Cyclic olefin-based copolymer, resin composition, molded body, film, sheet, antenna, and method for manufacturing cyclic olefin-based copolymer

Abstract

To provide: a cyclic olefin-based copolymer capable of improving a performance balance of folding resistance and heat resistance; and a method for manufacturing the cyclic olefin-based copolymer.SOLUTION: A cyclic olefin-based copolymer has a glass transition point of 120°C or above and lower than 170°C, and has a weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography of 1,000,000 or more.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a cyclic olefin copolymer, a resin composition, a molded article, a film, a sheet and an antenna, and a method for producing a cyclic olefin copolymer.

Background Art

[0002] A cyclic olefin copolymer (copolymer) obtained by copolymerizing an α-olefin and a cyclic olefin is a synthetic resin having excellent transparency and a well-balanced combination of low birefringence, heat resistance, heat aging resistance, chemical resistance, solvent resistance, rigidity, low dielectric properties, etc. Therefore, films and sheets made from resin compositions containing cyclic olefin copolymers are widely used in the field of optical materials such as optical memory disks and optical fibers and exhibit excellent performance.

[0003] Examples of such resin compositions containing cyclic olefin copolymers include the inventions described in Patent Documents 1 and 2.

[0004] Patent Document 1 discloses a cyclic olefin-based resin [A] (1) derived from a cyclic olefin having a specific structure, (2) having a softening point temperature (TMA) of 70 ° C or higher, and (3) having an intrinsic viscosity [η] (in decalin at 135 ° C) of 0.05 to 10 dl / g, and a rubber [B] having a rubber hardness defined by JISA of 98 or less. When the refractive index of the cyclic olefin-based resin [A] is n D [A] and the refractive index of the rubber [B] is n D [B], the difference in refractive index |n D [B] - n D [A]| is 0.015 or less, and the cyclic olefin-based resin composition is characterized by containing the rubber [B] in an amount of 0.01 to 10 parts by weight with respect to 100 parts by weight of the cyclic olefin-based resin [A]. According to the cyclic olefin resin composition of Patent Document 1, it is described that it is excellent in transparency, low birefringence, heat resistance, heat aging resistance, chemical resistance, solvent resistance, etc., and can stably maintain excellent transparency even under environmental changes.

[0005] Further, Patent Document 2 discloses a cyclic olefin copolymer obtained from (A) a linear or branched α-olefin having 2 to 20 carbon atoms, (B) a cyclic olefin represented by a specific formula, and (C) an aromatic vinyl compound, having an intrinsic viscosity [η] in the range of 0.1 to 10 dl / g, wherein the content ratio of the structural unit derived from the linear or branched α-olefin (A) is in the range of 30 to 89 mol%, the content ratio of the structural unit derived from the cyclic olefin (B) is in the range of 10 to 70 mol%, the content ratio of the structural unit derived from the aromatic vinyl compound (C) is in the range of 0.1 to 35 mol%, and the content ratio of the structural unit derived from the cyclic olefin (B) (B (mol%)) and the content ratio of the structural unit derived from the aromatic vinyl compound (C) (C (mol%)) satisfy the relationship represented by 0.5×B≧C≧0.01×B. According to the cyclic olefin copolymer of Patent Document 2, it is described that a cyclic olefin copolymer having high heat resistance, high transparency, and low birefringence can be provided.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0007] The present invention provides a cyclic olefin copolymer capable of improving the performance balance of folding resistance and heat resistance, and a method for producing the same. [Means for Solving the Problems]

[0008] [1] It has a glass transition point of 120°C or higher and less than 170°C, and has a weight average molecular weight (Mw) of 1,000,000 or more measured as a polystyrene equivalent value by gel permeation chromatography, A cyclic olefin copolymer. [2] The cyclic olefin copolymer is composed of at least one constitutional unit (a) derived from an olefin represented by the following general formula (Ia), and at least one constitutional unit selected from the group consisting of constitutional unit (b) and constitutional unit (c), The constitutional unit (b) includes at least one constitutional unit selected from the group consisting of a constitutional unit derived from a cyclic olefin monomer (AA) represented by the following general formula (IIa), a constitutional unit derived from a cyclic olefin monomer (AB) represented by the following general formula (IIIa), and a constitutional unit derived from a cyclic olefin monomer (AC) represented by the following general formula (IVa), The constitutional unit (c) includes at least one constitutional unit selected from the group consisting of a constitutional unit derived from a cyclic olefin monomer represented by the following general formula (C-1), a constitutional unit derived from a cyclic olefin monomer represented by the following general formula (C-2), and a constitutional unit derived from a cyclic olefin monomer represented by the following general formula (C-3). The cyclic olefin copolymer according to [1] above. [Chemical Formula] (In the general formula (Ia), R 300 represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms) [Chemical Formula] (In the general formula (IIa), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, R 61 ~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. R 75 ~R 78 may be bonded to each other to form a monocyclic or polycyclic ring)

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[10] having a glass transition point of 120 °C or higher and less than 170 °C, A method for producing a cyclic olefin copolymer having a weight average molecular weight (Mw) of 1,000,000 or more as measured in terms of polystyrene by gel permeation chromatography, wherein the production method comprises at least one olefin represented by the following general formula (Ia), and at least one cyclic olefin monomer selected from the group consisting of a cyclic olefin monomer (AA) represented by the following general formula (IIa), a cyclic olefin monomer (AB) represented by the following general formula (IIIa), and a cyclic olefin monomer (AC) represented by the following general formula (IVa), and / or at least one cyclic olefin monomer selected from the group consisting of a cyclic olefin monomer represented by the following general formula (C-1), a cyclic olefin monomer represented by the following general formula (C-2), and a cyclic olefin monomer represented by the following general formula (C-3), and copolymerizing them. [Chemical formula] (In the general formula (Ia), R 300 represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms) [Chemical formula] (In the general formula (IIa), 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, R 75 ~R 78may be combined with each other to form a monocyclic or polycyclic ring)

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[11] The step of copolymerizing is (A) a transition metal compound represented by the following general formula [A] and (B) (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) a compound that reacts with the transition metal compound to form an ion pair in the presence of an olefin polymerization catalyst comprising at least one compound selected from the group consisting of and is carried out to produce the cyclic olefin-based copolymer according to

[10] above.

Chemical formula

[12] The cyclic olefin monomer is At least one cyclic olefin monomer selected from the group consisting of the cyclic olefin monomer (AA), the cyclic olefin monomer (AB), and the cyclic olefin monomer (AC), and At least one cyclic olefin monomer selected from the group consisting of the cyclic olefin monomer represented by the general formula (C-1), the cyclic olefin monomer represented by the general formula (C-2), and the cyclic olefin monomer represented by the general formula (C-3) A method for producing the cyclic olefin copolymer according to

[10] or

[11] , comprising any one of the cyclic olefin monomers.

Advantages of the Invention

[0009] According to the present invention, a cyclic olefin copolymer capable of improving the performance balance between folding resistance and heat resistance, and a method for producing the same can be provided.

Embodiments for Carrying Out the Invention

[0010] In this embodiment, "A to B" indicating a numerical range represents A or more and B or less unless otherwise specified. In addition, in this embodiment, when a group such as an alkyl group "has a substituent", unless otherwise specified, it means that a hydrogen atom present in its structure is substituted with a substituent. The position and number of substituents are not particularly limited. When the substituent has a carbon atom, the number of carbon atoms of the substituent is not included in the number of carbon atoms of the group having the substituent. For example, in the case of an ethyl group having a phenyl group as a substituent, it is regarded as an alkyl group having 2 carbon atoms. Furthermore, various monomers in the present invention may be derived from fossil raw materials, may be derived from organisms such as biomass, or may be a mixture thereof. Furthermore, the description of "A and / or B" is a concept including either one of A and B and both A and B.

[0011] When producing a film or sheet from a resin composition, an extrusion molding method using this resin composition is widely adopted. In this case, since the obtained film is generally recovered by roll winding, sufficient durability against bending (also referred to as fold resistance and toughness) is required. Although it is a cyclic olefin copolymer having various characteristics as described above, in recent years, taking advantage of its heat resistance and low dielectric characteristics, the use of cyclic olefin copolymers as insulating substrate materials for printed circuits and antenna substrates in high-frequency bands has been studied. However, in these applications, cyclic olefin copolymers having even better fold resistance than conventional cyclic olefin copolymers are required.

[0012] As one means for improving the fold resistance of cyclic olefin copolymers, the inventor considered lowering the glass transition temperature (Tg) of cyclic olefin copolymers. However, according to the inventor's study, it was found that lowering the glass transition temperature (Tg) may reduce the heat resistance of cyclic olefin copolymers. That is, the inventor found that there is a trade-off relationship between the fold resistance and heat resistance of cyclic olefin copolymers. As a further study by the inventor, it was first found that by setting the glass transition temperature (Tg) and weight average molecular weight (Mw) of cyclic olefin copolymers within predetermined numerical ranges, the performance balance of the fold resistance and heat resistance of cyclic olefin copolymers can be improved, and the present invention was completed.

[0013] <Cyclic olefin copolymer> The cyclic olefin copolymer of this embodiment has a glass transition temperature of 120°C or higher and less than 170°C, and the weight average molecular weight (Mw) measured as a polystyrene equivalent value by gel permeation chromatography is 1,000,000 or higher.

[0014] [Glass transition temperature] The cyclic olefin copolymer of the present embodiment has a glass transition temperature (Tg) of 120°C or higher and lower than 170°C. From the viewpoint of further improving heat resistance, the Tg of the cyclic olefin copolymer is preferably 125°C or higher, more preferably 127°C or higher, still more preferably 130°C or higher, still more preferably 132°C or higher, still more preferably 135°C or higher, and from the viewpoint of further improving folding resistance, it is preferably 168°C or lower, more preferably 165°C or lower, still more preferably 162°C or lower, still more preferably 160°C or lower. The Tg of the cyclic olefin copolymer is preferably 125°C or higher and 168°C or lower, more preferably 127°C or higher and 165°C or lower, still more preferably 130°C or higher and 162°C or lower, still more preferably 132°C or higher and 160°C or lower, still more preferably 135°C or higher and 160°C or lower, from the viewpoint of further improving the performance balance between heat resistance and folding resistance. The Tg of the cyclic olefin copolymer can be adjusted by changing various conditions related to polymerization, such as the types and content ratios of the monomers constituting the copolymer and the type of polymerization catalyst.

[0015] [Molecular weight] (Weight average molecular weight) The cyclic olefin copolymer of the present embodiment has a weight average molecular weight (Mw) measured as a polystyrene equivalent value by gel permeation chromatography (GPC) of 1,000,000 or more. From the viewpoint of further improving heat resistance, the Mw of the cyclic olefin copolymer is preferably 1,250,000 or more, more preferably 1,500,000 or more, still more preferably 2,000,000 or more, still more preferably 2,500,000 or more, still more preferably 3,000,000 or more, still more preferably 3,500,000 or more, and the upper limit is not particularly limited, but for example, it is 10,000,000 or less, preferably 7,000,000 or less, more preferably 6,000,000 or less. From the viewpoint of further improving heat resistance, the Mw of the cyclic olefin copolymer is preferably 1,250,000 or more and 10,000,000 or less, more preferably 1,500,000 or more and 7,000,000 or less, still more preferably 2,000,000 or more and 7,000,000 or less, still more preferably 2,500,000 or more and 7,000,000 or less, still more preferably 3,000,000 or more and 7,000,000 or less, still more preferably 3,500,000 or more and 6,000,000 or less. The Mw of the cyclic olefin copolymer can be adjusted by changing various conditions related to polymerization such as the types and content ratios of the monomers constituting the copolymer and the type of polymerization catalyst.

[0016] (Number average molecular weight) The cyclic olefin copolymer of the present embodiment preferably has a number average molecular weight (Mn) measured as a polystyrene equivalent value by GPC of 250,000 to 5,000,000, more preferably 500,000 to 2,500,000. When Mn is within the said numerical range, moldability becomes favorable. The Mn of the cyclic olefin copolymer can be adjusted by changing various conditions related to polymerization such as the types and content ratios of the monomers constituting the copolymer and the type of polymerization catalyst.

[0017] (Molecular weight distribution) The cyclic olefin copolymer of the present embodiment preferably has a molecular weight distribution (Mw / Mn), which is the value obtained by dividing the above Mw by the above Mn, in the range of 1.50 to 8.00, more preferably in the range of 2.00 to 7.00, and even more preferably in the range of 2.50 to 7.00. When Mw / Mn is within the above numerical range, the moldability becomes good.

[0018] The cyclic olefin copolymer of the present embodiment preferably contains at least one constitutional unit (a) derived from at least one olefin represented by the following general formula (Ia), and at least one constitutional unit selected from the group consisting of constitutional unit (b) and constitutional unit (c). Constitutional unit (b) contains at least one constitutional unit selected from the group consisting of a constitutional unit derived from a cyclic olefin monomer (AA) represented by the general formula (IIa), a constitutional unit derived from a cyclic olefin monomer (AB) represented by the general formula (IIIa), and a constitutional unit derived from a cyclic olefin monomer (AC) represented by the general formula (IVa). Constitutional unit (c) contains at least one constitutional unit selected from the group consisting of a constitutional unit derived from a cyclic olefin monomer represented by the general formula (C-1), a constitutional unit derived from a cyclic olefin monomer represented by the general formula (C-2), and a constitutional unit derived from a cyclic olefin monomer represented by the general formula (C-3).

[0019] The cyclic olefin copolymer of the present embodiment more preferably contains constitutional unit (a) and any one constitutional unit selected from the group consisting of constitutional unit (b) and constitutional unit (c), and even more preferably contains constitutional unit (a) and constitutional unit (b). When the cyclic olefin copolymer has the above composition, the balance between the folding resistance and the heat resistance tends to be better. Hereinafter, each constitutional unit will be described in detail.

[0020] [Constitutional unit (a)] Constitutional unit (a) is a constitutional unit derived from at least one olefin represented by the following general formula (Ia).

[0021]

Chem.

[0022] In the general formula (Ia) above, R 300 represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms. The structural unit represented by the following general formula (I) corresponds to the olefin monomer represented by the general formula (Ia) above. That is, the olefin monomer represented by the general formula (Ia) undergoes addition polymerization to form a structural unit represented by the following general formula (I).

[0023]

Chem.

[0024] In the general formula (I) above, R 300 represents the same group as R 300 in the general formula (Ia) above.

[0025] Examples of the olefin represented by the general formula (Ia) above include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. Among these, from the viewpoint of further improving the performance balance of light transmittance and heat and humidity resistance, it preferably contains at least one selected from the group consisting of ethylene and propylene, and more preferably contains ethylene. Two or more kinds of the olefin monomers represented by the general formula (Ia) above may be used.

[0026] When the content of the constitutional unit (a) in the cyclic olefin copolymer of the present embodiment is based on 100 mol% of the content of all constitutional units in the cyclic olefin copolymer, it is preferably 40.0 mol% or more, more preferably 45.0 mol% or more, still more preferably 50.0 mol% or more, and preferably 80.0 mol% or less, more preferably 75.0 mol% or less. When the content of the constitutional unit (a) in the cyclic olefin copolymer of the present embodiment is based on 100 mol% of the content of all constitutional units in the cyclic olefin copolymer, it is preferably 40.0 mol% or more and 80.0 mol% or less, more preferably 45.0 mol% or more and 80.0 mol% or less, still more preferably 50.0 mol% or more and 75.0 mol% or less. When the content of the constitutional unit (a) in the cyclic olefin copolymer is within the above range, the moldability of the cyclic olefin copolymer becomes good. When the cyclic olefin copolymer of the present embodiment contains the constitutional units (a) and (b), the content of the constitutional unit (a) in the cyclic olefin copolymer is preferably 60.0 mol% or more, more preferably 63.0 mol% or more, and preferably 73.0 mol% or less, more preferably 70.0 mol% or less when the content of all constitutional units in the cyclic olefin copolymer is 100 mol%. When the cyclic olefin copolymer of the present embodiment contains the constitutional units (a) and (c), the content of the constitutional unit (a) in the cyclic olefin copolymer is preferably 50.0 mol% or more, more preferably 60.0 mol% or more, and preferably 68.0 mol% or less, more preferably 65.0 mol% or less when the content of all constitutional units in the cyclic olefin copolymer is 100 mol%. When the cyclic olefin copolymer of the present embodiment contains the constitutional units (a), (b) and (c), the content of the constitutional unit (a) in the cyclic olefin copolymer is preferably 55.0 mol% or more, more preferably 58.0 mol% or more, and preferably 65.0 mol% or less, more preferably 62.0 mol% or less when the content of all constitutional units in the cyclic olefin copolymer is 100 mol%.

[0027] [Constituent unit (b)] The constituent unit (b) contains at least one kind of constituent unit selected from the group consisting of a constituent unit derived from a cyclic olefin monomer (AA) represented by the general formula (IIa), a constituent unit derived from a cyclic olefin monomer (AB) represented by the general formula (IIIa), and a constituent unit derived from a cyclic olefin monomer (AC) represented by the general formula (IVa). Preferably, it contains at least one kind of constituent unit selected from the group consisting of a constituent unit derived from a cyclic olefin monomer (AA) represented by the general formula (IIa) and a constituent unit derived from a cyclic olefin monomer (AB) represented by the general formula (IIIa). More preferably, it contains a constituent unit derived from a cyclic olefin monomer (AA) represented by the general formula (IIa). Hereinafter, each cyclic olefin monomer will be described in detail.

[0028] (Cyclic olefin monomer (AA)) The cyclic olefin monomer (AA) is represented by the following general formula (IIa).

[0029] [Chemical formula]

[0030] In the above general formula (IIa), 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 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 78They may be combined with each other to form a monocyclic or polycyclic ring.

[0031] Specifically, examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, and an octadecyl group; examples of the halogenated alkyl group having 1 to 20 carbon atoms include halogenated products of the groups listed as the alkyl group having 1 to 20 carbon atoms; examples of the cycloalkyl group having 3 to 15 carbon atoms include a cyclohexyl group; and examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms include aryl groups such as a phenyl group, a tolyl group, a naphthyl group, a benzyl group, and a phenylethyl group, and aralkyl groups.

[0032] Specific examples of the cyclic olefin monomer represented by the general formula (IIa) include the compounds described in paragraphs 0037 to 0063 of International Publication No. 2006 / 118261. Further, the cyclic olefin monomer can be obtained, for example, from dicyclopentadiene and ethylene. As the ethylene, a structural unit derived from a biomass-derived monomer (ethylene) may be included.

[0033] The cyclic olefin monomer represented by the general formula (IIa) is preferably at least one selected from the group consisting of bicyclo[2.2.1]-2-heptene (also called norbornene) and tetracyclo[4.4.0.1 2,5 .1 7,10 -3-dodecene (also called tetracyclododecene), and more preferably includes tetracyclododecene. Since these cyclic olefin monomers have a rigid ring structure, the elastic modulus of the cyclic olefin copolymer and the molded article is likely to be maintained. Two or more kinds of the cyclic olefin monomers represented by the general formula (IIa) may be used.

[0034] The structural unit represented by the following general formula (II) corresponds to the cyclic olefin monomer represented by the above general formula (IIa). That is, the cyclic olefin monomer represented by the above general formula (IIa) undergoes addition polymerization to form a structural unit represented by the following general formula (II).

[0035] [Chemical formula]

[0036] In the above general formula (II), u, v, w, R 61 ~R 78 as well as R a1 and R b1 may represent the same groups or values as u, v, w, R 61 ~R 78 as well as R a1 and R b1 in the above general formula (IIa).

[0037] (Cyclic olefin monomer (AB)) The cyclic olefin monomer (AB) is represented by the following general formula (IIIa).

[0038] [Chemical formula]

[0039] In the above general formula (IIIa), x and d are each independently 0 or an integer of 1 or more, preferably an integer of 0 or more and 2 or less, more preferably 0 or 1, y and z are each independently 0, 1 or 2, R 81 ~R 99 may be the same as or different from each other, and are a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group which is an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms or an alkoxy group, R 89 and R 90 the carbon atom to which they are attached, and R93 The carbon atom to which it is bonded or R 91 The carbon atom to which it is bonded may be bonded directly or via an alkylene group having 1 to 3 carbon atoms, Also, when y = z = 0, R 95 and R 92 or R 95 and R 99 and R may be bonded to each other to form a monocyclic or polycyclic aromatic ring.

[0040] Specifically, examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, and an octadecyl group; examples of the cycloalkyl group having 3 to 15 carbon atoms include a cyclohexyl group; examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms include aryl groups such as a phenyl group, a tolyl group, a naphthyl group, a benzyl group, and a phenylethyl group, and aralkyl groups; examples of the alkoxy group include a methoxy group, an ethoxy group, and a propyloxy group.

[0041] Specific examples of the cyclic olefin monomer represented by the general formula (IIIa) include the compounds described in paragraphs 0037 to 0063 of International Publication No. 2006 / 118261. Two or more kinds of the cyclic olefin monomer represented by the general formula (IIIa) may be used.

[0042] The cyclic olefin monomer represented by the general formula (IIIa) corresponds to the structural unit represented by the following general formula (III). That is, the cyclic olefin monomer represented by the general formula (IIIa) undergoes addition polymerization to form a structural unit represented by the following general formula (III).

[0043]

Chemical formula

[0044] In the general formula (III) above, x, d, y, z, R 81 ~R99 may represent the same groups or values as x, d, y, z, and R in the general formula (IIIa) above. 81 ~R 99 and so on.

[0045] (Cyclic olefin monomer (AC)) The cyclic olefin monomer (AC) is represented by the following general formula (IVa).

[0046] [Chemical formula]

[0047] In the general formula (IVa) above, R 100 and R 101 may be the same as or different from each other, and represent a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and f satisfies 1 ≤ f ≤ 18.

[0048] Specifically, examples of the hydrocarbon group having 1 to 5 carbon atoms include a methyl group, an ethyl group, a propyl group, and an isopropyl group.

[0049] Specific examples of the cyclic olefin monomer represented by the general formula (IVa) include the compounds described in paragraphs 0037 to 0063 of WO 2006 / 118261. Two or more kinds of the olefin monomers represented by the general formula (IVa) may be used.

[0050] The constitutional unit represented by the following general formula (IV) corresponds to the cyclic olefin monomer represented by the general formula (IVa) above. That is, the cyclic olefin monomer represented by the general formula (IVa) undergoes addition polymerization to form a constitutional unit represented by the following general formula (IV).

[0051] [Chemical formula]

[0052] In the general formula (IV) above, R 100 and R101 and f is R in the general formula (IVa) above 100 and R 101 and may represent a group or value similar to f.

[0053] When the cyclic olefin copolymer contains the structural units (a) and (b), the content of the structural unit (b) in the cyclic olefin copolymer is preferably 25.0 mol% or more, more preferably 30.0 mol% or more, and 45.0 mol% or less, more preferably 40.0 mol% or less, when the content of all the structural units in the cyclic olefin copolymer is 100 mol%. When the cyclic olefin copolymer contains the structural units (a), (b) and (c), the content of the structural unit (b) in the cyclic olefin copolymer is preferably 18.0 mol% or more, more preferably 20.0 mol% or more, and 25.0 mol% or less, more preferably 23.0 mol% or less, when the content of all the structural units in the cyclic olefin copolymer is 100 mol%. When the content of the structural unit (b) in the cyclic olefin copolymer is within the above range, the moldability of the cyclic olefin copolymer can be improved, and the mechanical strength of the molded article can be enhanced.

[0054] [Structural unit (c)] The structural unit (c) contains at least one structural unit selected from the group consisting of a structural unit derived from a cyclic olefin monomer represented by the general formula (C-1), a structural unit derived from a cyclic olefin monomer represented by the general formula (C-2), and a structural unit derived from a cyclic olefin monomer represented by the general formula (C-3), preferably at least one structural unit selected from the group consisting of a structural unit derived from a cyclic olefin monomer represented by the following general formula (C-1) and a structural unit derived from a cyclic olefin monomer represented by the following general formula (C-3), and more preferably contains a structural unit derived from a cyclic olefin monomer represented by the following general formula (C-3). Hereinafter, each cyclic olefin monomer will be described in detail.

[0055] (Cyclic olefin monomer represented by general formula (C-1))

[0056]

Chemical formula

[0057] In the above general formula (C-1), n and q are each independently 0, 1, or 2, n is preferably 0 or 1, more preferably 0, q is preferably 0 or 1, more preferably 0, R 1 ~R 17 are each independently a hydrogen atom, a halogen atom excluding a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom excluding a fluorine atom, R 10 ~R 17 One of them is a bond, and it is preferable that R 15 is a bond, and R 1 ~R 17 are each independently preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrogen atom, When q = 0, R 10 and R 11 、R 11 and R 12 、R 12 and R 13 、R 13 and R 14 、R 14 and R 15 、R 15 and R 10 may be bonded to each other to form a monocyclic or polycyclic ring, When q = 1 or 2, R 10 and R 11 、R 11 and R 17 、R 17 and R 17 、R 17 and R 12 、R 12 and R 13 、R 13 and R 14, R 14 and R 15 , R 15 and R 16 , R 16 and R 16 , R 16 and R 10 may be bonded to each other to form a monocyclic or polycyclic ring, the above monocyclic or polycyclic ring may have a double bond, the above monocyclic or polycyclic ring may be an aromatic ring.

[0058] Examples of the hydrocarbon group having 1 to 20 carbon atoms include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, amyl group, hexyl group, octyl group, decyl group, dodecyl group and octadecyl group; cycloalkyl groups such as cyclohexyl group; aryl groups such as phenyl group, tolyl group, naphthyl group, benzyl group and phenylethyl group, and aromatic hydrocarbon groups such as aralkyl group; and the like. These groups may be substituted with halogen atoms excluding fluorine atoms.

[0059] Two or more kinds of the cyclic olefin monomer represented by the general formula (C-1) may be used.

[0060] Among the above general formula (C-1), the cyclic olefin monomer represented by the following general formula (C-1A) is preferable. Each substituent of the general formula (C-1A) is the same as the definition of the above general formula (C-1).

[0061] [Chemical formula]

[0062] (Cyclic olefin monomer represented by the general formula (C-2))

[0063] [Chemical formula]

[0064] In the above general formula (C-2), n and m are each independently 0, 1, or 2, q is 1, 2, or 3, m is preferably 0 or 1, more preferably 1, n is preferably 0 or 1, more preferably 0, q is preferably 1 or 2, more preferably 1, R 18 ~R 31 are each independently a hydrogen atom, a halogen atom excluding a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom excluding a fluorine atom, R 18 ~R 31 are each independently preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrogen atom, When q = 1, R 28 and R 29 、R 29 and R 30 、R 30 and R 31 may be bonded to each other to form a monocyclic or polycyclic ring, When q = 2 or 3, R 28 and R 28 、R 28 and R 29 、R 29 and R 30 、R 30 and R 31 、R 31 and R 31 may be bonded to each other to form a monocyclic or polycyclic ring, The above monocyclic or polycyclic ring may be an aromatic ring.

[0065] Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, and an octadecyl group; examples of the cycloalkyl group having 3 to 15 carbon atoms among the hydrocarbon groups having 1 to 20 carbon atoms include a cyclohexyl group; examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms among the hydrocarbon groups having 1 to 20 carbon atoms include aryl groups such as a phenyl group, a tolyl group, a naphthyl group, a benzyl group, and a phenylethyl group, and aralkyl groups. These groups may be substituted with halogen atoms other than fluorine atoms.

[0066] Two or more cyclic olefin monomers represented by the general formula (C-2) may be used.

[0067] (Cyclic olefin monomer represented by the general formula (C-3))

[0068]

Chemical formula

[0069] In the general formula (C-3), q is 1, 2, or 3, preferably 1 or 2, more preferably 1, R 32 ~R 39 are each independently a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom other than a fluorine atom, and R 32 ~R 39 are each independently preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrogen atom, When q = 1, R 36 and R 37 , R 37 and R 38 , R 38 and R 39 may be bonded to each other to form a monocyclic or polycyclic ring, When q = 2 or 3, R 36 and R 36 , R 36 and R 37 , R 37 and R 38 , R 38 and R 39 , R 39 and R 39 may be bonded to each other to form a monocyclic or polycyclic ring, The above monocyclic or polycyclic ring may have a double bond, The above monocyclic or polycyclic ring may be an aromatic ring.

[0070] Examples of the hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, and an octadecyl group; examples of the cycloalkyl group having 3 to 15 carbon atoms among the hydrocarbon groups having 1 to 20 carbon atoms include a cyclohexyl group; and examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms among the hydrocarbon groups having 1 to 20 carbon atoms include aryl groups such as a phenyl group, a tolyl group, a naphthyl group, a benzyl group, and a phenylethyl group, and aralkyl groups. These groups may be substituted with halogen atoms excluding fluorine atoms.

[0071] Two or more kinds of the cyclic olefin monomer represented by the general formula (C-3) may be used.

[0072] The structural unit (c) preferably contains a structural unit derived from at least one compound selected from the group consisting of methylphenylnorbornene, indenonorbornene, and benzonorbornadiene, and more preferably contains a structural unit derived from benzonorbornadiene.

[0073] When the cyclic olefin copolymer contains the structural units (a) and (c), the content of the structural unit (c) in the cyclic olefin copolymer is preferably 30.0 mol% or more, more preferably 35.0 mol% or more, and 45.0 mol% or less, more preferably 40.0 mol% or less, based on 100 mol% of the total content of all the structural units in the cyclic olefin copolymer. When the cyclic olefin copolymer contains the structural units (a), (b), and (c), the content of the structural unit (c) in the cyclic olefin copolymer is preferably 10.0 mol% or more, more preferably 15.0 mol% or more, and preferably 25.0 mol% or less, more preferably 20.0 mol% or less, based on 100 mol% of the total content of all the structural units in the cyclic olefin copolymer. When the content of the constitutional unit (c) in the cyclic olefin copolymer is within the above range, the moldability of the cyclic olefin copolymer can be improved, and the mechanical strength of the molded article can be enhanced.

[0074] When the total content of the constitutional units (a), (b), and (c) in the cyclic olefin copolymer of the present embodiment is 100 mol% based on the content of all the constitutional units in the cyclic olefin copolymer, it is preferably 90 mol% or more, more preferably 95 mol% or more, still more preferably 97 mol% or more, and preferably 100 mol% or less. However, within a range that does not interfere with the effects of the present invention, it may contain constitutional units derived from other monomer components that do not fall under any of the constitutional units (a), (b), and (c).

[0075] [Flexural resistance] The number of bending times of the cyclic olefin copolymer of the present embodiment is preferably 25 times or more, more preferably 26 times or more, still more preferably 27 times or more, still more preferably 28 times or more, still more preferably 29 times or more, still more preferably 30 times or more. And the upper limit is not particularly limited. For example, it may be 80 times or less, or may be 70 times or less. Here, the number of bending times of the cyclic olefin copolymer means a value measured in accordance with JIS P 8115 using a 0.1 mm thick sheet made of the cyclic olefin copolymer as a measurement sample. The 0.1 mm thick sheet made of the cyclic olefin copolymer can be produced, for example, by the method described in the examples. Specifically, it can be produced by sandwiching the cyclic olefin copolymer between films and performing vacuum press molding using a 0.10 mm spacer.

[0076] [Heat resistance] The elongation rate after the heat resistance test of the cyclic olefin copolymer of the present embodiment is preferably 5% or less, more preferably 4% or less, still more preferably 3% or less, still more preferably 2% or less, still more preferably 1% or less, and preferably 0% or more. The elongation rate after the heat resistance test of the cyclic olefin copolymer of the present embodiment means the value measured by the method described in the examples.

[0077] <Resin composition> The resin composition of the present embodiment contains the cyclic olefin copolymer of the present embodiment. The content of the cyclic olefin copolymer in the resin composition of the present embodiment is preferably 80% by mass or more, more preferably 95% by mass or more, and preferably 100% by mass or less from the viewpoint of improving moldability and transparency when the total content of all components in the resin composition is 100% by mass.

[0078] (Other components) The resin composition of the present embodiment can contain additives known as optional components within a range that does not impair the good physical properties of the resin composition of the present embodiment, in addition to the cyclic olefin copolymer. Examples of the additives include antioxidants, secondary antioxidants, lubricants, mold release agents, antifogging agents, weather stabilizers, light stabilizers, ultraviolet absorbers, antistatic agents, metal deactivators, and the like.

[0079] <Molded article> Next, the molded article of the present embodiment will be described. The molded article of the present embodiment contains the cyclic olefin copolymer of the present embodiment. Since the molded article of the present embodiment contains the cyclic olefin copolymer of the present embodiment, heat resistance and fold resistance can be achieved at the same time. Therefore, it can be suitably used as an antenna that can withstand use in various installation environments and requires low dielectric characteristics, transparency, and fold resistance. Specific examples of the antenna will be described later.

[0080] The method for obtaining the molded article of the present embodiment is not particularly limited, and a resin composition containing a cyclic olefin copolymer may be molded by a known method. Depending on its use and shape, for example, extrusion molding, injection molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, vacuum molding, powder slush molding, calendar molding, foam molding, etc. are applicable. Among these, from the viewpoints of moldability and productivity, the injection molding method is preferred. Also, the molding conditions are appropriately selected according to the purpose of use or the molding method. For example, the resin temperature in injection molding is appropriately selected within the range of, for example, 150°C to 400°C, preferably 200°C to 350°C, more preferably 230°C to 330°C.

[0081] <Film, sheet> The film or sheet of the present embodiment contains the cyclic olefin copolymer of the present embodiment. The film or sheet of the present embodiment has heat resistance, transparency, and low moisture absorption, and furthermore, its toughness is improved as shown by high folding strength and elongation at break. Therefore, even when cutting the film or sheet according to various optical film applications, cracks are less likely to occur, and it is suitable for applications of optical films that require durability for various processes. Optical films are suitable for application to optical devices from the viewpoints of transparency, heat resistance, etc. Note that the method for obtaining the film or sheet is not limited to T-die extrusion molding, and molding methods such as injection molding, inflation method, and press method can also be adopted. The film or sheet can be used in an unstretched state, or can be used after being subjected to stretching treatment, for example, uniaxial stretching or biaxial stretching, according to the use and purpose.

[0082] <Antenna> The antenna of the present embodiment contains the molded article of the present embodiment. Also, the antenna of the present embodiment contains the film or sheet of the present embodiment. Since the antenna of this embodiment has low dielectric characteristics, it can be suitably used for various antennas. For example, monopole antennas, dipole antennas, whip antennas, loop antennas, slot antennas, and the like can be mentioned. Examples of the uses of the antenna include WiFi antennas, GPS antennas, terrestrial digital antennas, one-segment and full-segment antennas, RFID antennas, small cell base station antennas, and the like. However, the shape and use of the antenna are not limited to those described above.

[0083] <Manufacturing method> The manufacturing method of the cyclic olefin copolymer of this embodiment is having a glass transition point of 120°C or higher and less than 170°C, a manufacturing method of a cyclic olefin copolymer having a weight average molecular weight (Mw) measured as a polystyrene equivalent value by gel permeation chromatography of 1,000,000 or more, wherein the manufacturing method is at least one olefin represented by the general formula (Ia), at least one cyclic olefin monomer selected from the group consisting of a cyclic olefin monomer (AA) represented by the general formula (IIa), a cyclic olefin monomer (AB) represented by the general formula (IIIa), and a cyclic olefin monomer (AC) represented by the general formula (IVa), and / or at least one cyclic olefin monomer selected from the group consisting of a cyclic olefin monomer represented by the general formula (C-1), a cyclic olefin monomer represented by the general formula (C-2), and a cyclic olefin monomer represented by the general formula (C-3), and a copolymerization step (hereinafter also referred to as the copolymerization step).

[0084] In the copolymerization step of this embodiment, the cyclic olefin monomer is preferably at least one cyclic olefin monomer selected from the group consisting of a cyclic olefin monomer (AA), a cyclic olefin monomer (AB), and a cyclic olefin monomer (AC), and At least one cyclic olefin monomer selected from the group consisting of a cyclic olefin monomer represented by general formula (C-1), a cyclic olefin monomer represented by general formula (C-2), and a cyclic olefin monomer represented by general formula (C-3) contains either one of the cyclic olefin monomers.

[0085] Preferred embodiments of the glass transition temperature, weight average molecular weight (Mw), and other physical property values of the cyclic olefin copolymer obtained by the production method of the present embodiment are the same as the preferred embodiments of the respective physical property values of the cyclic olefin copolymer of the present embodiment. In the production method of the present embodiment, the cyclic olefin monomer (AA) represented by general formula (IIa), the cyclic olefin monomer (AB) represented by general formula (IIIa), the cyclic olefin monomer (AC) represented by general formula (IVa), the cyclic olefin monomer represented by general formula (C-1), the cyclic olefin monomer represented by general formula (C-2), and the cyclic olefin monomer represented by general formula (C-3) are respectively the cyclic olefin monomer (AA) represented by general formula (IIa), the cyclic olefin monomer (AB) represented by general formula (IIIa), the cyclic olefin monomer (AC) represented by general formula (IVa), the cyclic olefin monomer represented by general formula (C-1), the cyclic olefin monomer represented by general formula (C-2), and the cyclic olefin monomer represented by general formula (C-3) in the cyclic olefin copolymer of the present embodiment, and are the same.

[0086] In the production method of the present embodiment, the cyclic olefin copolymer can be obtained, for example, by polymerizing the above cyclic olefin monomer and other monomers in the presence of a suitably known polymerization catalyst. The polymerization temperature, polymerization pressure, polymerization time, etc. are adjusted as appropriate. The polymerization catalyst used in the production method of the present invention, and polymerization conditions such as polymerization temperature, polymerization pressure, and polymerization time are, for example, in the case of cyclic olefin copolymers, as described in JP-A-60-168708, JP-A-61-120816, JP-A-61-115912, JP-A-61-115916, JP-A-61-271308, JP-A-61-272216, JP-A-62-252406, JP-A-62-252407, JP-A-2007-314806, JP-A-2010-241932, etc., and can be produced by appropriately selecting conditions according to the methods thereof.

[0087] Among them, the copolymerization step in the production method of the present embodiment is (A) a transition metal compound represented by the general formula [A] described below and (B) (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) a compound that reacts with the transition metal compound to form an ion pair in the presence of an olefin polymerization catalyst containing at least one compound selected from the group consisting of and. This makes it easy to adjust the glass transition point, weight average molecular weight (Mw), and other physical property values of the obtained cyclic olefin copolymer to a preferable range.

[0088] Hereinafter, the transition metal compound (A), the organometallic compound (B-1), the organoaluminum oxy compound (B-2), and the compound (B-3) that reacts with the transition metal compound (A) to form an ion pair will be described respectively.

[0089] The transition metal compound (A) is represented by the following general formula [A].

[0090]

Chemical formula

[0091] 《M》 In formula [A], M is preferably a titanium atom or a zirconium atom, and more preferably a titanium atom.

[0092] 《R 1‘ ~R 8‘ 》 In formula [A], R 1‘ ~R 8‘ are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, or a phosphorus-containing group, R 1‘ ~R 5‘ among which adjacent groups may be bonded to each other to form a ring.

[0093] Examples of the halogen atom include fluorine, chlorine, bromine, and iodine. Examples of the hydrocarbon group include linear or branched alkyl groups having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, and n-hexyl; Linear or branched alkenyl groups having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, such as vinyl, allyl, and isopropenyl; Linear or branched alkynyl groups having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, such as ethynyl and propargyl; Cyclic saturated hydrocarbon groups having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and adamantyl; Cyclic unsaturated hydrocarbon groups having 5 to 20 carbon atoms, such as cyclopentadienyl, indenyl, and fluorenyl; Aryl groups having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, such as phenyl, benzyl, naphthyl, biphenyl, terphenyl, phenanthryl, and anthracenyl; and Alkyl-substituted aryl groups such as tolyl, isopropylphenyl, t-butylphenyl, dimethylphenyl, and di-t-butylphenyl may be mentioned.

[0094] Also, those in which the hydrogen atoms of the exemplified hydrocarbon groups are substituted with hydrocarbon groups, such as aryl group-substituted alkyl groups such as benzyl and cumyl, may be mentioned. R 1‘ ~R 5‘ Examples of the cyclopentadienyl moiety having a ring formed by bonding adjacent groups among R

[0095]

Chemical formula

[0096] With the above structure, the polymerization activity is relatively high, and the molecular weight of the resulting polymer tends to increase. Examples of the halogen-containing group include halogenated hydrocarbon groups having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, such as trifluoromethyl, pentafluorophenyl, and chlorophenyl.

[0097] Examples of the silicon-containing group include a silyl group, a siloxy group, a hydrocarbon-substituted silyl group, and a hydrocarbon-substituted siloxy group. Among these, methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, dimethylphenylsilyl, triphenylsilyl, etc. are preferable. Particularly, trimethylsilyl, triethylsilyl, triphenylsilyl, and dimethylphenylsilyl are preferable. Specific examples of the hydrocarbon-substituted siloxy group include trimethylsiloxy.

[0098] Examples of the oxygen-containing group include 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, and a furyl group.

[0099] Examples of the sulfur-containing group include 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, and a sulfenyl group.

[0100] Examples of the nitrogen-containing group include an amino group, an imino group, an amide group, an imide group, a pyrrolidino 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, and an ammonium salt formed from an amino group.

[0101] Examples of the phosphorus-containing group include a phosphide group, a phosphoryl group, a thiophosphoryl group, and a phosphato group.

[0102] (R 1‘ ~R 5‘ ) R 1‘ ~R 5‘One or more of them are, in particular, linear or branched alkyl groups having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, neopentyl, n-hexyl, etc.; Aryl groups having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, such as phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, anthracenyl, etc.; It is preferable that one or more hydrogen atoms of these aryl groups are hydrocarbon groups having 1 to 20 carbon atoms such as substituted aryl groups in which the hydrogen atom is substituted with a halogen atom, an alkyl group, an alkoxy group, an aryl group or an aryloxy group, etc.

[0103] Also, R 1‘ ~R 5‘ It is also preferable that one or more of them are hydrogen atoms. In this embodiment, the hydrogen atom refers to hydrogen as a substituent represented by H-. Among the above aspects, R 1‘ is a hydrocarbon group having 1 to 20 carbon atoms, and R 2‘ ~R 5‘ are preferably hydrogen atoms. The above-mentioned R 1‘ is particularly preferably selected from a secondary hydrocarbon group and a tertiary hydrocarbon group, and particularly preferably a tertiary hydrocarbon group.

[0104] (R 6‘ ~R 8‘ ) In formula [A], one or more of R 6‘ ~R 8‘ are tertiary hydrocarbon groups. Such a hydrocarbon group is a tertiary hydrocarbon group having 4 to 20 carbon atoms, and specifically, a t-butyl group, a t-pentyl group, a t-hexyl group, an adamantyl group, a 1,1-dimethylbenzyl group, etc. can be mentioned. Of course, the tertiary hydrocarbon group may have a structure containing halogen, silicon, oxygen, nitrogen, sulfur, phosphorus. Preferably, it is a tertiary hydrocarbon group that does not contain the so-called heteroatoms as described above.

[0105] Among the above, R 6‘ and / or R7‘ is preferably a tertiary hydrocarbon group. Also, two or more of them are preferably tertiary hydrocarbons. In particular, R 6‘ and R 7‘ are both preferably tertiary hydrocarbon groups.

[0106] In formula [A], in addition to the above requirements, one or more of R 6‘ ~R 8‘ are preferably substituents selected from aryl groups or substituted aryl groups having 6 to 20 carbon atoms. Specifically, aryl groups having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, such as phenyl, benzyl, naphthyl, biphenyl, terphenyl, phenanthryl, anthracenyl, etc., and the above aryl groups having substituents such as hydrocarbon groups and oxygen-containing groups can be mentioned. Specific examples of the substituents are the same as the above-mentioned hydrocarbon groups and oxygen-containing groups. Among these, as the hydrocarbon group, tertiary hydrocarbon groups such as t-butyl group, t-pentyl group, t-hexyl group, dimethylbenzyl group, etc. are preferable, and as the oxygen-containing group, alkoxy groups such as methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, and tert-butoxy group are preferable. Among the above aryl groups, a substituted aryl group is preferable, and in particular, an aryl group having a tertiary hydrocarbon group is preferable.

[0107] When the above R 6‘ ~R 8‘ include such aryl groups or substituted aryl groups, a copolymer having a high content of constitutional units derived from cyclic olefins may be easily obtained by the copolymerization reaction of olefins and cyclic olefins described later, and the copolymer tends to have a relatively high molecular weight. Therefore, when providing a material having a high glass transition temperature and excellent strength, the above aspect is preferable.

[0108] 《n》 In formula [A], n is an integer of 1 to 4, and is selected so that the whole transition metal compound (A) is electrically neutral according to the valence of M and the type of X.

[0109] 《X》 In formula [A], each X is independently a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group, an aluminum-containing group, or a diene-based divalent derivative group.

[0110] Specific embodiments of these halogen atoms, hydrocarbon groups, halogen-containing groups, silicon-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, and phosphorus-containing groups are the same as the specific embodiments of the halogen atoms, hydrocarbon groups, halogen-containing groups, silicon-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, and phosphorus-containing groups as R 1‘ ~R 5‘ and R 8‘ respectively.

[0111] Examples of the boron-containing group include a borandiyl group, a borantriyl group, a diboranyl group, and groups such as an alkyl group-substituted boron, an aryl group-substituted boron, a boron halide, and an alkyl group-substituted boron halide.

[0112] Examples of the aluminum-containing group include groups such as an alkyl group-substituted aluminum, an aryl group-substituted aluminum, an aluminum halide, and an alkyl group-substituted aluminum halide.

[0113] Examples of the diene-based divalent derivative group include a 1,3-butadienyl group, an isoprenyl (2-methyl-1,3-butadienyl) group, a piperylenyl (1,3-pentadienyl) group, a 2,4-hexadienyl group, a 1,4-diphenyl-1,3-pentadienyl group, a cyclopentadienyl group, and a metallocyclopentene group.

[0114] Also, X may be a structure in which the groups exemplified as specific examples of X are bonded to each other and may form a ring together with M. For example, X may be an alkylene group having a structure in which two alkyl groups are bonded, and this alkylene group may form a ring together with M.

[0115] The transition metal compound represented by the general formula [A] can be produced by combining known methods. For example, it can be produced according to the description in JP-A-2022-155527.

[0116] 《Organometallic Compound (B-1)》 Examples of the organometallic compound (B-1) (hereinafter also referred to as "component (B-1)") include organometallic compounds of Groups 1, 2, 12, and 13 such as the organoaluminum compound (B-1a) represented by the general formula (B-1a), the complex alkylated product (B-1b) of a Group 1 metal and aluminum represented by the general formula (B-1b), and the dialkyl compound (B-1c) of a Group 2 or Group 12 metal represented by the general formula (B-1c).

[0117] (B-1a):R a m Al(OR b ) n H p X q In the formula (B-1a), R a and R b are each independently a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X is a halogen atom, m satisfies 0 < m ≦ 3, n satisfies 0 ≦ n < 3, p satisfies 0 ≦ p < 3, q satisfies 0 ≦ q < 3, and m + n + p + q = 3. Examples of the organoaluminum compound (B-1a) include trialkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, dialkylaluminum hydrides such as diisobutylaluminum hydride, and tricycloalkylaluminum.

[0118] (B-1b):M 2 AlR a 4 In the formula (B-1b), M 2 is Li, Na, or K, and R a is a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. Examples of the complex alkylated product (B-1b) include, for example, LiAl(C 2 H 5 )4 , LiAl(C 7 H 15 ) 4 and the like can be mentioned.

[0119] (B-1c): R a R b M 3 In formula (B-1c), R a and R b are each independently a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and M 3 is Mg, Zn or Cd. Examples of the compound (B-1c) include dimethylmagnesium, diethylmagnesium, di-n-butylmagnesium, ethyl n-butylmagnesium, diphenylmagnesium, dimethylzinc, diethylzinc, di-n-butylzinc, and diphenylzinc.

[0120] Among the organometallic compounds (B-1), organoaluminum compounds (B-1a) are preferred. The organometallic compound (B-1) may be used alone or in combination of two or more.

[0121] 《Organoaluminum Oxy Compound (B-2)》 As the organoaluminum oxy compound (B-2) (hereinafter also referred to as "component (B-2)"), conventionally known aluminoxane can be used as it is. Specifically, the following general formula [B2-1]

[0122]

Chemical formula

[0123]

Chemical formula

[0124] Further, examples of the organoaluminum oxy compound (B-2) include modified methylaluminoxane represented by the following general formula [B2-3].

[0125] [Chemical formula] (In the formula, R represents a hydrocarbon group having 1 to 10 carbon atoms, and m and n each independently represent an integer of 2 or more.)

[0126] This modified methylaluminoxane is prepared using trimethylaluminum and an alkylaluminum other than trimethylaluminum. Such a compound is generally called MMAO. Such MMAO can be prepared by the methods described in U.S. Patent No. 4,960,878 and U.S. Patent No. 5,041,584.

[0127] Furthermore, examples of the organoaluminum oxy compound (B-2) include an organoaluminum oxy compound containing boron represented by the following general formula [B2-4].

[0128] [Chemical formula] (In the formula, R c represents a hydrocarbon group having 1 to 10 carbon atoms. R d may be the same as or different from each other, and represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 10 carbon atoms.)

[0129] As the organoaluminum oxy compound (B-2), methylaluminoxane which is easily available as a commercial product and MMAO prepared using trimethylaluminum and triisobutylaluminum are preferable. Among these, MMAO with improved solubility in various solvents and storage stability is particularly preferable.

[0130] 《Compound (B-3) That Reacts with the Transition Metal Compound (A) to Form an Ion Pair》 Examples of the compound (B-3) that reacts with the transition metal compound (A) to form an ion pair (hereinafter also referred to as "ionic compound (B-3)" or "component (B-3)") include Lewis acids, ionic compounds, borane compounds, and carborane compounds described in JP-T-1-501950, JP-T-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, USP5321106, etc. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned. However, it does not include the aforementioned organoaluminum oxy compound (B-2).

[0131] Preferable examples of the ionic compound (B-3) include boron compounds represented by the following general formula [B3-1].

[0132]

Chemical formula

[0133] In the formula, R e+ includes H + , carbocation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, ferrocenium cation having a transition metal, etc. R f to R i may be the same as or different from each other, and are substituents selected from hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing groups, nitrogen-containing groups, oxygen-containing groups, halogen atoms, and halogen-containing groups, and are preferably substituted aryl groups.

[0134] Examples of the boron compound represented by the general formula [B3-1] include those described in

[0133] to

[0144] of International Publication No. 2015 / 122414. The ionic compound (B-3) may be used alone or in combination of two or more.

[0135] In the copolymerization step of this embodiment, the amount of the transition metal compound (A) is, for example, 10 -12 ~10 -2 mol, preferably 10 -10 ~10 -3 mol per liter of the reaction volume.

[0136] The molar ratio [(B-1) / M] of the organometallic compound (B-1) to all transition metal atoms (M) in the transition metal compound (A) is, for example, 0.01 to 50,000, preferably 0.05 to 10,000.

[0137] The molar ratio [(B-2) / M] of the aluminum atom in the organoaluminum oxy compound (B-2) to all transition metal atoms (M) in the transition metal compound (A) is, for example, 1 to 50,000, preferably 10 to 20,000.

[0138] The molar ratio [(B-3) / M] of the ionized ionic compound (B-3) to all transition metal atoms (M) in the transition metal compound (A) is, for example, 1 to 10,000, preferably 1 to 5,000.

Examples

[0139] Next, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples. In these examples, various physical properties were measured or evaluated by the following methods.

[0140] [Measurement] (Glass transition temperature Tg (°C)) Using a differential scanning calorimeter (manufactured by Shimadzu Corporation, DSC-6220), N 2The glass transition temperature Tg of the cyclic olefin copolymer was measured under a (nitrogen) atmosphere. The cyclic olefin copolymer was heated from room temperature to 250 °C at a heating rate of 10 °C / min, held for 5 minutes, then cooled to -20 °C at a cooling rate of 10 °C / min and held for 5 minutes. Then, the glass transition point (Tg) of the cyclic olefin copolymer was determined from the endothermic curve when heating to 250 °C at a heating rate of 10 °C / min.

[0141] (Content of structural units derived from each monomer of the cyclic olefin copolymer) For the cyclic olefin copolymer of each example, according to the description in paragraph

[0132] of WO2019 / 107363, 13 The content of structural units derived from the monomers constituting the cyclic olefin copolymer was determined by 13C-NMR spectrum.

[0142] (Measurement method of weight average molecular weight and number average molecular weight) For the cyclic olefin copolymer, the measurement methods of weight average molecular weight and number average molecular weight were measured by GPC measurement and obtained as standard polystyrene conversion values. The GPC measurement was carried out under the following conditions. Apparatus: GPC-IR6 MCT type gel permeation chromatograph (manufactured by Polymer Char) Detector: IR6 type MCT detector (manufactured by Polymer Char) Solvent: o-dichlorobenzene (containing 0.025% BHT) Columns: TSKgel MH6-HT × 2, TSKgel GMH6-HTL × 2 (both 7.5 mm I.D. × 30 cm, manufactured by Tosoh Corporation) Flow rate: 1.0 ml / min Sample: 1 mg / mL o-dichlorobenzene solution Injection volume: 400 μL Temperature: 140 °C Column calibration: Monodisperse polystyrene (manufactured by Tosoh Corporation); #4 std set 5th Molecular weight conversion: Polystyrene conversion / standard conversion method

[0143] [Molding] Each of the cyclic olefin copolymers obtained by the polymerization examples described below was sandwiched between films of Yu-pirex (trade name, manufactured by Ube Industries, Ltd.), and using a 0.10 mm spacer, vacuum press molding was carried out under the conditions of 270 °C, 10 MPa, and 12 minutes to obtain a 0.1 mm thick sheet made of a cyclic olefin copolymer. Using the obtained 0.1 mm thick sheet as a sample, the folding resistance and heat resistance were evaluated.

[0144] (Folding resistance, toughness (number of times)) In accordance with JIS P 8115, evaluation was carried out on strip-shaped samples (size: 15 mm × 100 mm) of the 0.1 mm thick sheet using a MIT tester. If the number of bending times at which the strip-shaped sample of the 0.1 mm thick sheet broke was 25 times or more, it was judged that the desired folding resistance was obtained. The folding resistance evaluation was carried out according to the following criteria. A: The number of bending times is 30 times or more B: The number of bending times is 25 times or more and 29 times or less C: The number of bending times is 24 times or less

[0145] (Heat resistance evaluation) A 10 g load was applied to a strip-shaped sample (size: 15 mm × 60 mm) of the 0.1 mm thick sheet in the longitudinal direction for 30 minutes in an oven at 120 °C as a heat resistance test. Evaluation was carried out according to the following criteria based on the elongation rate of the sample after the heat resistance test and the presence or absence of appearance defects. A: The evaluation result of the elongation rate according to the following evaluation criteria is A and there are no appearance defects B: The evaluation result of the elongation rate according to the following evaluation criteria is B or there are appearance defects C: The evaluation result of the elongation rate according to the following evaluation criteria is B and there are appearance defects (Elongation rate evaluation) A: The elongation rate of the sample after the heat resistance test is 0% or more and 5% or less B: The elongation rate of the sample after the heat resistance test exceeds 5% or is less than 0%, or the measurement of the elongation rate is impossible (Appearance evaluation) No appearance defects: When the sample was visually inspected after the heat resistance test, no change that impairs transparency occurred in the sample appearance. Appearance defect: When the sample was visually inspected after the heat resistance test, changes that impaired transparency were observed in the sample appearance.

[0146] [Polymerization Example] [Example 1-1] 300 mL of a cyclohexane / hexane (9 / 1) mixed solution and 52.49 mmol of tetracyclododecene were charged into a 500 mL glass reactor that had been sufficiently purged with nitrogen. The liquid and gas phases were saturated with ethylene at 51 L / hr. Then, 0.10 mmol of triisobutylaluminum in terms of aluminum atoms was added, followed by 0.0005 mmol of 3,5-bis-t-butyl-1-pyrazolate-t-butylcyclopentadienyltitanium dichloride (hereinafter referred to as transition metal compound (A-1)) as a polymerization catalyst and 0.004 mmol of triphenylcarbenium tetrakis(pentafluorophenyl)borate, and polymerization was initiated. Ethylene was continuously supplied at 51 L / hr, and polymerization was carried out at 50 °C for 10 minutes under normal pressure. Then, polymerization was terminated by adding a small amount of methanol. After the polymerization was completed, the reaction product was added to a polymerization solution containing a small amount of hydrochloric acid in a mixed solvent of acetone / methanol (3 / 1) with a four-fold volume to precipitate the polymer. After washing with the same solvent, it was dried under reduced pressure at 130 °C for 10 hours to obtain an ethylene·tetracyclododecene copolymer, which is a cyclic olefin copolymer. The physical property values and the like of the obtained ethylene·tetracyclododecene copolymer are shown in Table 1.

[0147] [Example 1-2] The same operations as in Example 1-1 were carried out except that triisobutylaluminum was changed to 0.20 mmol in terms of aluminum atoms, and an ethylene·tetracyclododecene copolymer, which is a cyclic olefin copolymer, was obtained. The physical property values and the like of the obtained ethylene·tetracyclododecene copolymer are shown in Table 1.

[0148] [Example 1-3] Except that the amounts were changed to 33.75 mmol of tetracyclododecene, 0.30 mmol of triisobutylaluminum in terms of aluminum atoms, and 0.00025 mmol of transition metal compound (A-1), the same operations as in Example 1-1 were carried out to obtain an ethylene-tetracyclododecene copolymer which is a cyclic olefin copolymer. The physical property values, etc. of the obtained ethylene-tetracyclododecene copolymer are shown in Table 1.

[0149] [Comparative Example 1-1] Into a 500 mL glass reactor with sufficient nitrogen substitution, 250 mL of a cyclohexane / hexane (9 / 1) mixed solution and 79.8 mmol of tetracyclododecene were charged, and the liquid phase and gas phase were saturated with ethylene at 51 L / hr and hydrogen at 3 L / hr. Then, 0.30 mmol of ethylaluminum sesquichloride (Al(C 2 H 5 ) 1.5 Cl 1.5 ) in terms of aluminum atoms was added, and subsequently, 0.03 mmol of VO(OC 2 H 5 )Cl 2 was added to initiate polymerization. Ethylene was continuously supplied at 51 L / hr and hydrogen at 2 L / hr, and polymerization was carried out at 25 °C for 10 minutes under normal pressure. Then, polymerization was terminated by adding a small amount of methanol. After the polymerization was completed, the reaction product was added to a polymerization solution containing a small amount of hydrochloric acid in a 4-fold volume amount of an acetone / methanol (3 / 1) mixed solvent to precipitate the polymer. After washing with the same solvent, it was dried under reduced pressure at 130 °C for 10 hours to obtain an ethylene-tetracyclododecene copolymer which is a cyclic olefin copolymer. The physical property values, etc. of the obtained ethylene-tetracyclododecene copolymer are shown in Table 1.

[0150] [Comparative Example 1-2] Except that the amount of tetracyclododecene was changed to 34.2 mmol, the same operations as in Comparative Example 1-1 were carried out to obtain an ethylene-tetracyclododecene copolymer which is a cyclic olefin copolymer. The physical property values, etc. of the obtained ethylene-tetracyclododecene copolymer are shown in Table 1.

[0151] [Comparative Examples 1-3] Using a glass reactor with an internal volume of 2000 mL, the same operations as in Example 1-1 were carried out except that 900 mL of a cyclohexane / hexane (9 / 1) mixed solution, 55.22 mmol of tetracyclododecene, 0.00075 mmol of the transition metal compound (A-1), and 0.012 mmol of triphenylcarbenium tetrakis(pentafluorophenyl)borate were used, and an ethylene-tetracyclododecene copolymer, which is a cyclic olefin copolymer, was obtained. The physical property values and the like of the obtained ethylene-tetracyclododecene copolymer are shown in Table 1.

[0152] [Comparative Example 1-4] The same operations as in Example 1-1 were carried out except that 89.99 mmol of tetracyclododecene, 0.20 mmol of triisobutylaluminum in terms of aluminum atoms, and 0.001 mmol of the transition metal compound (A-1) were used, and an ethylene-tetracyclododecene copolymer, which is a cyclic olefin copolymer, was obtained. The physical property values and the like of the obtained ethylene-tetracyclododecene copolymer are shown in Table 1.

[0153] [Example 2] A glass reactor with an internal volume of 500 mL that had been sufficiently purged with nitrogen was charged with 300 mL of a cyclohexane / hexane (9 / 1) mixed solution, 32.88 mmol of tetracyclododecene, and 113.46 mmol of benzonorbornadiene. The liquid and gas phases were saturated with ethylene at 51 liters / hr. Subsequently, 0.30 mmol of triisobutylaluminum in terms of aluminum atoms, followed by 0.00025 mmol of the above transition metal compound (A-1) and 0.004 mmol of triphenylcarbenium tetrakis(pentafluorophenyl)borate were added to initiate polymerization. Ethylene was continuously supplied at 51 liters / hr, and polymerization was carried out at 50 °C for 10 minutes under normal pressure. Then, polymerization was terminated by adding a small amount of methanol. After the polymerization was completed, the reaction product was added to a polymer solution containing a small amount of hydrochloric acid in a four-fold volume of an acetone / methanol (3 / 1) mixed solvent to precipitate the polymer. After washing with the same solvent, it was dried under reduced pressure at 130 °C for 10 hours to obtain an ethylene·tetracyclododecene·benzonorbornadiene copolymer, which is a cyclic olefin copolymer. The physical property values, etc. of the obtained ethylene·tetracyclododecene·benzonorbornadiene copolymer are shown in Table 2.

[0154] [Comparative Example 2-1] A 500 mL glass reactor fully purged with nitrogen was charged with 300 mL of a cyclohexane / hexane (9 / 1) mixed solution, 11.65 mmol of tetracyclododecene, and 52.21 mmol of benzonorbornadiene. The liquid and gas phases were saturated with ethylene at 90 L / hr and hydrogen at 0.24 L / hr. Subsequently, 0.50 mmol of triisobutylaluminum in terms of aluminum atoms was added, followed by 0.0005 mmol of 3,5-bis-i-propyl-1-pyrazolate-t-butylcyclopentadienyltitanium dichloride (hereinafter referred to as transition metal compound (A-2)) and 0.004 mmol of triphenylcarbenium tetrakis(pentafluorophenyl)borate to initiate polymerization. Ethylene was continuously supplied at 90 L / hr and hydrogen at 0.24 L / hr, and polymerization was carried out at 50 °C for 10 minutes under normal pressure. Then, polymerization was terminated by adding a small amount of methanol. After the polymerization was completed, the reaction product was added to a polymer solution containing a small amount of hydrochloric acid in a 4-fold volume of an acetone / methanol (3 / 1) mixed solvent to precipitate the polymer. After washing with the same solvent, it was dried under reduced pressure at 130 °C for 10 hours to obtain an ethylene·tetracyclododecene·benzonorbornadiene copolymer, which is a cyclic olefin copolymer. The physical property values, etc. of the obtained ethylene·tetracyclododecene·benzonorbornadiene copolymer are shown in Table 2.

[0155] [Comparative Example 2-2] The same procedure as in Comparative Example 2-1 was carried out except that 22.44 mmol of tetracyclododecene, 29.92 mmol of benzonorbornadiene, 0.30 mmol of triisobutylaluminum in terms of aluminum atoms, and 0.0001 mmol of the above transition metal compound (A-1) were used to obtain an ethylene·tetracyclododecene·benzonorbornadiene copolymer, which is a cyclic olefin copolymer. The physical property values, etc. of the obtained ethylene·tetracyclododecene·benzonorbornadiene copolymer are shown in Table 2.

[0156] [Comparative Example 2-3] The same operation as in Example 2 was carried out except that 16.87 mmol of tetracyclododecene, 16.87 mmol of benzonorbornadiene, and the transition metal compound (A-1) were changed to 0.0005 mmol, and an ethylene·tetracyclododecene·benzonorbornadiene copolymer, which is a cyclic olefin copolymer, was obtained. The physical property values, etc. of the obtained ethylene·tetracyclododecene·benzonorbornadiene copolymer are shown in Table 2.

[0157] [Comparative Example 2-4] The same operation as in Example 2 was carried out except that 101.24 mmol of tetracyclododecene, 101.24 mmol of benzonorbornadiene, and the transition metal compound (A-1) were changed to 0.0005 mmol, and an ethylene·tetracyclododecene·benzonorbornadiene copolymer, which is a cyclic olefin copolymer, was obtained. The physical property values, etc. of the obtained ethylene·tetracyclododecene·benzonorbornadiene copolymer are shown in Table 2.

[0158] [Example 3] 300 mL of a cyclohexane / hexane (9 / 1) mixed solution and 202.48 mmol of benzonorbornadiene were charged into a 500 mL glass reactor sufficiently purged with nitrogen, and ethylene was saturated in the liquid phase and the gas phase at 51 L / hr. Then, 0.20 mmol of triisobutylaluminum in terms of aluminum atom, subsequently 0.00025 mmol of the above transition metal compound (A-1), and 0.004 mmol of triphenylcarbenium tetrakis(pentafluorophenyl)borate were added to initiate polymerization. Ethylene was continuously supplied at 51 L / hr, and polymerization was carried out at 50 °C for 10 minutes under normal pressure, and then polymerization was stopped by adding a small amount of methanol. After completion of the polymerization, the reaction product was added to a polymerization solution containing a small amount of hydrochloric acid in a 4-fold volume of an acetone / methanol (3 / 1) mixed solvent to precipitate the polymer. After washing with the same solvent, it was dried under reduced pressure at 130 °C for 10 hours to obtain an ethylene·benzonorbornadiene copolymer, which is a cyclic olefin copolymer. Table 3 shows the physical property values and the like of the obtained ethylene-benzonorbornadiene copolymer.

[0159] [Comparative Example 3-1] The same operations as in Example 3 were carried out except that benzonorbornadiene was changed to 127.49 mmol, triisobutylaluminum was changed to 0.30 mmol in terms of aluminum atom, and the transition metal compound (A-1) was changed to 0.000125 mmol, to obtain an ethylene-benzonorbornadiene copolymer which is a cyclic olefin copolymer. Table 3 shows the physical property values and the like of the obtained ethylene-benzonorbornadiene copolymer.

[0160] [Comparative Example 3-2] The same operations as in Example 3 were carried out except that benzonorbornadiene was changed to 89.99 mmol, triisobutylaluminum was changed to 0.30 mmol in terms of aluminum atom, and the transition metal compound (A-1) was changed to 0.000125 mmol, to obtain an ethylene-benzonorbornadiene copolymer which is a cyclic olefin copolymer. Table 3 shows the physical property values and the like of the obtained ethylene-benzonorbornadiene copolymer.

[0161] [Comparative Example 3-3] A glass reactor with an internal volume of 500 mL that was fully purged with nitrogen was charged with 300 mL of a cyclohexane / hexane (9 / 1) mixed solution and 89.75 mmol of benzonorbornadiene. The liquid and gas phases were saturated with ethylene at 90 L / hr and hydrogen at 0.24 L / hr. Subsequently, 0.30 mmol of triisobutylaluminum in terms of aluminum atoms, followed by 0.000125 mmol of the above transition metal compound (A-2) and 0.004 mmol of triphenylcarbenium tetrakis(pentafluorophenyl)borate were added to initiate polymerization. Ethylene was continuously supplied at 90 L / hr and hydrogen at 0.24 L / hr, and polymerization was carried out at 50 °C for 10 minutes under normal pressure. Then, polymerization was terminated by adding a small amount of methanol. After the polymerization was completed, the reaction product was added to a polymer solution containing a small amount of hydrochloric acid in a four-fold volume of an acetone / methanol (3 / 1) mixed solvent to precipitate the polymer. After washing with the same solvent, it was dried under reduced pressure at 130 °C for 10 hours to obtain an ethylene-benzonorbornadiene copolymer, which is a cyclic olefin copolymer. The physical property values, etc. of the obtained ethylene-benzonorbornadiene copolymer are shown in Table 3.

[0162] In Tables 1 to 3, TD represents tetracyclododecene and BNBD represents benzonorbornadiene.

[0163]

Table 1

[0164]

Table 2

[0165]

Table 3

Claims

1. It has a glass transition point of 120° C. or more and less than 170° C. The weight average molecular weight (Mw) measured by gel permeation chromatography in terms of polystyrene is 1,000,000 or more. Cyclic olefin copolymer.

2. The cyclic olefin copolymer is At least one olefin-derived structural unit (a) represented by the following general formula (Ia); At least one structural unit selected from the group consisting of structural units (b) and (c), The structural unit (b) includes at least one structural unit selected from the group consisting of a structural unit derived from a cyclic olefin monomer (AA) represented by the following general formula (IIa), a structural unit derived from a cyclic olefin monomer (AB) represented by the following general formula (IIIa), and a structural unit derived from a cyclic olefin monomer (AC) represented by the following general formula (IVa): The cyclic olefin copolymer according to claim 1, wherein the structural unit (c) comprises at least one structural unit selected from the group consisting of a structural unit derived from a cyclic olefin monomer represented by the following general formula (C-1), a structural unit derived from a cyclic olefin monomer represented by the following general formula (C-2), and a structural unit derived from a cyclic olefin monomer represented by the following general formula (C-3): 【Chemistry 1】 (In the above general formula (Ia), R ３００ represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms. 【Chemistry 2】 (In the general formula (IIa), u is 0 or 1; v is 0 or a positive integer, w is 0 or 1; R ６１ ~R ７８ And R ａ１ and R ｂ１ may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, R ７５ ~R ７８ may be bonded to each other to form a monocyclic or polycyclic ring). 【Chemistry 3】 (In the general formula (IIIa), x and d each independently represent an integer of 0 or 1 or more; y and z are each independently 0, 1 or 2; R ８１ ~R ９９ may be the same or different and are a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group which is an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or an alkoxy group, R ８９ and R ９０ and a carbon atom to which R ９３ or the carbon atom to which R ９１ may be bonded directly or via an alkylene group having 1 to 3 carbon atoms, Also, 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) 【Chemistry 4】 (In the general formula (IVa), R １００ , R １０１ may be the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, f is 1≦f≦18) 【Chemistry 5】 (In the above general formula (C-1), n and q each independently represent 0, 1, or 2; R １ ~R １７ each independently represents a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom other than a fluorine atom, R １０ ~R １７ One of them is a bond, Also, when q = 0, R １０ and R １１ , R １１ and R １２ , R １２ and R １３ , R １３ and R １４ , R １４ and R １５ , R １５ and R １０ may be bonded to each other to form a monocyclic or polycyclic ring, Also, when q=1 or 2, R １０ and R １１ , R １１ and R １７ , R １７ and R １７ , R １７ and R １２ , R １２ and R １３ , R １３ and R １４ , R １４ and R １５ , R １５ and R １６ , R １６ and R １６ , R １６ and R １０ may be bonded to each other to form a monocyclic or polycyclic ring, The monocyclic or polycyclic ring may have a double bond. The monocyclic or polycyclic ring may be an aromatic ring. 【Chemistry 6】 (In the general formula (C-2), n and m are each independently 0, 1 or 2; q is 1, 2 or 3; R １８ ~R ３１ each independently represents a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom other than a fluorine atom, Also, when q = 1, R ２８ and R ２９ , R ２９ and R ３０ , R ３０ and R ３１ may be bonded to each other to form a monocyclic or polycyclic ring, When q=2 or 3, R ２８ and R ２８ , R ２８ and R ２９ , R ２９ and R ３０ , R ３０ and R ３１ , R ３１ and R ３１ may be bonded to each other to form a monocyclic or polycyclic ring, The monocyclic or polycyclic ring may be an aromatic ring. 【Chemistry 7】 (In the general formula (C-3), q is 1, 2 or 3; R ３２ ~R ３９ each independently represents a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom other than a fluorine atom, Also, when q = 1, R ３６ and R ３７ , R ３７ and R ３８ , R ３８ and R ３９ may be bonded to each other to form a monocyclic or polycyclic ring, When q=2 or 3, R ３６ and R ３６ , R ３６ and R ３７ , R ３７ and R ３８ , R ３８ and R ３９ , R ３９ and R ３９ may be bonded to each other to form a monocyclic or polycyclic ring, The monocyclic ring or the polycyclic ring may have a double bond, The monocyclic or polycyclic ring may be an aromatic ring.

3. The cyclic olefin copolymer according to claim 2, wherein the content of the structural unit (a) in the cyclic olefin copolymer is 40.0 mol % or more and 80.0 mol % or less, when the content of all structural units in the cyclic olefin copolymer is 100 mol %.

4. The cyclic olefin copolymer is The structural unit (a), any one of the structural units selected from the group consisting of the structural unit (b) and the structural unit (c); The cyclic olefin-based copolymer of claim 2 , comprising:

5. A resin composition comprising the cyclic olefin copolymer according to claim 1 or 2.

6. A molded article comprising the cyclic olefin copolymer according to claim 1 or 2.

7. A film or sheet comprising the cyclic olefin copolymer according to claim 1 or 2.

8. An antenna comprising the molded article according to claim 6.

9. An antenna comprising the film or sheet of claim 7.

10. It has a glass transition point of 120° C. or more and less than 170° C. A method for producing a cyclic olefin copolymer having a weight average molecular weight (Mw) of 1,000,000 or more as measured by gel permeation chromatography in terms of polystyrene, comprising the steps of: The manufacturing method comprises: At least one olefin represented by the following general formula (Ia): A method for producing a cyclic olefin copolymer, comprising a step of copolymerizing at least one cyclic olefin monomer selected from the group consisting of a cyclic olefin monomer (AA) represented by the following general formula (IIa), a cyclic olefin monomer (AB) represented by the following general formula (IIIa), and a cyclic olefin monomer (AC) represented by the following general formula (IVa), and / or at least one cyclic olefin monomer selected from the group consisting of a cyclic olefin monomer represented by the following general formula (C-1), a cyclic olefin monomer represented by the following general formula (C-2), and a cyclic olefin monomer represented by the following general formula (C-3): 【Chemistry 8】 (In the above general formula (Ia), R ３００ represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms. 【Chemistry 9】 (In the general formula (IIa), u is 0 or 1; v is 0 or a positive integer, w is 0 or 1; R ６１ ~R ７８ And R ａ１ and R ｂ１ may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, R ７５ ~R ７８ may be bonded to each other to form a monocyclic or polycyclic ring). 【Chemistry 10】 (In the general formula (IIIa), x and d each independently represent an integer of 0 or 1 or more; y and z are each independently 0, 1 or 2; R ８１ ~R ９９ may be the same or different and are a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group which is an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or an alkoxy group, R ８９ and R ９０ and a carbon atom to which R ９３ or the carbon atom to which R ９１ may be bonded directly or via an alkylene group having 1 to 3 carbon atoms, Also, 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) 【Chemistry 11】 (In the general formula (IVa), R １００ , R １０１ may be the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, f is 1≦f≦18) 【Chemistry 12】 (In the above general formula (C-1), n and q each independently represent 0, 1, or 2; R １ ~R １７ each independently represents a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom other than a fluorine atom, R １０ ~R １７ One of them is a bond, Also, when q = 0, R １０ and R １１ , R １１ and R １２ , R １２ and R １３ , R １３ and R １４ , R １４ and R １５ , R １５ and R １０ may be bonded to each other to form a monocyclic or polycyclic ring, Also, when q=1 or 2, R １０ and R １１ , R １１ and R １７ , R １７ and R １７ , R １７ and R １２ , R １２ and R １３ , R １３ and R １４ , R １４ and R １５ , R １５ and R １６ , R １６ and R １６ , R １６ and R １０ may be bonded to each other to form a monocyclic or polycyclic ring, The monocyclic or polycyclic ring may have a double bond. The monocyclic or polycyclic ring may be an aromatic ring. 【Chemistry 13】 (In the general formula (C-2), n and m are each independently 0, 1 or 2; q is 1, 2 or 3; R １８ ~R ３１ each independently represents a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom other than a fluorine atom, Also, when q = 1, R ２８ and R ２９ , R ２９ and R ３０ , R ３０ and R ３１ may be bonded to each other to form a monocyclic or polycyclic ring, When q=2 or 3, R ２８ and R ２８ , R ２８ and R ２９ , R ２９ and R ３０ , R ３０ and R ３１ , R ３１ and R ３１ may be bonded to each other to form a monocyclic or polycyclic ring, The monocyclic or polycyclic ring may be an aromatic ring. 【Chemistry 14】 (In the general formula (C-3), q is 1, 2 or 3; R ３２ ~R ３９ each independently represents a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom other than a fluorine atom, Also, when q = 1, R ３６ and R ３７ , R ３７ and R ３８ , R ３８ and R ３９ may be bonded to each other to form a monocyclic or polycyclic ring, When q=2 or 3, R ３６ and R ３６ , R ３６ and R ３７ , R ３７ and R ３８ , R ３８ and R ３９ , R ３９ and R ３９ may be bonded to each other to form a monocyclic or polycyclic ring, The monocyclic ring or the polycyclic ring may have a double bond, The monocyclic or polycyclic ring may be an aromatic ring.

11. The copolymerization step comprises: (A) a transition metal compound represented by the following general formula [A]: (B) (B-1) organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) A compound that reacts with the transition metal compound to form an ion pair At least one compound selected from the group consisting of The method for producing a cyclic olefin copolymer according to claim 10, which is carried out in the presence of an olefin polymerization catalyst comprising: 【Chemistry 15】 (In the above general formula [A], M is a titanium atom, a zirconium atom, or a hafnium atom; n is an integer from 1 to 4, X's each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group, an aluminum-containing group, or a diene-based divalent derivative group; R １‘ ~R ８‘ each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, or a phosphorus-containing group, R １‘ ~R ５‘ adjacent groups among these may be bonded to each other to form a ring, R ６‘ ~R ８‘ At least one of the groups is a tertiary hydrocarbon group.

12. The cyclic olefin monomer is at least one cyclic olefin monomer selected from the group consisting of the cyclic olefin monomer (AA), the cyclic olefin monomer (AB) and the cyclic olefin monomer (AC); and At least one cyclic olefin monomer selected from the group consisting of a cyclic olefin monomer represented by the general formula (C-1), a cyclic olefin monomer represented by the general formula (C-2), and a cyclic olefin monomer represented by the general formula (C-3). The method for producing a cyclic olefin copolymer according to claim 10 or 11, comprising the cyclic olefin monomer comprising either one of the following:

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