials, hard coating materials, foaming modifiers, etc. In particular, since it has good temporal stability of dielectric properties and also good heat resistance, transparency, mechanical properties, etc., it can be suitably used for high-frequency applications such as high-frequency circuit boards. Furthermore, since it also has excellent gas barrier properties, it can be suitably used as a substrate, film or sheet for liquid crystal displays and solar cells.

[0113] The embodiments of the present invention have been described above. These are merely examples of the present invention, and various configurations other than those described above can be adopted. Further, the present invention is not limited to the above-described embodiments, and modifications, improvements, etc. within the scope that can achieve the object of the present invention are included in the present invention.

Example

[0114] Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the examples.

[0115] The composition of the cyclic olefin copolymer in each example and comparative example was measured by the following method. The contents of the structural units derived from α-olefin (A), the structural units derived from cyclic non-conjugated diene (B), and the structural units derived from cyclic olefin (C) were measured using a "ECA-500" nuclear magnetic resonance apparatus manufactured by JEOL Ltd. under the following conditions. Frequency: 500.16 MHz Number of integrations: 512 times Measurement temperature: 120 °C From the 1 1H-NMR spectrum obtained by 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.

[0116] The number average molecular weight (Mn) and weight average molecular weight (Mw) of the cyclic olefin copolymer in each example and comparative example were measured by GPC measurement and determined as standard polystyrene conversion values. 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

[0117] The intrinsic viscosity [η] of the cyclic olefin copolymer of each example and comparative example was measured in decalin at 135°C.

[0118] The glass transition temperature Tg of the cyclic olefin copolymer of each example and comparative example was measured by DSC. Apparatus: DSC7020 (manufactured by Hitachi High-Tech Science Corporation) Measurement atmosphere: Nitrogen Heating rate: 10°C / min

[0119] The raw materials used for the synthesis of the cyclic olefin copolymer of each example and comparative example are as follows.

[0120] Transition metal compound (1): Synthesized by the method described in JP-A-2004-331965.

[0121]

Chemical formula

[0122] Ethylene (manufactured by Mitsui Chemicals, Inc.) Modified methylaluminoxane (product name: MMAO-3A, manufactured by Tosoh Finechem Corporation) Toluene (manufactured by Wako Pure Chemical Industries, Ltd.: Wako special grade) 5-Vinyl-2-norbornene (manufactured by Tokyo Chemical Industry Co., Ltd.) 2-Norbornene (manufactured by Tokyo Chemical Industry Co., Ltd.) Tetracyclo[4.4.0.1 2,5 .1 7,10 -3-dodecene (manufactured by Mitsui Chemicals, Inc.) 2,6-Di-tert-butyl-4-methylphenol (abbreviation: BHT, manufactured by Wako Pure Chemical Industries, Ltd.) Pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) (product name: Irganox 1010, manufactured by BASF) Acetone (manufactured by Wako Pure Chemical Industries, Ltd.: Wako special grade) Methanol (manufactured by Wako Pure Chemical Industries, Ltd.: Wako special grade)

[0123] [Example 1] Into a 1 L SUS autoclave with sufficient nitrogen substitution, 433 mL of toluene, 15 mL of 5-vinyl-2-norbornene (hereinafter also referred to as VNB), 52 mL of a 5 M toluene solution of 2-norbornene (hereinafter also referred to as NB), 0.029 mmol of 2,6-di-tert-butyl-4-methylphenol (hereinafter also referred to as BHT), a hexane solution of MMAO-3A in an amount of 1.2 mmol in terms of Al, and 1.5 L of hydrogen were inserted. Then, ethylene was introduced into the system until the total pressure reached 0.78 MPaG. 4 μmol of the transition metal compound (1) dissolved in toluene was added to initiate polymerization. After 40 minutes, 70 minutes, and 100 minutes from the start of polymerization, 4 μmol of the transition metal compound (1) was added each time. After polymerization was carried out for 130 minutes from the start of polymerization, a small amount of methanol was added to stop the polymerization. The reaction solution was poured into a mixed solvent of acetone and methanol with hydrochloric acid added to precipitate the polymer, and the polymer was recovered by filtration. The total obtained polymer was dried under reduced pressure at 80 °C for 10 hours to obtain 2.1 g of an ethylene / NB / VNB copolymer. The composition ratio of the NB-derived structure in the polymer determined by NMR was 35.2 mol%, the composition ratio of the VNB-derived structure was 8.8 mol%, the number average molecular weight (Mn) determined by GPC measurement was 8,080, the molecular weight distribution Mw / Mn was 1.6, and the intrinsic viscosity [η] was 0.13 dL / g.

[0124] [Example 2] An ethylene / NB / VNB copolymer of 34 g was obtained in the same manner as in Example 1 except that 0.100 mmol of BHT and a hexane solution of MMAO-3A in an amount of 1.5 mmol in terms of Al were used. The composition ratio of the NB-derived structure in the polymer determined by NMR was 34.3 mol%, the composition ratio of the VNB-derived structure was 10.4 mol%, the number average molecular weight (Mn) determined by GPC measurement was 10,200, the molecular weight distribution Mw / Mn was 1.7, the intrinsic viscosity [η] was 0.17 dL / g, and the Tg was 87 °C.

[0125] [Example 3] Except that 0.150 mmol of BHT and a hexane solution of MMAO-3A were 1.5 mmol in terms of Al, the same procedure as in Example 1 was carried out to obtain 30 g of an ethylene / NB / VNB copolymer. The composition ratio of the NB-derived structure in the polymer determined by NMR was 32.9 mol%, the composition ratio of the VNB-derived structure was 9.7 mol%, the number average molecular weight (Mn) determined by GPC measurement was 8,030, the molecular weight distribution Mw / Mn was 1.6, the intrinsic viscosity [η] was 0.13 dL / g, and the Tg was 72 °C.

[0126] [Example 4] Except that 0.210 mmol of BHT and a hexane solution of MMAO-3A were 1.5 mmol in terms of Al, the same procedure as in Example 1 was carried out to obtain 29 g of an ethylene / NB / VNB copolymer. The composition ratio of the NB-derived structure in the polymer determined by NMR was 33.7 mol%, the composition ratio of the VNB-derived structure was 9.8 mol%, the number average molecular weight (Mn) determined by GPC measurement was 8,010, the molecular weight distribution Mw / Mn was 1.6, the intrinsic viscosity [η] was 0.14 dL / g, and the Tg was 78 °C.

[0127] [Example 5] Except that 0.300 mmol of BHT and a hexane solution of MMAO-3A were 2.0 mmol in terms of Al, the same procedure as in Example 1 was carried out to obtain 29 g of an ethylene / NB / VNB copolymer. The composition ratio of the NB-derived structure in the polymer determined by NMR was 32.4 mol%, the composition ratio of the VNB-derived structure was 9.6 mol%, the number average molecular weight (Mn) determined by GPC measurement was 7,980, the molecular weight distribution Mw / Mn was 1.6, the intrinsic viscosity [η] was 0.13 dL / g, and the Tg was 72 °C.

[0128] [Example 6] In a 1 L SUS autoclave with sufficient nitrogen substitution, 429 mL of toluene, 36 mL of VNB, tetracyclo[4.4.0.1 2,5 .1 7,10-3-Dodecene (hereinafter also referred to as TD), 20 mL, BHT 0.210 mmol, a hexane solution of MMAO-3A 1.5 mmol in terms of Al, and hydrogen 1.3 L were inserted, and then ethylene was introduced into the system until the total pressure reached 0.80 MPaG. 7 μmol of the transition metal compound (1) dissolved in toluene was added to initiate the polymerization. After 50 minutes, 80 minutes, and 110 minutes from the start of polymerization, 10 μmol each of the transition metal compound (1) was added. After polymerization was carried out for 150 minutes from the start of polymerization, a small amount of methanol was added to stop the polymerization. The reaction solution was poured into a mixed solvent of acetone and methanol containing hydrochloric acid to precipitate the polymer, and the polymer was recovered by filtration. The total polymer obtained was dried under reduced pressure at 80 °C for 10 hours to obtain 46 g of an ethylene / TD / VNB copolymer. The composition ratio of the TD-derived structure in the polymer determined by NMR was 11.5 mol%, the composition ratio of the VNB-derived structure was 25.6 mol%, the number average molecular weight (Mn) determined by GPC measurement was 9,310, the molecular weight distribution Mw / Mn was 2.7, the intrinsic viscosity [η] was 0.16 dL / g, and the Tg was 91 °C.

[0129] [Example 7] Into a 1 L SUS autoclave with a sufficiently nitrogen-substituted internal volume, 429 mL of toluene, 36 mL of VNB, 20 mL of TD, 0.026 mmol of pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) (hereinafter also referred to as Irganox 1010), 1.5 mmol of a hexane solution of MMAO-3A in terms of Al, and 1.3 L of hydrogen were inserted. Then, ethylene was introduced into the system until the total pressure reached 0.80 MPaG. 7 μmol of the transition metal compound (1) dissolved in toluene was added to initiate polymerization. After 50 minutes, 80 minutes, and 110 minutes from the start of polymerization, 10 μmol of the transition metal compound (1) was added each time. After polymerization was carried out for 150 minutes from the start of polymerization, a small amount of methanol was added to stop the polymerization. The reaction solution was poured into a mixed solvent of acetone and methanol containing hydrochloric acid to precipitate the polymer, and the polymer was recovered by filtration. The total obtained polymer was dried under reduced pressure at 80 °C for 10 hours to obtain 45 g of an ethylene / TD / VNB copolymer. The composition ratio of the TD-derived structure in the polymer determined by NMR was 11.4 mol%, the composition ratio of the VNB-derived structure was 25.7 mol%, the number average molecular weight (Mn) determined by GPC measurement was 9,650, the molecular weight distribution Mw / Mn was 2.1, the intrinsic viscosity [η] was 0.16 dL / g, and the Tg was 90 °C.

[0130] [Example 8] An ethylene / TD / VNB copolymer of 42 g was obtained in the same manner as in Example 7 except that Irganox 1010 was 0.052 mmol. The composition ratio of the TD-derived structure in the polymer determined by NMR was 11.2 mol%, the composition ratio of the VNB-derived structure was 25.2 mol%, the number average molecular weight (Mn) determined by GPC measurement was 9,720, the molecular weight distribution Mw / Mn was 1.8, the intrinsic viscosity [η] was 0.15 dL / g, and the Tg was 87 °C.

[0131] [Comparative Example 1] Except for not adding 2,6-di-tert-butyl-4-methylphenol, 35 g of an ethylene / NB / VNB copolymer was obtained in the same manner as in Example 1. The composition ratio of the NB-derived structure in the polymer determined by NMR was 33.8 mol%, the composition ratio of the VNB-derived structure was 10.9 mol%, the number average molecular weight (Mn) determined by GPC measurement was 20,500, the molecular weight distribution Mw / Mn was 3.7, and the intrinsic viscosity [η] was 0.43 dL / g.

[0132] [Comparative Example 2] Except for not adding 2,6-di-tert-butyl-4-methylphenol, 31 g of an ethylene / NB / VNB copolymer was obtained in the same manner as in Example 2. The composition ratio of the NB-derived structure in the polymer determined by NMR was 34.3 mol%, the composition ratio of the VNB-derived structure was 10.1 mol%, the number average molecular weight (Mn) determined by GPC measurement was 29,300, the molecular weight distribution Mw / Mn was 22.0, the intrinsic viscosity [η] was 1.58 dL / g, and the Tg was 88 °C.

[0133] [Table 1]

[0134] Compared with the cyclic olefin copolymer of the comparative example, the increase in the number average molecular weight Mn of the cyclic olefin copolymer of the example was suppressed. From this, it can be seen that according to the method for producing a cyclic olefin copolymer of the present embodiment, an increase in the number average molecular weight Mn of the obtained cyclic olefin copolymer can be suppressed.

[0135] In addition, compared with the cyclic olefin copolymer of the comparative example, the ratio (Mw / Mn) of the number average molecular weight Mn to the weight average molecular weight Mw, which is an index indicating the sharpness of the molecular weight distribution, of the cyclic olefin copolymer of the example was small. From this, it can be seen that according to the method for producing a cyclic olefin copolymer of the present embodiment, the Mw / Mn of the obtained cyclic olefin copolymer can be reduced.

Claims

1. A method for producing a cyclic olefin copolymer comprising a structural unit derived from an α-olefin (A), a structural unit derived from a cyclic non-conjugated diene (B), and a structural unit derived from a cyclic olefin (C), comprising a step of polymerizing the cyclic olefin copolymer in the presence of a transition metal compound (D), an organoaluminum compound (E), a hindered phenol compound (F), and hydrogen.

2. The method for producing a cyclic olefin copolymer according to claim 1, wherein the molar number of phenolic hydroxyl groups in the hindered phenol compound (F) with respect to 1 mol of aluminum atoms in the organoaluminum compound (E) is 0.020 mol or more and less than 0.50 mol.

3. The method for producing a cyclic olefin copolymer according to claim 1 or 2, wherein the hindered phenol compound (F) contains a structure represented by the following formula (1). 【Chemical formula 1】

4. The method for producing a cyclic olefin copolymer according to any one of claims 1 to 3, wherein the hindered phenol compound (F) contains one or two selected from the group consisting of 2,6-di-tert-butyl-4-methylphenol and pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate).

5. The method for producing a cyclic olefin copolymer according to any one of claims 1 to 4, wherein the structural unit derived from the α-olefin (A) contains a structural unit derived from an α-olefin represented by the following general formula (I). 【Chemical formula 2】 (In the general formula (I), R ３００ is a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms)

6. The method for producing a cyclic olefin copolymer according to any one of claims 1 to 5, wherein the structural unit derived from the cyclic non-conjugated diene (B) contains a structural unit derived from a non-conjugated diene represented by the following general formula (III). 【Chemical formula 3】 (In the general formula (III), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, 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 of 0 to 10, R ７５ and R ７６ may be bonded to each other to form a monocyclic or polycyclic ring)

7. The method for producing a cyclic olefin copolymer according to claim 6, wherein the structural unit derived from the cyclic non-conjugated diene (B) contains one or two selected from the group consisting of a structural unit derived from 5-vinyl-2-norbornene and a structural unit derived from 5-ethylidene-2-norbornene.

8. When the total content of all structural units in the cyclic olefin copolymer is 100 mol%, the content of the structural unit derived from the cyclic non-conjugated diene (B) is 1 mol% or more and 40 mol% or less. The method for producing a cyclic olefin copolymer according to any one of claims 1 to 7.

9. The method for producing a cyclic olefin copolymer according to any one of claims 1 to 8, wherein the structural unit derived from the cyclic olefin (C) contains a structural unit derived from a cyclic olefin represented by the following general formula (V). 【Chemical formula 4】 (In the general formula (V), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, R ６１ to R ７８ and 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 to R ７８ may be bonded to each other to form a monocyclic or polycyclic ring)

10. The structural unit derived from the cyclic olefin (C) comprises one or two selected from the group consisting of a structural unit derived from bicyclo[2.2.1]-2-heptene and a structural unit derived from tetracyclo[4.4.0.1 ２，５ .1 ７，１０ -3-dodecene. The method for producing a cyclic olefin copolymer according to claim 9.

11. The transition metal compound (D) contains a transition metal compound represented by the following general formula (VIII). The method for producing a cyclic olefin copolymer according to any one of claims 1 to 10. 【Chemical formula 5】 (In the general formula (VIII), M is a transition metal of Group 3 to Group 11, m is an integer of 1 to 4, and R １ to R ６ may be the same as or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group or a tin-containing group, and R １ to R ６ may be bonded to each other to form a monocyclic or polycyclic ring. When m is 2 or more, one of R １ to R ６ in one ligand and one of R １ to R ６ in another ligand may be linked, and R １ to each other, R ２ to each other, R ３ to each other, R ４ to each other, R ５ each other, R ６ may be the same or different from each other, n is a number that satisfies the valence of M, X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group. When n is 2 or more, the plurality of groups represented by X may be the same or different from each other, and X may be bonded to each other to form a monocyclic or polycyclic ring). Claim 12 The method for producing a cyclic olefin copolymer according to any one of claims 1 to 11, wherein the organoaluminum compound (E) contains an organoaluminum oxy compound. Claim 13 The method for producing a cyclic olefin copolymer according to any one of claims 1 to 12, wherein the number average molecular weight Mn of the cyclic olefin copolymer is 3,000 or more and 16,000 or less. Claim 14 The method for producing a cyclic olefin copolymer according to any one of claims 1 to 13, wherein Mw / Mn, which is the ratio of the number average molecular weight Mn to the weight average molecular weight Mw of the cyclic olefin copolymer, is 5.0 or less. Claim 15 A cyclic olefin copolymer obtained by the method for producing a cyclic olefin copolymer according to any one of claims 1 to 14. Claim 16 A resin composition comprising a cyclic olefin copolymer containing a structural unit derived from α-olefin (A), a structural unit derived from cyclic non-conjugated diene (B), and a structural unit derived from cyclic olefin (C), and a hindered phenol compound (F), wherein the number average molecular weight Mn of the cyclic olefin copolymer is 3,000 or more and 16,000 or less, and when the content of the cyclic olefin copolymer is 100 parts by mass, the content of the hindered phenol compound (F) is 0.010 parts by mass or more and 0.50 parts by mass or less. Claim 17 The resin composition according to claim 16, wherein Mw / Mn, which is the ratio of the number average molecular weight Mn to the weight average molecular weight Mw of the cyclic olefin copolymer, is 5.0 or less.

18. The resin composition according to claim 16 or 17, further comprising an organic solvent.

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