Cyclic olefin polymer, cyclic olefin polymer composition and molded product

Abstract

A cyclic olefin polymer, which is a cyclic olefin polymer having a norbornene backbone, is characterized in that: the cyclic olefin polymer is a cyclic olefin copolymer or a cyclic olefin ring-opening polymer, and satisfies the following necessary condition (a). (Necessary condition (a)) The cyclic olefin polymer comprises a chain olefin constituting unit (A) and a cyclic olefin constituting unit (B) containing a norbornene backbone, and the ratio of meso-racemic structures to racemic structures in the chain of the constituting unit (B)-the constituting unit (A)-the constituting unit (B) determined by 13C-NMR is 0.01 to 100.

Description

[Technical Field]

[0001] This invention relates to a cyclic olefin polymer, a cyclic olefin polymer composition, and a molded body. [Previous Technology]

[0002] Cyclic olefin copolymers are used in optical lenses such as camera lenses, fθ lenses, and pickup lenses. The cyclic olefin copolymers used in the molding of such optical lenses require properties such as high transparency, excellent dimensional stability, excellent heat resistance, and excellent moisture resistance.

[0003] As a resin composition comprising such a cyclic olefin copolymer, there is, for example, the invention described in Patent Document 1. Patent Document 1 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.

[0004] In addition, Patent Document 2 discloses a method for manufacturing a cyclic olefin copolymer, characterized in that: α-olefins and cyclic olefins are copolymerized in the presence of a catalyst formed by (A) a coordination metal compound of group IVB of the periodic table and (B) an organoaluminooxy compound, wherein the coordination metal compound of group IVB of the periodic table is configured as a ligand of a polydentate coordination compound formed by bonding at least two different cycloalkadienyl groups or their substitutes via hydrocarbon groups or silicate groups or substituted silicate groups.

[0005] In addition, Patent Document 3 discloses an ethylene-cyclic olefin copolymer, which is formed by random copolymerization of (a) ethylene and an aromatic norbornene derivative represented by a specific formula.

[0006] In addition, Patent Document 4 discloses a method for manufacturing an olefin polymer, comprising: a contacting step in which a transition metal complex, an organoaluminum in a proportion of 10,000 moles or less relative to 1 mole of the transition metal atoms in the transition metal complex, and a solvent are contacted; and a polymerization step in which the olefin is polymerized in the presence of a solution containing the transition metal complex that has undergone the contacting step and containing an organoaluminum at a concentration of 0.005 mmol / L or more based on aluminum atoms.

[0007] In addition, Patent Document 5 discloses a cyclic olefin copolymer having a constituent unit (A) derived from an α-olefin having 2 to 20 carbon atoms, a constituent unit (B) derived from a cyclic olefin without an aromatic ring, and a constituent unit (C) derived from a cyclic olefin with an aromatic ring.

[0008] Furthermore, Patent Document 5 discloses a cyclic olefin copolymer composition characterized by comprising [A] a cyclic olefin polymer selected from a specific structure and having a softening temperature of 120°C to 300°C, and [B] a cyclic olefin polymer with a glass transition point of 50°C or less. The absolute value of the difference between the refractive index of the cyclic olefin copolymer [B] and the refractive index of the cyclic olefin copolymer [A], as determined according to American Society for Testing and Materials (ASTM) D542, is below a specific range, and [B] is contained in an amount of 5 parts by weight to 50 parts by weight relative to 50 parts by weight of [A]. [Prior Art Documents] [Patent Documents]

[0009] Patent Document 1: Japanese Patent Application Publication No. 10-287713; Patent Document 2: Japanese Patent Application Publication No. 2-173112; Patent Document 3: Japanese Patent Application Publication No. 2005-330465; Patent Document 4: Japanese Patent Application Publication No. 2018-165308; Patent Document 5: International Publication No. 2008 / 068897 [Non-Patent Document]

[0010] Non-patent literature 1: Walter Kaminsky, Rudiger Engehausen, and Jurgen Kopf, “A Tailor-Made Metallocene for the Copolymerization of Ethene with Bulky Cycloalkenes”, Angewandte Chemie International Edition in English Volume 34, Issue 20 p.2273-2275. Non-Patent Literature 2: Incoronata Tritto, Laura Boggioni, Cristina Zampa, and Dino R. Ferro, “Ethylene-Norbornen Copolymers by Cs-Symmetric Metallocenes: Determination of the Copolymerization Parameters and Mechanistic Considerations on the Basis of Tetrad Analysis” Macromolecules, 2005, 38, 9910-9919. [Summary of the Invention]

[0011] [Problem to be Solved by the Invention] It is known that cyclic olefin copolymers or ring-opening polymers having a norbornene structure generally have low solubility in solvents. According to the research of the inventors, it has been found that in the inventions described in Patent Documents 1 to 5, especially in solvents used when coating polymers such as methylcyclohexane and toluene are difficult to dissolve at or near room temperature, it is impossible to obtain a homogeneous solution.

[0012] The present invention has been made in view of the above circumstances, and its object is to provide a cyclic olefin polymer having a norbornene backbone with improved solubility in solvents. [Means for Solving the Problem]

[0013] The inventors have made repeated efforts to solve the aforementioned problem. As a result, they discovered that cyclic olefin copolymers having a norbornene structure or ring-opening polymers having a norbornene backbone exhibit high solubility in solvents, thus completing the present invention. That is, according to the present invention, cyclic olefin polymers, cyclic olefin polymer compositions, and molded articles are provided as shown below.

[0014] [1] A cyclic olefin polymer, which is a cyclic olefin polymer having a norbornene skeleton, characterized in that: the cyclic olefin polymer is a cyclic olefin copolymer or a cyclic olefin ring-opening polymer, and satisfies the following necessary condition (a), (necessary condition (a)) The cyclic olefin polymer comprises a chain olefin constitutive unit (A) and a cyclic olefin constitutive unit (B) containing a norbornene skeleton, and the ratio of meso-racemic structure to racemic structure in the chain of the constitutive unit (B)-the constitutive unit (A)-the constitutive unit (B) as determined by 13C-Nuclear Magnetic Resonance (13C-NMR) is 0.01 to 100.[2] The cyclic olefin polymer as described in [1], wherein the cyclic olefin polymer is a cyclic olefin copolymer comprising 30 mol% to 80 mol% of the constituent unit (A) derived from ethylene or an α-olefin having 3 to 30 carbon atoms, and 20 mol% to 70 mol% of the constituent unit (B) derived from one or more cyclic monomers selected from the group consisting of general formulas [ZI], [Z-II], [Z-III] and [Z-IV]. [Chemical 1] (In the formula [ZI], u is 0 or 1, v is 0 or a positive integer, w is 0 or 1; R61 to R78 and Ra1 and Rb1 each independently contain one or more of the group consisting of hydrogen atoms, halogen atoms and hydrocarbon groups; R75 to R78 can be bonded to each other to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring can also have double bonds; in addition, R75 and R76, or R77 and R78 can also form alkylene groups) [Chemical 2] (In the formula [Z-II], x and d are integers of 0 or 1 or more, y and z are 0, 1 or 2; R81 to R99 are independently selected from hydrogen atoms, halogen atoms, and hydrocarbon groups, and the carbon atoms bonded by R89 and R90 can be bonded directly or via alkyl groups with 1 to 3 carbon atoms; in addition, when y=z=0, R95 and R92 or R95 and R99 can also be bonded to each other to form a monocyclic or polycyclic aromatic ring) [Chemical 3] (In the formula [Z-III], n and m are independently 0, 1 or 2, q is 1, 2 or 3; R18 to R31 are independently hydrogen atoms, halogen atoms other than fluorine atoms, or hydrocarbon groups with 1 to 20 carbon atoms that can be substituted by halogen atoms other than fluorine atoms) [Chemical 4] (In general formula [Z-IV], x is an integer greater than or equal to 0 or 1, R111 to R118 are independently selected from hydrogen atoms, halogen atoms and hydrocarbon groups respectively; R121 to R124 are independently selected from hydrogen atoms, halogen atoms and hydrocarbon groups respectively, and two adjacent groups may also bond to each other to form a monocyclic or polycyclic aromatic ring) The total of the constituent unit (A) and the constituent unit (B) is 100 mol%. [3] The cyclic olefin polymer described in [1] or [2] is characterized in that: the following necessary condition (b) is satisfied, (necessary condition (b)) The proportion of the chain of the constituent unit (B) in the constituent unit (B) as determined by 13C-NMR is more than 0.1 mol% and less than 20.0 mol%.[4] A cyclic olefin polymer as described in any one of [1] to [3], wherein the glass transition temperature of the cyclic olefin copolymer or the cyclic olefin ring-opening polymer, as determined by a differential scanning calorimeter (DSC), is 50°C or higher and 250°C or lower. [5] A cyclic olefin polymer as described in any one of [1] to [4], wherein the glass transition temperature of the cyclic olefin copolymer or the cyclic olefin ring-opening polymer, as determined by a differential scanning calorimeter (DSC), is 50°C or higher and 180°C or lower. [6] A cyclic olefin polymer as described in any one of [1] to [5], wherein the limiting viscosity of the cyclic olefin copolymer or the cyclic olefin ring-opening polymer is 0.1 [dL / g] or higher and 5.0 [dL / g] or lower. [7] A cyclic olefin polymer composition comprising a cyclic olefin polymer as described in any one of [1] to [6]. [8] The cyclic olefin polymer composition described in [7] is used in optical components, film packaging materials, optical films, or medical components. [9] A molded article comprising the cyclic olefin polymer described in any one of [1] to [6].

[10] The molded article described in [9] is an optical component, film packaging material, optical film, or medical component. [Effects of the Invention].

[0015] The cyclic olefin polymer with a norbornene backbone of the present invention exhibits higher solubility in solvents than previous cyclic olefin copolymers or ring-opening polymers. Therefore, it can be readily dissolved in solvents such as methylcyclohexane or toluene used for coating polymers at or near room temperature. Furthermore, since a homogeneous solution containing the cyclic olefin copolymer or ring-opening polymer can be obtained, there is no inhomogeneity when forming films or other molded articles, resulting in excellent mechanical strength or elongation.

Implementation Method

[0016] Hereinafter, the present invention will be described based on embodiments. Furthermore, in this embodiment, unless otherwise specified, "A to B" indicating a numerical range means A or more and B or less. In addition, unless otherwise specified, "cyclic olefin polymer" refers to copolymers and / or ring-opening polymers.

[0017] As described above, according to the insights of the inventors, it is known that previous cyclic olefin copolymers or ring-opening polymers generally have low solubility in solvents. The inventors have repeatedly conducted research to solve this problem. As a result, it was discovered that cyclic olefin polymers with specific stereoregularity have higher solubility in solvents, thus completing the present invention.

[0018] That is, the cyclic olefin polymer involved in this embodiment is as follows.

[0019] <Cyclic Olefin Polymer with Norbornene Backbone> A cyclic olefin polymer, which is a cyclic olefin polymer with a norbornene backbone, characterized in that: the cyclic olefin polymer is a cyclic olefin copolymer or a cyclic olefin ring-opening polymer, and satisfies the following necessary condition (a). (Necessary condition (a)) The cyclic olefin polymer comprises a chain olefin constitutive unit (A) and a cyclic olefin constitutive unit (B) containing a norbornene backbone, and the ratio of meso-racemic structures to racemic structures in the chain of the constitutive unit (B)-the constitutive unit (A)-the constitutive unit (B) determined by 13C-NMR is 0.01 to 100.

[0020] If the polymer is a cyclic olefin polymer with a norbornene backbone as described in this embodiment, its solubility in the solvent is increased due to its specific stereoregularity. In particular, it can be readily dissolved in solvents (e.g., methylcyclohexane, toluene, etc.) used when coating polymers at or near room temperature. Therefore, since a homogeneously dissolved solvent can be obtained, there is no inhomogeneity when forming films or other molded articles, resulting in excellent mechanical strength or elongation.

[0021] Cyclic olefin copolymers with specific stereoregularity are soluble not only in methylcyclohexane but also in other solvents such as toluene. Because the solubility parameter (SP value) of cyclic olefin copolymers differs depending on the constituent components or composition of the chain olefin (A) and the cyclic olefin containing the norbornene backbone (B), their solubility relative to toluene solvent can sometimes be higher depending on the difference in SP value.

[0022] First, the specific stereoregularity involved in this embodiment will be explained. For example, a polymer having a structure represented by the following general formula (I) will be used as an example. The so-called meso compound structure in the chain of constituent unit (B)-constituent unit (A)-constituent unit (B) refers to the structure shown as αβm in Figure 5 of Non-Patent Document 2. In addition, the so-called exo compound structure refers to the structure shown as αβr in that figure.

[0023] [Chemical 5]

[0024] In the general formula (I), m and n represent repeating units. Here, if the structure derived from norbornene is designated as NB and the structure derived from ethylene is designated as E, then in the example, they are linked in the manner of …-NB-E-NB-E-NB-E-… The meso and racemic structures are determined by 13C-NMR. An example of this bonding pattern is shown below.

[0025] [Chemical 6]

[0026] Typically, cyclic olefin copolymers with a norbornene skeleton or cyclic olefin ring-opening polymers with a norbornene skeleton synthesized without controlling stereoregularity are only meso or racemic and have low solubility in solvents. On the other hand, regarding the cyclic olefin polymer with a norbornene backbone according to this embodiment, generally speaking, the ratio of the portion of the structure in a racemic relationship to the portion of the structure in a meso relationship, that is, the ratio of the racemic structure to the meso structure representing stereoregularity [racemic / meso], is 0.01 to 100 (i.e., racemic:meso = 1:100 to 100:1), preferably 0.05 to 50.0, more preferably 0.1 to 10.0, even more preferably 0.25 to 5.0, even more preferably 0.3 to 3.0, even more preferably 0.4 to 1.5, even more preferably 0.4 to 1.2, even more preferably 0.5 to 1.0, even more preferably 0.5 to 0.9. By having a racemic / meso ratio within the aforementioned range, the solubility in the solvent is improved. The stereoregularity can be appropriately adjusted by selecting the catalyst or co-catalyst during polymerization, as described later.

[0027] There are no particular limitations on the 13C-NMR determination if it can distinguish between meso and racemic structures. Examples of such 13C-NMR determinations are as follows. More detailed 13C-NMR determinations will be explained using the stereoregularity described later. Apparatus: Bruker BioSpin AVANCE IIIcryo-500 NMR spectrometer; Nucleus: 13C; Frequency: 125 MHz; Measurement Mode: Single-pulse proton (with reverse gate); Decoupling Pulse Width: 90 degrees; Number of Points: 64,000; Measurement Range: -55 ppm to 195 ppm (total 250 ppm); Repetition Time: 12 seconds; Number of Repetitions: 256; Solvent: 1,1,2,2-Tetrachloroethane-d2; Concentration: 10% w / v; Temperature: 120℃; Chemical Shift Standard: Tetramethylsilyl standard (consistent with 1,1,2,2-tetrachloroethane-d2: 74.2 ppm).

[0028] [Cyclic Olefin Polymers with Norbornene Backbone] The cyclic olefin copolymers with a norbornene backbone (hereinafter also simply referred to as cyclic olefin copolymers) or cyclic olefin ring-opening polymers with a norbornene backbone (hereinafter also simply referred to as cyclic olefin ring-opening polymers) according to this embodiment will be described in detail. The cyclic olefin copolymers and cyclic olefin ring-opening polymers comprise a constitutive unit (A) having a norbornene backbone and being a chain olefin, and a constitutive unit (B) containing a cyclic olefin having a norbornene backbone.

[0029] (Cyclic olefin copolymer) From the viewpoint that the transparency and refractive index of the obtained optical component can be well maintained and the heat resistance or formability can be further improved, the cyclic olefin copolymer involved in this embodiment preferably has the following constituent unit (A) and constituent unit (B).

[0030] Construential unit (A): A constituent unit derived from ethylene or an α-olefin having 3 to 30 carbon atoms. Construential unit (B): A constituent unit derived from at least one of the groups consisting of constituent units represented by the following general formula (ZI), constituent units represented by the following general formula (Z-II), constituent units represented by the following general formula (Z-III), and constituent units represented by the following general formula (Z-IV).

[0031] [Chemical 7]

[0032] In the formula [ZI], u is 0 or 1, v is 0 or a positive integer, preferably an integer greater than 1, more preferably 1 or 2, and even more preferably 1, w is 0 or 1. R61 to R78 and Ra1 and Rb1 are independently selected from hydrogen atoms, halogen atoms and hydrocarbon groups, respectively.

[0033] [Chemical 8]

[0034] In the [Z-II] formula, x and d are integers of 0 or 1 or more, and y and z are 0, 1 or 2. x is preferably an integer of 1 or more, more preferably 1 or 2, and even more preferably 1. R81 to R99 are independently selected from hydrogen atoms, halogen atoms, and hydrocarbon groups, respectively. The carbon atoms bonded to R89 and R90 can also be bonded directly to the carbon atoms bonded to R93 or R91, or via alkyl groups having 1 to 3 carbon atoms. Furthermore, when y=z=0, R95 and R92 or R95 and R99 can also be bonded to each other to form monocyclic or polycyclic aromatic rings.

[0035] [Chemical 9]

[0036] In the formula [Z-III], n and m are independently 0, 1, or 2, and q is 1, 2, or 3. R18 to R31 are independently hydrogen atoms, halogen atoms other than fluorine atoms, or hydrocarbon groups with 1 to 20 carbon atoms that can be substituted by halogen atoms other than fluorine atoms. In addition, when q=1, R28 and R29, R29 and R30, and R30 and R31 can also bond with each other to form monocyclic or polycyclic rings. In addition, when q=2 or 3, R28 and R28, R28 and R29, R29 and R30, R30 and R31, and R31 and R31 can also bond with each other to form monocyclic or polycyclic rings. The monocyclic or polycyclic rings can also have double bonds, and the monocyclic or polycyclic rings can also be aromatic rings. In formula [Z-III], it is preferable that n and m are 0 and q is 1, 2 or 3, and even more preferably that n and m are 0 and q is 1.

[0037] [Chemical 10]

[0038] In the formula [Z-IV], x is an integer greater than or equal to 0 or 1. In addition, R111 to R118 are independently selected from hydrogen atoms, halogen atoms and hydrocarbon groups, respectively, and R121 to R124 are independently selected from hydrogen atoms, halogen atoms and hydrocarbon groups, respectively. Two adjacent groups can also be bonded to each other to form a monocyclic or polycyclic aromatic ring.

[0039] By using the cyclic olefin monomers represented by the [ZI] formula, the [Z-II] formula, the [Z-III] formula or the [Z-IV] formula as copolymer components, the solubility of the cyclic olefin copolymer in the solvent is further improved, thereby improving the formability and increasing the yield of the product.

[0040] The total percentage of constituent unit (A) and constituent unit (B) is set to 100 mol%, and the constituent unit (A) is preferably 30 mol% to 80 mol%, more preferably 40 mol% to 77 mol%, and even more preferably 50 mol% to 75 mol%, while the constituent unit (B) is preferably 20 mol% to 70 mol%, more preferably 23 mol% to 60 mol%, and even more preferably 25 mol% to 50 mol%. By setting the ratio of constituent unit (A) and constituent unit (B) within the aforementioned numerical range, the solubility of the cyclic olefin copolymer in the solvent is further improved, thereby improving the formability and increasing the yield of the product. The proportion of constituent unit (A) derived from olefins can be determined by 13C-NMR.

[0041] The olefin monomer, which is one of the copolymerization raw materials of the olefin copolymer involved in this embodiment, is a substance that forms the constituent unit (A) by addition polymerization. Specifically, for example, an olefin monomer represented by the following general formula (Ia) can be exemplified.

[0042] [Chemical 11]

[0043] In the general formula (Ia), R300 represents a straight-chain or branched hydrocarbon group having 1 to 28 hydrogen atoms or carbon atoms. Examples of olefin monomers represented by the general formula (Ia) include: ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc. From the viewpoint of obtaining optical components with superior heat resistance, mechanical properties, and optical properties, ethylene and propylene are preferred, and ethylene is particularly preferred. The olefin monomer represented by the general formula (Ia) may be two or more. From the viewpoint of obtaining optical parts with superior formability and optical properties, the olefin monomer represented by the general formula (Ia) is preferably free of acyclic dienes.

[0044] Specific examples of cyclic olefin monomers represented by the [ZI] formula, the [Z-II] formula, the [Z-III] formula, or the [Z-IV] formula may include, for example: bicyclo-2-heptene derivatives (bicyclo-heptene-2-ene derivatives), tricyclo-3-decene derivatives, tricyclo-3-undecene derivatives, tetracyclo-3-dodecene derivatives, pentacyclo-4-pentadene derivatives, pentacyclopentadecanadiene derivatives, pentacyclo-3-pentadene derivatives, pentacyclo-4-hexadecene derivatives, pentacyclo- 3-Hexadecene derivatives, hexacyclic-4-heptadecene derivatives, heptacyclic-5-eicosene derivatives, heptacyclic-4-eicosene derivatives, heptacyclic-5-timocosene derivatives, octacyclic-5-timocosene derivatives, nonacyclic-5-timocosene derivatives, nonacyclic-6-timocosene derivatives, cyclopentadiene-acenaphthene adducts, 1,4-methylbridged-1,4,4a,9a-tetrahydrofluorene derivatives, 1,4-methylbridged-1,4,4a,5,10,10a-hexahydroanthracene derivatives, and cycloalkyl derivatives with 3 to 20 carbon atoms.

[0045] The weight average molecular weight of the cyclic olefin monomer represented by the [ZI] formula, the [Z-II] formula, the [Z-III] formula, or the [Z-IV] formula is preferably 50 g / mol or more and 500 g / mol or less, more preferably 100 g / mol or more and 300 g / mol or less, and most preferably 100 g / mol or more and 250 g / mol or less. Furthermore, when the cyclic olefin polymer comprises one or more cyclic olefin monomers selected from the group consisting of general formulas [ZI], [Z-II], [Z-III], or [Z-IV], it is preferable that the weight average molecular weight of at least one of these cyclic olefin monomers is 100 g / mol or more and 500 g / mol or less.

[0046] A cyclic olefin monomer selected from one or both of the following formulas: [ZI], [Z-II], [Z-III] or [Z-IV], preferably a cyclic olefin monomer selected from one or both of the following formulas: [ZI] and [Z-IV].

[0047] The cyclic olefin monomer represented by the [ZI] formula is preferably selected from one or more of the following: bicyclo[2.2.1]-2-heptene (also known as norbornene), tetracyclo[4.4.0.12,5.17,10]-3-dodecene (also known as tetracyclododecene), 5-phenyl-bicyclo[2.2.1]hept-2-ene, 5-methyl-bicyclo[2.2.1]hept-2-ene, 5-tolyl-bicyclo[2.2.1]hept-2-ene, and 5-(ethylphenyl)-bicyclo[2.2.1]hept-2-ene, with tetracyclo[4.4.0.12,5.17,10]-3-dodecene being more preferred. These cyclic olefins have a rigid ring structure, thus having the advantage of easily maintaining the elastic modulus of copolymers and optical components. From the viewpoint of obtaining optical parts with superior formability and optical properties, the cyclic olefin monomer represented by the [ZI] formula is preferably without a polar group.

[0048] The copolymer type involved in this embodiment is not particularly limited, and examples include random copolymers and block copolymers. In this embodiment, since optical components with excellent optical properties such as transparency, refractive index and birefringence and high precision can be obtained, random copolymers are preferred as the copolymer involved in this embodiment.

[0049] The copolymers involved in this embodiment are preferably random copolymers of ethylene and tetracyclo[4.4.0.12,5.17,10]-3-dodecene (hereinafter also referred to as TD), random copolymers of ethylene and bicyclo[2.2.1]-2-heptene (hereinafter referred to as norbornene or NB), copolymers of ethylene and 5-phenyl-bicyclo[2.2.1]hept-2-ene, copolymers of ethylene and 5-methyl-bicyclo[2.2.1]hept-2-ene, copolymers of ethylene and 5-tolyl-bicyclo[2.2.1]hept-2-ene, and copolymers of ethylene and 5-(ethylphenyl)-bicyclo[2.2.1]hept-2-ene. Copolymers of ethylene with 5-(isopropylphenyl)-bicyclo[2.2.1]hept-2-ene, copolymers of ethylene with 5-(α-naphthyl)-bicyclo[2.2.1]hept-2-ene, copolymers of ethylene with 1,4-methylbridged-1,4,4a,9a-tetrahydrofluorene, copolymers of ethylene with 1,4-methylbridged-1,4,4a,5,10,10a-hexahydroanthracene, copolymers of ethylene with 1,4,4a,9a-tetrahydro-1,4-methylbridged fluorene (hereinafter referred to as indnorbornene or IndNB), copolymers of ethylene with 1,4-dihydro-1,4-methylbridged naphthalene (hereinafter referred to as benzonorbornene or BNBD), copolymers of ethylene with tetracyclo[4.4.0.12,5] The copolymers of ethylene and tetracyclo[4.4.0.12,5.17,10]-3-dodecene with 1,4-dihydro-1,4-methylnaphthalene, ethylene and tetracyclo[4.4.0.12,5.17,10]-3-dodecene with 1,4,4a,9a-tetrahydro-1,4-methylnaphthalene (hereinafter referred to as indobornene), ethylene and norbornene with 1,4-dihydro-1,4-methylnaphthalene, ethylene and norbornene with indobornene, ethylene and tetracyclo[4.4.0.12,5.17,10]-3-dodecene with norbornene, and more preferably, random copolymers of ethylene and tetracyclo[4.4.0.12,5.17,10]-3-dodecene. The copolymers of ethylene and 1,4-dihydro-1,4-methylbridged naphthalene, the copolymers of ethylene and tetracyclo[4.4.0.12,5.17,10]-3-dodecene and 1,4-dihydro-1,4-methylbridged naphthalene, the copolymers of ethylene and tetracyclo[4.4.0.12,5.17,10]-3-dodecene and norbornene, and preferably random copolymers of ethylene and tetracyclo[4.4.0.12,5.17,10]-3-dodecene, the copolymers of ethylene and 1,4-dihydro-1,4-methylbridged naphthalene, and the copolymers of ethylene and tetracyclo[4.4.0.12,5.17,10]-3-dodecene and 1,4-dihydro-1,4-methylbridged naphthalene.

[0050] The copolymers involved in this embodiment may be used alone or in combination of two or more.

[0051] The copolymer involved in this embodiment can be manufactured by appropriately selecting conditions, for example, according to Japanese Patent Application Publication No. 60-168708, Japanese Patent Application Publication No. 61-120816, Japanese Patent Application Publication No. 61-115912, Japanese Patent Application Publication No. 61-115916, Japanese Patent Application Publication No. 61-271308, Japanese Patent Application Publication No. 61-272216, Japanese Patent Application Publication No. 62-252406, Japanese Patent Application Publication No. 62-252407, Japanese Patent Application Publication No. 2018-145349, International Publication No. 2015 / 122415, Japanese Patent Application Publication No. 2007-063409, and Japanese Patent Application Publication No. 2-173112.

[0052] (Cyclic Olefin Ring-Opening Polymer) The cyclic olefin ring-opening polymer involved in this embodiment is a cyclic olefin ring-opening polymer having a norbornene backbone. From the viewpoint of maintaining a good balance between the transparency and refractive index of the obtained optical parts and further improving heat resistance or formability, it is preferable to have a structure derived from at least one of the group consisting of the constituent units represented by the general formula (ZI), the general formula (Z-II), and the general formula (Z-IV). This excludes u=v=0 in the general formula (ZI), x=0 in the general formula (Z-II), and x=0 in the general formula (Z-IV). The carbon-carbon bonds formed by the ring-opening of the carbon-carbon double bonds in the general formulas (ZI), (Z-II), and (Z-IV) correspond to the constituent unit (A), and the portions other than those corresponding to the constituent unit (A) correspond to the constituent unit (B).

[0053] That is, the ring-opening polymer preferably has constituent units derived from the same constituent units as the copolymer.

[0054] {Stage Regularity} The stereoregularity involved in this embodiment is determined by 13C-NMR. There are no particular limitations on the 13C-NMR measurement as long as it can distinguish between meso and racemic structures. An example of specific measurement conditions is as described above. Here, the 13C-NMR signal positions indicating meso and racemic structures differ depending on the polymer (polymer, ring-opening polymer). The 13C-NMR signal positions and measurement methods are described below in several embodiments.

[0055] (A: The case of a polymer of ethylene and TD) is a cyclic olefin polymer having the structure represented by the [ZI] formula, and u=0, v=1, and the [ZI] formula does not have an aromatic ring (i.e., the case of a polymer of ethylene and TD). In the 13C-NMR spectrum, the integral values ​​(XA) of the signal in the range of 38.7 ppm to 39.7 ppm and the integral values ​​(YA) of the signal in the range of 40.3 ppm to 41.2 ppm are defined as stereoregularity = XA / YA, where the ratio is 0.01 or higher and 100 or lower, preferably 0.1 or higher and 10.0 or lower, more preferably 0.2 or higher and 5.0 or lower, further preferably 0.3 or higher and 3.0 or lower, further preferably 0.4 or higher and 1.5 or lower, further preferably 0.4 or higher and 1.2 or lower, further preferably 0.5 or higher and 1.0 or lower, and most preferably 0.5 or higher and 0.9 or lower. In the case of the polymer of ethylene and TD, only one peak appears in the range, therefore it is used as the integral value of the signal.

[0056] (B: Polymer of ethylene and NB) This refers to a cyclic olefin polymer having ethylene and the constituent unit represented by the [ZI] formula, where u=v=0, and the [ZI] formula does not have an aromatic ring (i.e., a polymer of ethylene and NB). In the 13C-NMR spectrum, the total integral values ​​of the signals in the range of 44.6 ppm to 45.6 ppm (XB) and the total integral values ​​of the signals in the range of 45.6 ppm to 46.0 ppm (YB) are defined as stereoregularity = XB / YB, where the ratio is 0.01 or more and 100 or less, preferably 0.01 or more and 50.0 or less, more preferably 0.05 or more and 5.0 or less, more preferably 0.25 or more and 4.0 or less, and most preferably 0.3 or more and 3.0 or less. In the case of B: polymer of ethylene and NB, multiple peaks appear within the range, therefore the total integral values ​​of the signals are used.

[0057] (C: In the case of a polymer of ethylene and BNBD) This refers to a cyclic olefin polymer having ethylene and the constituent unit represented by the [Z-III] formula (i.e., a polymer of ethylene and BNBD). In the 13C-NMR spectrum, the integral value (XC) of the signal in the range of 30.8 ppm to 31.3 ppm minus the integral value (Z) of the signal in the range of 30.1 ppm to 30.8 ppm (XC-Z) and the integral value (YC) of the signal in the range of 31.3 ppm to 31.8 ppm are defined as stereoregularity = (XC-Z) / YC, where the ratio is 0.01 or more and 100 or less, preferably 0.01 or more and 10.0 or less. More preferably 0.05 or more and 5.0 or less, even more preferably 0.1 or more and 1.0 or less. Most preferably 0.3 or more and 1.0 or less. It is the integral value (Z) obtained by subtracting the signal in the range of 30.1 ppm to 30.8 ppm from the signal that contains a portion of the peak value in the range of 30.8 ppm to 31.3 ppm that corresponds to BNBD-ethyl n-BNBE- (n=2 or more).

[0058] (D: In the case of polymers of ethylene, TD and BNBD) The case is a cyclic olefin polymer having ethylene, a structure represented by the [ZI] formula where u=0, v=1 and no aromatic ring, and a constituent unit represented by the [Z-III] formula (i.e., a polymer of ethylene, TD and BNBD). In the 13C-NMR spectrum, the integral value (XD) of the signal in the range of 38.7 ppm to 39.7 ppm and the integral value (YD) of the signal in the range of 40.3 ppm to 41.2 ppm, the XD / YD ratio is 0.01 or more and 100 or less, preferably 0.01 or more and 10.0 or less, more preferably 0.05 or more and 5.0 or less, more preferably 0.1 or more and 1.0 or less, and most preferably 0.3 or more and 1.0 or less.

[0059] Furthermore, in the 13C-NMR spectrum, the integral value (MD) of the signal in the range of 43.6 ppm to 43.8 ppm and the integral value (ND) of the signal in the range of 44.5 ppm to 45.0 ppm, the ratio of MD / ND is 0.01 or more and 100 or less, preferably 0.01 or more and 10.0 or less, more preferably 0.05 or more and 5.0 or less, more preferably 0.1 or more and 1.0 or less, and most preferably 0.3 or more and 1.0 or less. In the case of polymers of D: ethylene, TD and BNBD, peaks of TD-ethylene-TD and BNBD-ethylene-BNBD appear in the range. Therefore, XD and YD are set as the integral values ​​of the TD-ethylene-TD signal, and MD and ND are set as the integral values ​​of BNBD-ethylene-BNBD, and stereoregularity is defined as XD / YD + MD / ND. The stereoregularity = XD / YD + MD / ND is preferably 0.01 or higher and 100 or lower, more preferably 0.01 or higher and 10.0 or lower, even more preferably 0.05 or higher and 5.0 or lower, even more preferably 0.1 or higher and 1.0 or lower, and most preferably 0.3 or higher and 1.0 or lower.

[0060] The cyclic olefin polymer involved in this embodiment preferably satisfies the following necessary condition (b). (Necessary condition (b)) The proportion of the chain of the constituent unit (B) in the constituent unit (B) as determined by 13C-NMR is 0.1 mol% or more and 20.0 mol% or less. Here, when a signal is detected in the range of 51.2 ppm to 55.5 ppm, the proportion of the chain of the constituent unit (B) in the constituent unit (B) as determined by 13C-NMR can be calculated by using the sum of the integral values ​​(P) of the signals detected in the range of 51.2 ppm to 55.5 ppm and the sum of the integral values ​​(Q) of the signals detected in the range of 54.0 ppm to 54.6 ppm, and dividing the value of (PQ) obtained by subtracting (Q) from (P) by (P). At this point, the proportion of the chain of the constituent unit (B) in the constituent unit (B), as determined by 13C-NMR, is preferably 0.1 mol% or more and 20 mol% or less, more preferably 0.3 mol% or more and 10 mol% or less, further preferably 0.6 mol% or more and 5.0 mol% or less, further preferably 0.8 mol% or more and 4.5 mol% or less, and further preferably 1.0 mol% or more and 3.6 mol% or less. This corresponds to the content of cyclic olefin compounds linked together having a norbornene skeleton, for example, the content of TD linked together with TD. By being within these ranges, aggregation is suppressed, and the solubility of the polymer is further increased.

[0061] In addition, when a signal is detected in the range of 40.0 ppm to 50.0 ppm, the proportion of the chain of the constituent unit (B) in the constituent unit (B) determined by 13C-NMR can be calculated by using the sum of the integral values ​​(T) of the signals detected in the range of 40.0 ppm to 50.0 ppm and the sum of the integral values ​​(U) of the signals detected in the range of 45.0 ppm to 46.0 ppm in the 13C-NMR spectrum, and setting the value of (U / T) obtained by dividing (U) by (T) to 2.5 times, and then multiplying it by the composition ratio of BNBD and dividing by 100. At this point, the proportion of the chain of the constituent unit (B) in the constituent unit (B), as determined by 13C-NMR, is preferably 0.1 mol% or more and 20 mol% or less, more preferably 0.3 mol% or more and 10 mol% or less, further preferably 0.6 mol% or more and 5.0 mol% or less, further preferably 0.8 mol% or more and 4.5 mol% or less, and further preferably 1.0 mol% or more and 3.6 mol% or less. This corresponds to the content of cyclic olefin compounds linked together having a norbornene skeleton, for example, the content of BNBD linked together with BNBD. By being within these ranges, aggregation is suppressed, and the solubility of the polymer is further increased.

[0062] Here, when a signal is detected in both the range of 40.0 ppm to 50.0 ppm and the range of 51.2 ppm to 55.5 ppm, the proportion of the chain of the constituent unit (B) in the constituent unit (B) as determined by 13C-NMR can be calculated by summing the proportions calculated separately using the method. In this case, the proportion of the chain of the constituent unit (B) in the constituent unit (B) as determined by 13C-NMR is preferably 0.1 mol% or more and 20 mol% or less, more preferably 0.3 mol% or more and 10 mol% or less, more preferably 0.6 mol% or more and 5.0 mol% or less, more preferably 0.8 mol% or more and 4.5 mol% or less, and more preferably 1.0 mol% or more and 3.6 mol% or less. This corresponds to the content of cyclic olefin compounds linked together with a norbornene backbone, for example, the total content of TD linked with TD and BNBD linked with BNBD. By having these components within the stated range, aggregation is suppressed, and the solubility of the polymer is further increased.

[0063] The lower limit of the glass transition temperature (Tg) of the cyclic olefin polymer involved in this embodiment is preferably 50°C or higher, more preferably 83°C or higher, and particularly preferably 110°C or higher. Furthermore, the upper limit of Tg is preferably 250°C or lower, more preferably 200°C or lower, further preferably 180°C or lower, further preferably 169°C or lower, further preferably 165°C or lower, and particularly preferably 160°C or lower. When the cyclic olefin polymer involved in this embodiment is a cyclic olefin copolymer having the aforementioned constituent unit (A) and the aforementioned constituent unit (B), by having Tg at or above the aforementioned lower limit, good solubility in the solvent can be achieved without excessively increasing the crystallinity of the cyclic olefin copolymer. Furthermore, by having Tg at or below the aforementioned upper limit, aggregation can be suppressed, further improving the solubility of the polymer. Moreover, if Tg is within the aforementioned range, sufficient heat resistance and good formability can be obtained when used as a part requiring heat resistance. Typically, the temperature gradient (Tg) of cyclic olefin polymers varies depending on the composition of the constituent units (A) and (B), with a tendency for Tg to increase as the content of constituent unit (B) increases. Even with the same composition, the Tg tends to increase further when the number of chains in constituent unit (B) increases, although the reason is uncertain. This Tg can be obtained by setting the proportion of the chains of constituent unit (B) derived from one or more cyclic monomers selected from the group consisting of [ZI], [Z-II], [Z-III], or [Z-IV] in the total constituent unit (B) contained in the cyclic olefin copolymer to, for example, 0.1 mol% or more and 20.0 mol% or less.

[0064] The glass transition temperature can be determined using a differential scanning calorimeter (DSC). For specific measurement conditions, for example, using a Hitachi High-Tech Science DSC-7020, the temperature is increased from room temperature to 250°C at a rate of 10°C / min under nitrogen conditions, held for 5 minutes, then decreased to -20°C at a rate of 10°C / min, and held for 5 minutes. The glass transition temperature (Tg) of the cyclic olefin polymer can then be determined from the endothermic curve obtained when the temperature is increased to 300°C at a rate of 10°C / min.

[0065] The molecular weight of the cyclic olefin polymer involved in this embodiment is not particularly limited. When using limiting viscosity [η][dL / g] as a substitute indicator for molecular weight, the value of [η][dL / g] measured according to ASTM J1601 is preferably 0.1 or more and 5.0 or less, more preferably 0.2 or more and 3.0 or less, and most preferably 0.2 or more and 2.0 or less. When the cyclic olefin polymer involved in this embodiment is a cyclic olefin copolymer having the aforementioned constituent unit (A) and the aforementioned constituent unit (B), the weight-average molecular weight (Mw) determined by gel permeation chromatography (GPC) is preferably in the range of 1,000 ≤ Mw ≤ 4,500,000, more preferably 3,000 ≤ Mw ≤ 3,000,000, even more preferably 5,000 ≤ Mw ≤ 2,000,000, further preferably 10,000 ≤ Mw ≤ 1,000,000, and most preferably 30,000 ≤ Mw ≤ 500,000. If the limiting viscosity or the weight-average molecular weight (Mw) is above the aforementioned lower limit, the solubility in the solvent or the mechanical strength of the molded article can be improved. Furthermore, if the limiting viscosity is below the aforementioned upper limit value, the formability can be improved.

[0066] Furthermore, the cyclic olefin polymer involved in this embodiment preferably has a Tg of 169°C or less and a Mw of 300,000 or less, more preferably a Tg of 165°C or less and a Mw of 300,000 or less, and even more preferably a Tg of 160°C or less and a Mw of 300,000 or less. By having the cyclic olefin polymer involved in this embodiment simultaneously satisfy the aforementioned numerical ranges for Tg and Mw, both its solubility in the solvent and the mechanical strength of the molded article can be improved.

[0067] Regarding the density of the cyclic olefin polymer involved in this embodiment, the density value measured in water at 23°C using the water displacement method based on Japanese Industrial Standards (JIS) K7112 is preferably 1000 kg / m³ or more and 1200 kg / m³ or less, more preferably 1020 kg / m³ or more and 1100 kg / m³ or less, even more preferably 1040 kg / m³ or more and 1080 kg / m³ or less, even more preferably 1050 kg / m³ or more and 1070 kg / m³ or less, even more preferably 1055 kg / m³ or more and 1065 kg / m³ or less. If the density value is within the aforementioned range, the balance between the transparency and refractive index of the obtained optical component can be well maintained, and the heat resistance can be further improved. Furthermore, the test piece can be obtained, for example, by sandwiching the cyclic olefin polymer involved in this embodiment into an ultra-heat resistant polyimide film (trade name: Upilex, manufactured by Ube Industries Co., Ltd.), using a 0.1 mm spacer, and vacuum pressing it at 260°C, 10 MPa, and 3 minutes.

[0068] (Other components) The cyclic olefin polymer involved in this embodiment may be formulated with hydrophilic agents, stabilizers, weather stabilizers, heat stabilizers, antioxidants, metal passivators, hydrochloric acid absorbers, antistatic agents, flame retardants, slip agents, anti-blocking agents, anti-fogging agents, lubricants, natural oils, synthetic oils, waxes, organic or inorganic fillers, etc., as needed, without compromising the purpose of this embodiment. The formulation ratio shall be appropriate.

[0069] The composition of the cyclic olefin polymer involved in this embodiment preferably includes a hydrophilic agent. By including a hydrophilic agent, the deterioration of the properties of the molded article under high temperature and high humidity conditions can be suppressed. As a hydrophilic agent, a fatty acid ester of a fatty acid and a polyol is preferred. More preferably, a fatty acid ester of a fatty acid and a polyol having one or more ether groups is preferred.

[0070] Examples of fatty acid esters include: monoglyceride fatty acid esters, diglyceride fatty acid esters, triglyceride fatty acid esters, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tripearate, etc. Fatty acid esters of fatty acids and polyols having one or more ether groups are esters of fatty acids and polyols having one or more ether groups. Furthermore, the ether group of the polyol does not contain the ether group. Examples of polyols having one or more ether groups include: monoglyceride, diglyceride, triglyceride, tetraglyceride, anhydrous sorbitol, etc. In this embodiment, the fatty acid ester preferably includes monoglyceride fatty acid esters, diglyceride fatty acid esters, and triglyceride fatty acid esters. The diglyceride fatty acid ester is formed by esterification of at least one of the four hydroxyl groups contained in diglyceride with a fatty acid.

[0071] As fatty acids, examples include: saturated fatty acids such as butyric acid, valeric acid, hexanoic acid, heptanoic acid, caprylic acid, nonanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, and stearic acid; monounsaturated fatty acids such as butenoic acid, myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, gadooleic acid, and eicosenoic acid; diunsaturated fatty acids such as linoleic acid, eicosadienoic acid, and docosadienoic acid; triunsaturated fatty acids such as linolenic acid, pinolenic acid, eleostearic acid, and eicosatrienoic acid; and stearidonic acid and arachidonic acid. Tetraunsaturated fatty acids such as eicosatetraenoic acid and other tetraunsaturated fatty acids.

[0072] Examples of diglyceride fatty acid esters include diglyceride monocaprylate, diglyceride dicaprylate, diglyceride monodecanoate, diglyceride didecanoate, diglyceride monolaurate, diglyceride dilaurate, diglyceride monomyristate, diglyceride dimyristate, diglyceride monopalmitate, diglyceride dipalmitate, diglyceride monostearate, diglyceride distearate, diglyceride monododecanoate, diglyceride di-dodecanoate, and other diglyceride saturated fatty acid esters; diglyceride monooleate, diglyceride dioleate, and other diglyceride unsaturated fatty acid esters. One or more of these can be used. In this embodiment, the diglyceride fatty acid ester is preferably an ester of diglyceride and a saturated or unsaturated fatty acid selected from the above-described groups having 12 to 18 carbon atoms.

[0073] Furthermore, from the viewpoint of the effectiveness of this embodiment, it is preferable to include diglyceride unsaturated fatty acid esters as the main component, and more preferably, diglyceride monooleate esters as the main component. Since the diglyceride skeleton is hydrophilic and the fatty acids improve the compatibility with the resin, transparency is maintained, and the resistance to damp heat is excellent.

[0074] The composition of the cyclic olefin polymer involved in this embodiment may include at least one diglyceride fatty acid ester. As a preferred example of at least one diglyceride fatty acid ester, examples include monoester alone or a combination of monoester and diester.

[0075] Triglyceride fatty acid ester is an ester of fatty acid and triglyceride. The triglyceride fatty acid ester involved in this embodiment is formed by esterification of at least one of the three hydroxyl groups contained in triglyceride with fatty acid.

[0076] As triglyceride fatty acid esters, examples include: triglyceride monocaprylate, triglyceride dicaprylate, triglyceride tricaprylate, triglyceride monodecanoate, triglyceride didecanoate, triglyceride tridecanoate, triglyceride monolaurate, triglyceride dilaurate, triglyceride trilaurate, triglyceride monomyristate, triglyceride dimyristate, triglyceride trimyristate, triglyceride monopalmitate, triglyceride dipalmitate, triglyceride tripalmitate, triglyceride monostearate, triglyceride distearate, triglyceride tristearate, triglyceride monododecanoate, triglyceride didodecanoate, triglyceride tridodecanoate, etc., saturated triglyceride fatty acid esters; triglyceride monooleate, triglyceride dioleate, triglyceride trioleate, etc., and one or more of these may be used. The triglyceride fatty acid ester involved in this embodiment is preferably an ester containing triglyceride and saturated or unsaturated fatty acids with 8 or more and 24 carbon atoms, and more preferably an ester containing triglyceride and saturated or unsaturated fatty acids with 12 or more and 18 carbon atoms.

[0077] Examples of triglyceride fatty acid esters according to this embodiment include monoesters alone, mixtures of monoesters and diesters, or mixtures of monoesters, diesters, and triesters. Examples of such triglyceride fatty acid esters include compounds described in Japanese Patent Application Publication No. 2006-232714, Japanese Patent Application Publication No. 2002-275308, and Japanese Patent Application Publication No. Hei 10-165152. Examples of commercially available hydrophilic agents according to this embodiment include RIKEMAL DO-100 (manufactured by Riken Vitamin Co., Ltd.) and EXCEPARL PE-MS (manufactured by Kao Corporation). In the composition of the cyclic olefin polymer according to this embodiment, the lower limit of the hydrophilic agent content relative to 100 parts by weight of the cyclic olefin polymer composition is preferably 0.05 parts by weight or more, more preferably 0.4 parts by weight or more. In addition, the upper limit of the content of hydrophilic agent relative to 100 parts by weight of cyclic olefin polymer composition is preferably 3.0 parts by weight or less, more preferably 2.5 parts by weight or less, and even more preferably 1.2 parts by weight or less.

[0078] As an antioxidant, known antioxidants may be used. Specifically, hindered phenolic compounds, sulfur-based antioxidants, lactone-based antioxidants, organophosphite compounds, organophosphonate compounds, or combinations thereof may be used.

[0079] As a lubricant, examples include sodium, calcium, and magnesium salts of saturated or unsaturated fatty acids such as lauric acid, palmitic acid, oleic acid, and stearic acid. These can be used alone or in combination of two or more. The amount of lubricant is not particularly limited, but relative to 100 parts by weight of the olefin polymer, it can be set to, for example, 0.01 to 3 parts by weight, preferably about 0.01 to 2 parts by weight.

[0080] As a lubricant, amides of saturated or unsaturated fatty acids such as lauric acid, palmitic acid, oleic acid, stearic acid, erucic acid, and docosinate, or bisamides of such saturated or unsaturated fatty acids, are preferred. Among these, erucic acid amide and ethyl bis-stearic acid amide are particularly preferred. These fatty acids are typically formulated in the range of 0.01 to 5 parts by weight relative to 100 parts by weight of the cyclic olefin polymer.

[0081] Examples of anti-blocking agents include: micronized silica, micronized alumina, micronized clay, powdered or liquid silicone resin, tetrafluoroethylene resin, and micronized cross-linked resin powder (e.g., cross-linked acrylic acid, methacrylic acid resin powder, etc.). Among these, micronized silica and micronized cross-linked resin powder are preferred.

[0082] The cyclic olefin copolymers with a norbornene backbone and the ring-opening polymers with a norbornene backbone involved in this embodiment can be used in various forms such as lens shape, spherical shape, rod shape, plate shape, cylindrical shape, tubular shape, fibrous shape, film shape, or sheet shape. Among them, it is preferred that they can be used in optical components, films, and medical components. For example, as optical components, examples include: eyeglass lenses, fθ lenses, pickup lenses, camera lenses, sensor lenses, digital camera lenses, projector lenses, CD pickup lenses, automotive camera lenses, etc., as well as prisms, light guide plates, XR devices, etc. As films, examples include: phase difference films for displays, visibility enhancement films for displays, touch sensor films, base films for solar cells, circuit boards, high-frequency substrates, substrates or films or sheets for liquid crystal displays or solar cells, tablet packaging sheets (press-through packaging (PTP)), shrink films, easy-tear films for food packaging, film capacitors, etc. Examples of medical components include: drug-loaded syringes, plastic vials, infusion bags, blood analysis tanks, catheter components, tablet vials, examination containers, sterile tablets, bioplates, and biochips. Cyclic olefin copolymers and ring-opening polymers of cyclic olefins exhibit high solubility in solvents, and therefore readily dissolve, especially at or near room temperature, in solvents used for coating polymers (e.g., methylcyclohexane, toluene, etc.). Consequently, because homogeneous solvents are obtained, there is no unevenness when forming films or other molded bodies, resulting in excellent mechanical strength and elongation.

[0083] The molded article according to this embodiment is obtained by molding a composition containing a cyclic olefin polymer into a predetermined shape. There is no particular limitation on the method for molding the composition containing the cyclic olefin polymer to obtain the molded article, and known methods can be used. While depending on the application and shape, methods such as extrusion molding, injection molding, compression molding, pneumatic molding, blow molding, extrusion blow molding, injection blow molding, compression molding, vacuum molding, powder-slush molding, calendering, and foam molding can be applied. Of these, injection molding and extrusion molding are preferred from the viewpoint of formability and productivity. Furthermore, the molding conditions can be appropriately selected according to the intended use or molding method. For example, in injection molding, the composition temperature is typically selected within the range of 150°C to 400°C, preferably 200°C to 350°C, and more preferably 230°C to 330°C.

[0084] Cyclic olefin copolymers and cyclic olefin ring-opening polymers can be used in the preparation of coating agents, or they can be mixed in a solvent in the preparation of coating agents.

[0085] The solvent used to prepare the coating agent is not particularly limited, and examples include: aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as hexane, heptane, octane, and decane; alicyclic hydrocarbons such as cyclohexane, cyclohexene, and methylcyclohexane; alcohols such as methanol, ethanol, isopropanol, butanol, pentanol, hexanol, propylene glycol, and phenol; ketone solvents such as acetone, methyl isobutyl ketone, methyl ethyl ketone, pentanol, hexanone, isophorone, and acetophenone; cellosols such as methyl cellosol and ethyl cellosol; esters such as methyl acetate, ethyl acetate, butyl acetate, methyl propionate, and butyl formate; and halogenated hydrocarbons such as trichloroethylene, dichloroethylene, and chlorobenzene. Among these, aromatic hydrocarbons, aliphatic hydrocarbons, and ketones are preferred. One of these can be used alone, or two or more can be combined.

[0086] When preparing a coating agent, there are no particular limitations on the coating method, and known methods can be used. For example, after coating by methods such as mold coating, flow coating, spray coating, bar coating, gravure coating, gravure reverse coating, coincident reverse coating, micro-gravure coating, roller coating, doctor blade coating, doctor blade coating, roller knife coating, air knife coating, corner roller coating, reverse roller coating, transfer roller coating, coincident roller coating, curtain coating, and dip coating, the coating film can be obtained by drying by a suitable method such as natural drying or forced drying.

[0087] <Method for Manufacturing Cyclic Olefin Polymer> The cyclic olefin polymer involved in this embodiment can be obtained, for example, by the following methods: a method for melt-mixing the cyclic olefin polymer and other components to be added as needed using a known mixing device such as an extruder and a Banbury mixer; a method for dissolving the cyclic olefin polymer and other components to be added as needed in a common solvent and then evaporating the solvent; a method for adding a solution of the cyclic olefin polymer and other components to be added as needed to a poor solvent and causing it to precipitate, etc.

[0088] Subsequently, for example, the obtained molded article is annealed for 2 to 8 hours within the range of (glass transition temperature (Tg) of the cyclic olefin polymer - 40) °C to (glass transition temperature (Tg) of the cyclic olefin polymer - 5) °C, thereby obtaining a component. By performing the annealing treatment, the molecules of the cyclic olefin polymer in the molded article become less dense, and the free volume decreases. Therefore, even if heat treatment is performed, it is difficult to cause a change in specific gravity (volume change). Here, if the annealing conditions are too strict, the molded article will deform and cannot recover; therefore, it is preferable to perform the annealing under the aforementioned conditions and within a range where the molded article will not deform. That is, it is preferable to perform the annealing treatment at a temperature and time that does not cause deformation of the molded article.

[0089] During polymerization, in the cyclic olefin polymers involved in this embodiment, the stereoregularity (ratio of racemic to meso structures) can be adjusted by selecting a catalyst and a co-catalyst. The catalyst and co-catalyst will be described in detail below.

[0090] [Catalyst] The catalyst involved in this embodiment (hereinafter also referred to as the main catalyst) is not particularly limited as long as the ratio of racemic to meso structures of the cyclic olefin polymer can be adjusted. Specific examples of such a main catalyst include: semi-metallocene titanium compounds, zirconium compounds, and hafnium compounds; and metallocene titanium compounds, zirconium compounds, and hafnium compounds. Among these, semi-metallocene titanium compounds, zirconium compounds, and hafnium compounds having cyclopentadienyl or pyrazolyl groups, and metallocene titanium compounds, zirconium compounds, and hafnium compounds having fluorene are particularly preferred. With these main catalysts, the ratio of racemic to meso structures can be easily adjusted.

[0091] Specific examples of the main catalyst include: 3,5-dimethylethyl-1-pyrazolate-tert-butylcyclopentadiene titanium dichloride (paragraphs 0385-0388 of Japanese Patent Application Publication No. 2019-172954), bis-tert-butylacetone imine cyclopentadiene titanium dichloride (paragraphs 0003-0004 of Japanese Patent Application Publication No. 2018-150273), dimethylmethylenefluorenylcyclopentadiene zirconium dimethyl, diphenylmethylenefluorenylcyclopentylzirconium dimethyl (paragraphs 0088-0109 of Japanese Patent Application Publication No. 2019-172954), and dimethylmethylenefluorenylcyclopentadiene zirconium dimethyl. Methylmethylene bisindylzirconium dichloride (paragraphs 0081 to 0087 of Japanese Patent Application Publication No. 2019-172954), diphenylmethylene indylcyclopentylzirconium dichloride (paragraphs 0092 to 0093 of International Publication No. 2014 / 185253), 3,5-bis-tert-butyl-1-pyrazole-tert-butylcyclopentadiene titanium dichloride, 3,5-bis-tert-butyl-1-pyrazole-indyltitanium dichloride, 3-(4-methoxyphenyl)-5-(4-tert-butylphenyl)-1-pyrazole-tert-butylcyclopentadiene titanium dichloride, 3,5-diphenyl-1-pyrazole-tert-butylcyclopentadiene titanium dichloride, etc.

[0092] [Co-catalyst] The co-catalyst involved in this embodiment is not particularly limited as long as it can improve the catalytic ability of the main catalyst. Examples of such co-catalysts include ionic compounds, preferably aluminum or boron compounds. Examples include: trimethylaluminum, triethylaluminum, triisobutylaluminum, and other trialkylaluminum compounds and mixtures thereof; triphenylcarbaconium tetra(pentafluorophenyl)borate, and N,N-dimethylphenylammonium tetra(pentafluorophenyl)borate, preferably borate compounds containing pentafluorophenyl groups. Using such a co-catalyst allows for more suitable control of stereoregularity.

[0093] Specific examples of such co-catalysts include: triphenylcarbazide tetra(pentafluorophenyl)borate, N,N-dimethylphenylammonium tetra(pentafluorophenyl)borate, MMAO (modified methylaluminoxane), and PMAO (polymethylaluminoxane).

[0094] As a combination of the main catalyst and the co-catalyst involved in this embodiment, it is preferably a combination selected from one or more of the following: semi-metallocene titanium compounds, zirconium compounds, and hafnium compounds having cyclopentadienyl or pyrazolyl groups as the main catalyst, or metallocene titanium compounds, zirconium compounds, and hafnium compounds having fluorene; and a borate compound having pentafluorophenyl groups as the co-catalyst. Specific examples of a preferred combination of the main catalyst and the co-catalyst include the following combinations. • Main catalyst: 3,5-bismethylethyl-1-pyrazole-tert-butylcyclopentadienyl titanium dichloride, bis-tert-butylacetone imine cyclopentadienyl titanium diethyl, dimethylmethylenefluorenylcyclopentadienyl zirconium dimethyl, diphenylmethylenefluorenylcyclopentyl zirconium dimethyl, dimethylmethylenebisindenyl zirconium dichloride, diphenylmethyleneindenylcyclopentyl zirconium dichloride, 3,5-bis-tert-butyl-1-pyrazole-tert-butylcyclopentadienyl titanium dichloride, 3, 5-Bis-tert-butyl-1-pyrazole-indene titanium dichloride, 3-(4-methoxyphenyl)-5-(4-tert-butylphenyl)-1-pyrazole-tert-butylcyclopentadiene titanium dichloride, 3,5-diphenyl-1-pyrazole-tert-butylcyclopentadiene titanium dichloride; Co-catalyst: triphenylcarbazide tetratetra(pentafluorophenyl)borate, N,N-dimethylphenylammonium tetratetra(pentafluorophenyl)borate. Here, one or more of the main catalyst and co-catalyst can be used. By using the combination of the main catalyst and co-catalyst as described above, the solubility of the cyclic olefin polymer can be made more suitable. The mechanism is not necessarily clear, but it is believed that the reason is that by using the co-catalyst as described above, the proportion of meso compounds in the cyclic olefin polymer can be reduced.

[0095] The method for manufacturing cyclic olefin polymers according to this embodiment is characterized in that: olefins are copolymerized with cyclic olefins in the presence of the main catalyst and the co-catalyst.

[0096] In the method for manufacturing the cyclic olefin polymer according to this embodiment, copolymers can also be produced by copolymerizing two or more olefins with cyclic olefins. The method of using each component constituting the catalyst for olefin polymerization according to the present invention and the order of addition to the polymerizer can be arbitrarily selected, and the following general methods can be exemplified. Hereinafter, the main catalyst (A), co-catalyst (B), carrier (C) and organic compound component (D) are referred to as "component (A) to component (D)" respectively. (1) A method of adding component (A) to the polymerizer alone. (2) A method of adding component (A) and component (B) to the polymerizer in any order. (3) A method of adding a catalyst component formed by loading component (A) onto component (C) and component (B) to the polymerizer in any order. (4) A method of adding a catalyst component formed by loading component (B) onto component (C) and component (A) to the polymerizer in any order. (5) A method of adding a catalyst component, which is formed by loading component (A) and component (B) onto component (C), into a polymerizer.

[0097] In each of the methods, component (D) may be added at any stage. In each of the methods, at least two of the catalyst components may be pre-contacted. In methods (4) and (5) with component (B) loaded, unloaded component (B) may be added in any order as needed. In this case, component (B) may be the same or different. Furthermore, regarding solid catalyst components with component (A) loaded on component (C), and solid catalyst components with components (A) and (B) loaded on component (C), olefins may be prepolymerized, and catalyst components may be further loaded onto the prepolymerized solid catalyst components.

[0098] The copolymerization of olefins and cyclic olefins can be carried out by any of the following methods: liquid-phase polymerization such as solution polymerization and suspension polymerization, or gas-phase polymerization. Examples of inert hydrocarbon media used in liquid-phase polymerization include: aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; and halogenated hydrocarbons such as vinyl chloride, chlorobenzene, and dichloromethane. One inert hydrocarbon media can be used alone, or two or more can be mixed.

[0099] When polymerizing olefins using a catalyst for olefin polymerization as described above, the main catalyst (A) is used in an amount that is typically 10⁻¹² mol to 10⁻² mol, preferably 10⁻¹⁰ mol to 10⁻³ mol, per liter of reaction volume.

[0100] When using a carrier (C), the amount of main catalyst (A) to carrier (C) in weight ratio [(A) / (C)] is preferably 0.0001 to 1, more preferably 0.0005 to 0.5, and even more preferably 0.001 to 0.1.

[0101] In the manufacturing method of this embodiment, the polymerization temperature in the polymerization step is typically -50°C to +200°C, preferably 0°C to 180°C; the polymerization pressure is typically atmospheric pressure to 10 MPa gauge pressure, preferably atmospheric pressure to 5 MPa gauge pressure. The polymerization reaction can be carried out using any of the batch, semi-continuous, or continuous methods. Furthermore, the polymerization can also be carried out in two or more stages with different reaction conditions.

[0102] The molecular weight of the obtained cyclic olefin polymer can be adjusted by introducing hydrogen into the polymerization system, changing the polymerization temperature, or using the amount of co-catalyst (B). In the case of adding hydrogen, the appropriate amount is about 0.001 NL to 5,000 NL per 1 kg of copolymer produced.

[0103] The embodiments of the present invention have been described above, but these are merely examples, and various structures other than those described may also be used. Furthermore, the present invention is not limited to the described embodiments, and modifications and alterations within the scope of achieving the objectives of the present invention are also included in the present invention. [Examples]

[0104] Hereinafter, this embodiment will be described in detail with reference to examples, etc. However, this embodiment is not limited in any way by the descriptions in these examples.

[0105] First, the measurement methods performed in the examples will be described.

[0106] [13C-NMR Measurement] The 13C-NMR measurement was performed under the following conditions: Apparatus: Bruker BioSpin AVANCE IIIcryo-500 NMR spectrometer; Nucleus: 13C (125 MHz); Measurement mode: Single-pulse proton (with reverse gate); Decoupling pulse width: 90 degrees; Number of points: 64,000; Measurement range: -55 ppm to 195 ppm (total 250 ppm); Repetition time: 12 seconds; Number of repetitions: 256; Solvent: 1,1,2,2-tetrachloroethane-d2; Concentration: 10% w / v; Temperature: 120℃; Chemical shift standard: Tetramethylsilyl standard (equivalent to 1,1,2,2-tetrachloroethane-d2: 74.2 ppm).

[0107] Under the conditions described, 13C-NMR measurements were performed to determine the proportion of [CO]-[CO] constituent units (the total of [CO]-[CO] structures, [E]-[CO] structures, and [E]-[E] structures was set to 100 mol%), and the proportion of [CO]-[E]-[CO] racemic structures to [CO]-[E]-[CO] meso structures (the total of [CO]-[E]-[CO] racemic structures and [CO]-[E]n-[CO]n (n≧2) was set to 100 mol%). Furthermore, [CO] refers to constituent units derived from cyclic olefins, and [E] refers to constituent units derived from ethylene. Furthermore, when a signal is detected in the range of 51.2 ppm to 55.5 ppm, the total integral value (P) of the signal detected in the range of 51.2 ppm to 55.5 ppm and the total integral value (Q) of the signal detected in the range of 54.0 ppm to 54.6 ppm are measured, and the proportion of the chain constituting unit (B) is calculated by dividing the value of (PQ) obtained by subtracting (Q) from (P) by (P). Alternatively, if a signal is detected in the range of 40.0 ppm to 50.0 ppm, the sum of the integral values ​​(T) of signals detected in the range of 40.0 ppm to 50.0 ppm and the sum of the integral values ​​(U) of signals detected in the range of 45.0 ppm to 46.0 ppm are used. The value of (U / T) obtained by dividing (U) by (T) is set to 2.5 times, and then multiplied by the composition ratio of BNBD and divided by 100 to calculate the chain proportion of the constituent unit (B). Alternatively, if a signal is detected in both the range of 40.0 ppm to 50.0 ppm and the range of 51.2 ppm to 55.5 ppm, the proportions of the constituent unit (B) calculated using the above method are summed to calculate the chain proportion of the constituent unit (B).

[0108] [Solubility Test] Evaluate the solubility relative to methylcyclohexane and toluene under the following conditions. <Solubility relative to methylcyclohexane> • In the cases of examples and comparative examples using polymers of ethylene and TD (i.e., Examples 1, 2, 5-9, 11-13, and Comparative Example 1), Sample: Cyclic olefin copolymer produced in each of the examples and comparative examples described below. Solvent: Methylcyclohexane solution. Concentration: 10 wt%. Temperature: 25°C. Solubility evaluation criteria: Solubility confirmed by visual inspection and after standing for one day. A: No polymer residue, transparent state. B: No polymer residue immediately after dissolution, opaque state after standing for one day. C: Polymer residue, turbid state. • In the cases of examples and comparative examples using polymers of ethylene and BNBD, and polymers of ethylene, TD, and BNBD (i.e., Examples 3, 4, 10, 14, and Comparative Example 2), Sample: Cyclic olefin copolymer produced in each of the examples and comparative examples described below. Solvent: Methylcyclohexane solution. Concentration: 1 wt%. Temperature: 50°C. Solubility evaluation criteria: Solubility confirmed by visual inspection and after standing for one day. A: No polymer residue, transparent state. B: No polymer residue immediately after dissolution, opaque state after standing for one day. C: Polymer residue present, turbid state <relative to toluene solubility>. Sample: Cyclic olefin copolymers prepared in the examples and comparative examples described below. Solvent: Toluene. Solution concentration: 10 wt%. Temperature: 25°C. Solubility evaluation criteria: Solubility confirmed by visual inspection and after standing for one day. A: No polymer residue, transparent state. B: No polymer residue immediately after dissolution, opaque state after standing for one day. C: Polymer residue present, turbid state.

[0109] [Formability] The cyclic olefin copolymers obtained in each example and comparative example were sandwiched into an ultra-heat resistant polyimide film (trade name: Upilex, manufactured by Ube Industries, Inc.), and vacuum-pressed at 260°C, 10 MPa, and 3 minutes using a 0.1 mm spacer. A: No cracks were observed visually, and more than 80% of the area maintained the film shape. B: Cracks were observed visually, and more than 30% but less than 80% of the area maintained the film shape. C: Cracks were observed visually, and more than 70% of the area did not maintain the film shape. [Density] The cyclic olefin copolymers obtained in each example and comparative example were sandwiched into an ultra-heat resistant polyimide film (trade name: Upilex, manufactured by Ube Industries, Inc.), and vacuum-pressed at 260°C, 10 MPa, and 3 minutes using a 0.1 mm spacer to obtain test pieces. For this test piece, the density was determined in water at 23°C based on JIS K7112. Furthermore, the density was determined by the water displacement method.

[0110] [Limiting Viscosity [η]] A mobile viscometer (manufactured by Lihe Company, type VNR053U) was used, and the sample was prepared by dissolving 0.25 g to 0.30 g of a cyclic olefin copolymer in 25 ml of decahydronaphthalene. The specific viscosity of the cyclic olefin copolymer was determined at 135°C according to ASTM J1601, and the ratio of this viscosity to the concentration was extrapolated to a concentration of 0 to determine the limiting viscosity [η] of the cyclic olefin copolymer. [Weight Average Molecular Weight (Mw), Molecular Weight Distribution (Mw / Mn) of Polymer] The weight average molecular weight (Mw) and number average molecular weight (Mn) of the olefin polymer were determined by gel permeation chromatography (GPC). The molecular weight distribution was calculated based on the molecular weight distribution curve obtained using a Waters Alliance GPC 2000 gel permeation chromatography system (high-temperature size exclusion chromatography system). The operating conditions are as follows: <Apparatus and Conditions> Measuring apparatus: Alliance GPC 2000 gel permeation chromatography system (Waters Corporation) Analytical software: Empower chromatography data system (trademark, Waters Corporation) Column: TSKgel GMH6-HT×2 + TSKgel GMH6-HT×2 (inner diameter 7.5 mm × length 30 cm, Tosoh Corporation) Mobile phase: o-dichlorobenzene [=ODCB] (Wako Pure Reagent Grade) Detector: Differential refractometer (built into the device) Column temperature: 140℃ Flow rate: 1.0 mL / min Injection volume: 400 μL Sampling time interval: 1 second; Sample concentration: 0.15% (w / v); Molecular weight correction: Monodisperse polystyrene (Tosoh Corporation) / Molecular weight 495 to 20.6 million.

[0111] [Glass Transition Temperature Tg (°C)] The glass transition temperature (Tg) of cyclic olefin copolymers was measured under nitrogen atmosphere using a DSC-7020 manufactured by Hitachi High-Tech Science. For cyclic olefin copolymers, the temperature was increased from room temperature to 250°C at a heating rate of 10°C / min and held for 5 minutes. Then, the temperature was decreased to -20°C at a cooling rate of 10°C / min and held for 5 minutes. The glass transition temperature (Tg) of the cyclic olefin copolymers was then determined based on the endothermic curve when the temperature was increased to 300°C at a heating rate of 10°C / min.

[0112] (Example 1) In a 500 mL glass reactor that had undergone thorough nitrogen replacement, 300 mL of a mixed solution of cyclohexane / hexane in a 9 / 1 ratio and 2.2 g of tetracyclo[4.4.0.12,5.17,10]-3-dodecene (hereinafter simply referred to as "tetracyclododecene"; Mw: 160.2 (g / mol)) were added. The liquid and gas phases were saturated with ethylene at 90 L / hr and hydrogen at 0.24 L / hr. 59.4 mg (0.3 mmol) of TIBAL (triisobutylaluminum) was added. Then, 0.003 mmol of 3,5-dimethylethyl-1-pyrazole-tert-butylcyclopentadienyl titanium dichloride was added, along with 0.012 mmol of tetra(pentafluorophenyl)borate triphenylcarbamate (hereinafter referred to as borate compound (1); synthesized with reference to Japanese Patent Application Publication No. 2018-105273) and polymerization was initiated.

[0113] Ethylene was continuously supplied at 90 L / hr and hydrogen at 0.24 L / hr. Polymerization was carried out at atmospheric pressure and 50 °C for 5 minutes. A small amount of isobutanol was added to stop the polymerization. After polymerization, the reactants were added to a 1 L acetone / methanol (3 / 1) mixed solvent containing a small amount of hydrochloric acid to precipitate the polymer. After washing with this solvent, the polymer was dried under reduced pressure at 130 °C for 10 hours to obtain 0.346 g of ethylene-tetracyclododecene copolymer. The polymerization activity was 1.38 kg / mmol·hr. The limiting viscosity [η] of the obtained ethylene-tetracyclododecene copolymer (constituent unit (A): 62 mol% ethylene, constituent unit (B): 38 mol% tetracyclododecene) was 0.92 (dL / g), Mw was 217,000 (g / mol), and Mw / Mn was 2.43. The glass transition temperature, determined using a differential scanning calorimeter (DSC), was 153 °C. The racemic / meta-racemic ratio, determined by 13C-NMR, was 0.89. Furthermore, the racemic / meta-racemic ratio was calculated based on the case of the polymer of ethylene and TD. Additionally, the proportion of the chain of constituent unit (B) in constituent unit (B), determined by 13C-NMR, was 1.0. The film exhibited good solubility relative to methylcyclohexane (solubility relative to methylcyclohexane: A). It also exhibited good solubility relative to toluene (solubility relative to toluene: A). Furthermore, the film showed good formability (film formability: A). The density was 1046 (kg / m³). The results are shown in Table 1.

[0114] (Example 2) In a 500 mL glass reactor that had undergone sufficient nitrogen replacement, 245 mL of a cyclohexane / hexane (9 / 1) mixed solution and 5.0 g of tetracyclododecene were added, and the liquid and gas phases were saturated with ethylene at a rate of 50 L / hr. 39.6 mg (0.2 mmol) of TIBAL was added. 0.0005 mmol of bis-tert-butylacetone imine cyclopentadienyltitanium diethyl was added, and 0.002 mmol of borate compound (1) was added, and polymerization was started.

[0115] Ethylene was continuously supplied at a rate of 50 L / hr, and polymerization was carried out at atmospheric pressure and 50 °C for 10 minutes. Subsequently, a small amount of isobutanol was added to stop the polymerization. After polymerization, the reactants were added to a 1 L acetone / methanol (3 / 1) mixed solvent containing a small amount of hydrochloric acid to precipitate the polymer. After washing with this solvent, the polymer was dried under reduced pressure at 130 °C for 10 hours to obtain 0.41 g of ethylene-tetracyclododecene copolymer. The polymerization activity was 4.91 kg / mmol·hr, and the limiting viscosity [η] of the obtained ethylene-tetracyclododecene copolymer (constituent unit (A): 62 mol% ethylene, constituent unit (B): 38 mol% tetracyclododecene) was 0.45 (dL / g), Mw was 124,000 (g / mol), and Mw / Mn was 2.07. The glass transition temperature obtained by DSC was 151 °C, and the ratio of racemic to meso structures obtained by 13C-NMR was 0.72. Furthermore, the racemic / meso ratio was calculated based on the case of the polymer of ethylene and TD. Additionally, the proportion of the chain of constituent unit (B) in constituent unit (B) determined by 13C-NMR was 1.9, indicating good solubility in methylcyclohexane (relative to methylcyclohexane solubility: A). It also showed good solubility in toluene (relative to toluene solubility: A). Furthermore, the film exhibited good formability (film formability: A). The results are shown in Table 1.

[0116] (Example 3) In a 500 mL glass reactor that had been fully nitrogen-replaced, 289 mL of a cyclohexane / hexane (9 / 1) mixture and 20.9 g of benzonorbornene (hereinafter also referred to as BNBD; Mw: 142.2 (g / mol)) were added, and the liquid and gas phases were saturated with ethylene at 51 L / hr and hydrogen at 2 L / hr. 59.4 mg (0.3 mmol) of TIBAL was added, followed by 0.003 mmol of 3,5-bis-1-methylethyl-1-pyrazole-tert-butylcyclopentadienyl titanium dichloride, and 0.012 mmol of borate compound (1) was added to start polymerization. The polymerization was carried out for 10 minutes at atmospheric pressure and 50 °C with a continuous supply of ethylene at 51 L / hr and hydrogen at 2 L / hr. Subsequently, a small amount of isobutanol was added to stop the polymerization. After polymerization, the reactants were added to a 1-liter acetone / methanol (3 / 1) mixed solvent containing a small amount of hydrochloric acid to precipitate the polymer. After washing with this solvent, the polymer was dried under reduced pressure at 130°C for 10 hours to obtain 0.658 g of ethylene-benzonorbornadiene copolymer. The polymerization activity was 6.58 kg / mmol·hr. The limiting viscosity [η] of the obtained ethylene-benzonorbornadiene copolymer (constituent (A): 67 mol% ethylene, constituent (B): 33 mol% benzonorbornadiene) was 0.20 (dL / g), Mw was 34,300 (g / mol), and Mw / Mn was 1.76. The glass transition temperature obtained by DSC was 106°C, and the racemic / meta-component ratio obtained by 13C-NMR was 0.79. Furthermore, the racemic / meta-component ratio was calculated based on the case of the polymer of C: ethylene and BNBD. Furthermore, the proportion of the (B)-(B) chain in the constituent unit (B), as determined by 13C-NMR, is 2.2, indicating good solubility in methylcyclohexane (relative to methylcyclohexane solubility: A). Additionally, it exhibits good solubility in toluene (relative to toluene solubility: A). Furthermore, the membrane exhibits good formability (membrane formability: A). The results are shown in Table 1.

[0117] (Example 4) In a 500 mL glass reactor that had undergone nitrogen replacement, 300 mL of a cyclohexane / hexane (9 / 1) mixed solution and 18.0 g of benzonorbornene were added. The liquid and gas phases were saturated with ethylene at 90 L / hr and hydrogen at 0.24 L / hr. 297.0 mg (1.5 mmol) of TIBAL was added, followed by 0.001 mmol of 3,5-bis-1-methylethyl-1-pyrazole-tert-butylcyclopentadienyl titanium dichloride, and 0.004 mmol of borate compound (1) was added, and polymerization was started.

[0118] Ethylene was continuously supplied at 90 L / hr and hydrogen at 0.24 L / hr, and polymerization was carried out at atmospheric pressure and 50 °C for 3 minutes. Subsequently, a small amount of isobutanol was added to stop the polymerization. After polymerization, the reactants were added to a 1 L acetone / methanol (3 / 1) mixed solvent containing a small amount of hydrochloric acid to precipitate the polymer. After washing with this solvent, the polymer was dried under reduced pressure at 130 °C for 10 hours to obtain 4.490 g of ethylene-benzonorbornadiene copolymer. The polymerization activity was 89.8 kg / mmol·hr. The limiting viscosity [η] of the obtained ethylene-benzonorbornadiene copolymer (constituent unit (A): 57 mol% ethylene, constituent unit (B): 43 mol% benzonorbornadiene) was 0.72 (dL / g), Mw was 310,000 (g / mol), and Mw / Mn was 1.84. The glass transition temperature obtained by DSC was 152 °C, and the ratio of racemic to meso structures obtained by 13C-NMR was 0.89. Furthermore, the racemic / meso ratio was calculated based on the case of the C: ethylene and BNBD polymer. Additionally, the proportion of unit (B)-unit (B) chains in unit (B) determined by 13C-NMR was 4.0, indicating good solubility in methylcyclohexane (relative to methylcyclohexane solubility: A). It also showed good solubility in toluene (relative to toluene solubility: A). Furthermore, the film exhibited good formability (film formability: A). The density was 1060 (kg / m³). The results are shown in Table 1.

[0119] (Example 5) In a 500 mL glass reactor that had undergone sufficient nitrogen replacement, 150 mL of a cyclohexane / hexane (9 / 1) mixed solution and 4.9 g of tetracyclododecene were added. The liquid and gas phases were saturated with ethylene at a flow rate of 51 L / hr and hydrogen at a flow rate of 9.96 L / hr. 297.0 mg (1.5 mmol) of TIBAL was added, followed by 0.003 mmol of dimethylmethylenefluorenylcyclopentadienylzirconium dimethyl, and 0.012 mmol of borate compound (1) was added, and polymerization was started.

[0120] Ethylene was continuously supplied at 51 L / hr and hydrogen at 9.96 L / hr, and polymerization was carried out at atmospheric pressure and 50 °C for 5 minutes. Subsequently, a small amount of isobutanol was added to stop the polymerization. After polymerization, the reactants were added to 0.75 L of acetone / methanol (3 / 1) mixed solvent containing a small amount of hydrochloric acid to precipitate the polymer. After washing with this solvent, the polymer was dried under reduced pressure at 130 °C for 10 hours to obtain 0.235 g of ethylene-tetracyclododecene copolymer. The polymerization activity was 0.94 kg / mmol·hr. The limiting viscosity [η] of the obtained ethylene-tetracyclododecene copolymer (constituent unit (A): 62 mol% ethylene, constituent unit (B): 38 mol% tetracyclododecene) was 0.58 (dL / g), Mw was 84,800 (g / mol), and Mw / Mn was 4.75. The glass transition temperature obtained by DSC was 145°C, and the ratio of racemic to meso structures obtained by 13C-NMR was 0.64. Furthermore, the racemic / meso ratio was calculated based on the case of the polymer of ethylene and TD. Additionally, the proportion of the chain of constituent unit (B) in constituent unit (B) determined by 13C-NMR was 0.5, indicating good solubility in methylcyclohexane (relative to methylcyclohexane solubility: A). Regarding solubility in toluene, it was good immediately after dissolution, but became opaque after standing for one day (relative to toluene solubility: B). Furthermore, the film exhibited good formability (film formability: A). The results are shown in Table 1.

[0121] (Example 6) In a 500 mL glass reactor that had undergone sufficient nitrogen replacement, 150 mL of a cyclohexane / hexane (9 / 1) mixed solution and 9.8 g of tetracyclododecene were added. The liquid and gas phases were saturated with ethylene at a flow rate of 90 L / hr and hydrogen at a flow rate of 0.24 L / hr. 198.0 mg (1.0 mmol) of TIBAL was added, followed by 0.002 mmol of diphenylmethylenefluorenylcyclopentylzirconium dimethyl, and 0.008 mmol of borate compound (1) was added, and polymerization was started.

[0122] Ethylene was continuously supplied at 90 L / hr and hydrogen at 0.24 L / hr, and polymerization was carried out at atmospheric pressure and 50 °C for 10 minutes. Subsequently, a small amount of isobutanol was added to stop the polymerization. After polymerization, the reactants were added to a 0.75 L acetone / methanol (3 / 1) mixed solvent containing a small amount of hydrochloric acid to precipitate the polymer. After washing with this solvent, the polymer was dried under reduced pressure at 130 °C for 10 hours to obtain 0.362 g of ethylene-tetracyclododecene copolymer. The polymerization activity was 1.09 kg / mmol·hr. The limiting viscosity [η] of the obtained ethylene-tetracyclododecene copolymer (constituent unit (A): 59 mol% ethylene, constituent unit (B): 41 mol% tetracyclododecene) was 0.51 (dL / g), Mw was 112,000 (g / mol), and Mw / Mn was 4.38. The glass transition temperature obtained by DSC was 158 °C, and the ratio of racemic to meso structures obtained by 13C-NMR was 0.54. Furthermore, the racemic / meso ratio was calculated based on the case of the polymer of ethylene and TD. Additionally, the proportion of the chain of constituent unit (B) in constituent unit (B) determined by 13C-NMR was 2.0, indicating good solubility in methylcyclohexane (relative to methylcyclohexane solubility: A). It also showed good solubility in toluene (relative to toluene solubility: A). Furthermore, the film exhibited good formability (film formability: A). The results are shown in Table 1.

[0123] (Example 7) In a 500 mL glass reactor that had undergone sufficient nitrogen replacement, 276 mL of a cyclohexane / hexane (9 / 1) mixed solution and 22.4 g of tetracyclododecene were added. The liquid and gas phases were saturated with ethylene at 90 L / hr and hydrogen at 0.24 L / hr. 59.4 mg (0.3 mmol) of TIBAL was added, followed by 0.000125 mmol of 3,5-bis(tert-butyl)-1-pyrazole-tert-butylcyclopentadienyl titanium dichloride, and 0.004 mmol of borate compound (1) was added and polymerization was started.

[0124] Ethylene was continuously supplied at 90 L / hr and hydrogen at 0.24 L / hr, and polymerization was carried out at atmospheric pressure and 50 °C for 10 minutes. Subsequently, a small amount of isobutanol was added to stop the polymerization. After polymerization, the reactants were added to 1.25 L of acetone / methanol (3 / 1) mixed solvent containing a small amount of hydrochloric acid to precipitate the polymer. After washing with this solvent, the polymer was dried under reduced pressure at 130 °C for 10 hours to obtain 0.932 g of ethylene-tetracyclododecene copolymer. The polymerization activity was 44.7 kg / mmol·hr. The limiting viscosity [η] of the obtained ethylene-tetracyclododecene copolymer (constituent unit (A): 54 mol% ethylene, constituent unit (B): 46 mol% tetracyclododecene) was 0.20 (dL / g), Mw was 35,800 (g / mol), and Mw / Mn was 2.19. The glass transition temperature obtained by DSC was 176 °C, and the ratio of racemic to meso structures obtained by 13C-NMR was 1.00. Furthermore, the racemic / meso ratio was calculated based on the case of the polymer of ethylene and TD. Additionally, the proportion of the chain of constituent unit (B) in constituent unit (B) determined by 13C-NMR was 1.2, indicating good solubility in methylcyclohexane (relative to methylcyclohexane solubility: A). It also showed good solubility in toluene (relative to toluene solubility: A). Furthermore, the membrane formability was good in some aspects (membrane formability: B). The results are shown in Table 1.

[0125] (Example 8) In a 500 mL glass reactor that had undergone sufficient nitrogen replacement, 300 mL of a cyclohexane / hexane (9 / 1) mixed solution and 2.9 g of tetracyclododecene were added, and the liquid and gas phases were saturated with ethylene at a rate of 90 L / hr. 59.4 mg (0.3 mmol) of TIBAL was added, followed by 0.003 mmol of 3,5-bisphenyl-1-pyrazole-tert-butylcyclopentadienyl titanium dichloride, and 0.012 mmol of borate compound (1) was added, and polymerization was started.

[0126] Ethylene was continuously supplied at 90 L / hr, and polymerization was carried out at atmospheric pressure and 50 °C for 10 minutes. Subsequently, a small amount of isobutanol was added to stop the polymerization. After polymerization, the reactants were added to 1.25 L of acetone / methanol (3 / 1) mixed solvent containing a small amount of hydrochloric acid to precipitate the polymer. After washing with this solvent, the polymer was dried under reduced pressure at 130 °C for 10 hours to obtain 0.326 g of ethylene-tetracyclododecene copolymer. The polymerization activity was 0.65 kg / mmol·hr, and the limiting viscosity [η] of the obtained ethylene-tetracyclododecene copolymer (constituent unit (A): 58 mol% ethylene, constituent unit (B): 42 mol% tetracyclododecene) was 1.44 (dL / g), Mw was 450,000 (g / mol), and Mw / Mn was 3.55. The glass transition temperature obtained by DSC was 173 °C, and the ratio of racemic to meso structures obtained by 13C-NMR was 1.00. Furthermore, the racemic / meso ratio was calculated based on the case of the polymer of ethylene and TD. Additionally, the proportion of the chain of constituent unit (B)-constituent unit (B) within constituent unit (B), determined by 13C-NMR, was 2.6, indicating good solubility in methylcyclohexane (relative to methylcyclohexane solubility: A). Regarding solubility in toluene, it was good immediately after dissolution, but became opaque after standing for one day (relative to toluene solubility: B). Furthermore, the membrane formation properties were good (membrane formation properties: A). The results are shown in Table 1.

[0127] (Example 9) In a 500 mL glass reactor that had undergone sufficient nitrogen replacement, 300 mL of a cyclohexane / hexane (9 / 1) mixed solution and 1.9 g of tetracyclododecene were added, and the liquid and gas phases were saturated with ethylene at a rate of 90 L / hr. 59.4 mg (0.3 mmol) of TIBAL was added, followed by 0.003 mmol of 3,5-bisphenyl-1-pyrazole-tert-butylcyclopentadienyl titanium dichloride, and 0.012 mmol of borate compound (1) was added, and polymerization was started.

[0128] Ethylene was continuously supplied at 90 L / hr, and polymerization was carried out at atmospheric pressure and 50 °C for 10 minutes. Subsequently, a small amount of isobutanol was added to stop the polymerization. After polymerization, the reactants were added to a 1.25 L acetone / methanol (3 / 1) mixed solvent containing a small amount of hydrochloric acid to precipitate the polymer. After washing with this solvent, the polymer was dried under reduced pressure at 130 °C for 10 hours to obtain 0.545 g of ethylene-tetracyclododecene copolymer. The polymerization activity was 1.09 kg / mmol·hr. The limiting viscosity [η] of the obtained ethylene-tetracyclododecene copolymer (constituent (A): 62 mol% ethylene, constituent (B): 38 mol% tetracyclododecene) was 2.03 (dL / g), Mw was 634,000 (g / mol), and Mw / Mn was 2.33. The glass transition temperature obtained by DSC was 154 °C, and the ratio of racemic to meso structures obtained by 13C-NMR was 1.00. Furthermore, the racemic to meso structure ratio was calculated based on the case of the polymer of ethylene and TD. Additionally, the proportion of the chain of constituent unit (B) in constituent unit (B) determined by 13C-NMR was 1.7, indicating good solubility in methylcyclohexane (relative to methylcyclohexane solubility: A). It also showed good solubility in toluene (relative to toluene solubility: A). Furthermore, the membrane exhibited good formability (membrane formability: A). The results are shown in Table 1.

[0129] (Example 10) In a 500 mL glass reactor that had undergone nitrogen replacement, 300 mL of a mixed solution of cyclohexane / hexane in a 9 / 1 ratio, 3.3 g of tetracyclododecene, and 5.7 g of benzonorbornene were added. The liquid and gas phases were saturated with ethylene at a rate of 50 L / hr and hydrogen at a rate of 0.24 L / hr. 59.4 mg (0.3 mmol) of TIBAL was added. Subsequently, 0.003 mmol of 3,5-dimethylethyl-1-pyrazole-tert-butylcyclopentadienyl titanium dichloride was added, along with 0.012 mmol of borate compound (1), and the polymerization reaction was initiated.

[0130] Ethylene was continuously supplied at 50 L / hr and hydrogen at 0.24 L / hr. Polymerization was carried out at atmospheric pressure and 50 °C for 10 minutes. A small amount of isobutanol was added to stop the polymerization. After polymerization, the reactants were added to a 1 L acetone / methanol (3 / 1) mixed solvent containing a small amount of hydrochloric acid to precipitate the polymer. After washing with this solvent, the polymer was dried under reduced pressure at 130 °C for 10 hours to obtain 1.671 g of ethylene-tetracyclododecene-benzonorbornene copolymer. The polymerization activity was 3.34 kg / mmol·hr. The limiting viscosity [η] of the obtained ethylene-tetracyclododecene-benzonorbornene copolymer (constituent (A): ethylene 59 mol%, constituent (B): tetracyclododecene 25 mol%, benzonorbornene: 16 mol%) was 0.40 (dL / g), Mw was 95,500 (g / mol), and Mw / Mn was 2.90. The glass transition temperature obtained by differential scanning calorimetry (DSC) was 163 °C, and the racemic / mesomeric ratio determined by 13C-NMR was 0.50. Furthermore, the racemic / mesomeric ratio was calculated based on the case of the polymer of A: ethylene, TD, and BNBD. Furthermore, the proportion of the (B)-(B) chain in the constituent unit (B), as determined by 13C-NMR, is 3.2, indicating good solubility relative to methylcyclohexane (solubility relative to methylcyclohexane: A). It also exhibits good solubility relative to toluene (solubility relative to toluene: A). Additionally, the membrane shows good formability (membrane formability: A). The density is 1057 (kg / m³). The results are shown in Table 1.

[0131] (Example 11) In a 500 mL glass reactor that had undergone nitrogen replacement, 250 mL of a cyclohexane / hexane (9 / 1) mixed solution, 5 g of tetracyclododecene, and 331 mg (1.50 mmol) of BHT were added, and the liquid and gas phases were saturated with ethylene at a rate of 50 L / hr. Subsequently, 1.5 mmol of methylaluminoxane was added on an aluminum atom conversion basis, followed by 0.0030 mmol of 3,5-dimethylethyl-1-pyrazole-tert-butylcyclopentadienyl titanium dichloride, and 0.012 mmol of borate compound (1) was added, and the polymerization reaction was initiated.

[0132] Ethylene was continuously supplied at 50 L / hr, and polymerization was carried out at atmospheric pressure and 50 °C for 10 minutes. A small amount of isobutanol was added to stop the polymerization. After polymerization, the reactants were added to a 1 L acetone / methanol (3 / 1) mixed solvent containing a small amount of hydrochloric acid to precipitate the polymer. After washing with this solvent, the polymer was dried under reduced pressure at 130 °C for 10 hours to obtain 1.292 g of ethylene-tetracyclododecene copolymer. The polymerization activity was 2.58 kg / mmol-Ti･hr. The limiting viscosity [η] of the obtained ethylene-tetracyclododecene copolymer (constituent unit (A): 55 mol% ethylene, constituent unit (B): 45 mol% tetracyclododecene) was 1.05 (dL / g), Mw was 320,000 (g / mol), and Mw / Mn was 2.17. The glass transition temperature, determined using a differential scanning calorimeter (DSC), was 188°C. The racemic / meta-racemic ratio, determined by 13C-NMR, was 1.00. Furthermore, the racemic / meta-racemic ratio was calculated based on the case of the polymer of ethylene and TD. Additionally, the proportion of unit (B)-unit (B) chains within unit (B), determined by 13C-NMR, was 3.7, indicating good solubility in methylcyclohexane (solubility in methylcyclohexane: A). Regarding solubility in toluene, it was good immediately after dissolution, but became opaque after standing for one day (solubility in toluene: B). Furthermore, the membrane exhibited good formability (membrane formability: A). The results are shown in Table 1.

[0133] (Example 12) In a 500 mL glass reactor that had undergone sufficient nitrogen replacement, 245 mL of a mixed solution of cyclohexane / hexane in a 9 / 1 ratio and 5.0 g of tetracyclododecene were added, and the liquid and gas phases were saturated with ethylene at a rate of 50 L / hr. 39.6 mg (0.2 mmol) of TIBAL was added. Subsequently, 0.0005 mmol of diphenylmethylene indenylcyclopentylzirconium dichloride was added, and 0.002 mmol of borate compound (1) was added, and the polymerization reaction was started.

[0134] Ethylene was continuously supplied at a rate of 50 L / hr, and polymerization was carried out at atmospheric pressure and 50 °C for 10 minutes. A small amount of isobutanol was then added to stop the polymerization. After polymerization, the reactants were added to a 1 L acetone / methanol (3 / 1) mixed solvent containing a small amount of hydrochloric acid to precipitate the polymer. After washing with this solvent, the polymer was dried under reduced pressure at 130 °C for 10 hours to obtain 1.1 g of ethylene-tetracyclododecene copolymer. The polymerization activity was 13.18 kg / mmol·hr. The limiting viscosity [η] of the obtained ethylene-tetracyclododecene copolymer (constituent (A): 62 mol% ethylene, constituent (B): 38 mol% tetracyclododecene) was 0.36 (dL / g), Mw was 62,200 (g / mol), and Mw / Mn was 2.05. The glass transition temperature, determined using a differential scanning calorimeter (DSC), was 150°C. The racemic / meta-racemic ratio, determined by 13C-NMR, was 0.14. Furthermore, the racemic / meta-racemic ratio was calculated based on the case of the polymer of ethylene and TD. Additionally, the proportion of the chain of constituent unit (B)-constituent unit (B) within constituent unit (B), determined by 13C-NMR, was 1.4. Regarding solubility with respect to methylcyclohexane, it was good immediately after dissolution, but became opaque after standing for one day (solubility with respect to methylcyclohexane: B). Similarly, regarding solubility with respect to toluene, it was good immediately after dissolution, but became opaque after standing for one day (solubility with respect to toluene: B). Furthermore, regarding membrane formability, it was good in some areas (membrane formability: B). The results are shown in Table 1.

[0135] (Example 13) In a 500 mL glass reactor that had undergone nitrogen replacement, 300 mL of a mixed solution of cyclohexane / hexane in a 9 / 1 ratio and 11.4 g of tetracyclododecene were added. The liquid and gas phases were saturated with ethylene at a flow rate of 90 L / hr and hydrogen at a flow rate of 0.24 L / hr. 59.4 mg (0.3 mmol) of TIBAL was added. Subsequently, 0.003 mmol of 3,5-dimethylethyl-1-pyrazole-tert-butylcyclopentadienyl titanium dichloride was added, and 0.012 mmol of borate compound (1) was added, and the polymerization reaction was started.

[0136] Ethylene was continuously supplied at 90 L / hr and hydrogen at 0.24 L / hr. Polymerization was carried out at atmospheric pressure and 50 °C for 10 minutes. A small amount of isobutanol was added to stop the polymerization. After polymerization, the reactants were added to a 1 L acetone / methanol (3 / 1) mixed solvent containing a small amount of hydrochloric acid to precipitate the polymer. After washing with this solvent, the polymer was dried under reduced pressure at 130 °C for 10 hours to obtain 1.483 g of ethylene-tetracyclododecene copolymer. The polymerization activity was 2.97 kg / mmol·hr. The limiting viscosity [η] of the obtained ethylene-tetracyclododecene copolymer (constituent unit (A): 51 mol% ethylene, constituent unit (B): 49 mol% tetracyclododecene) was 0.30 (dL / g), Mw was 67,200 (g / mol), and Mw / Mn was 3.03. The glass transition temperature, determined using differential scanning calorimetry (DSC), was 203 °C. The racemic / meta-race structure ratio, determined by 13C-NMR, was 1.00. Furthermore, the racemic / meta-race structure ratio was calculated based on the case of the polymer of ethylene and TD. Additionally, the proportion of unit (B)-unit (B) chains within unit (B), determined by 13C-NMR, was 5.1, indicating good solubility in methylcyclohexane (solubility in methylcyclohexane: A). Regarding solubility in toluene, it was good immediately after dissolution, but became opaque after standing for one day (solubility in toluene: B). Furthermore, the film formation was poor (film formation: C). The results are shown in Table 1.

[0137] (Example 14) In a 500 mL glass reactor that had undergone nitrogen replacement, 300 mL of a cyclohexane / hexane (9 / 1) mixed solution and 3.0 g of benzonorbornene were added, and the liquid and gas phases were saturated with ethylene at a flow rate of 50 L / hr and hydrogen at a flow rate of 6.0 L / hr. 9.9 mg (0.5 mmol) of TIBAL was added, followed by 0.0005 mmol of diphenylmethylene indenylcyclopentylzirconium dichloride, and 0.002 mmol of borate compound (1) was added, and polymerization was started.

[0138] Ethylene was continuously supplied at 50 L / hr and hydrogen at 6.0 L / hr, and polymerization was carried out at atmospheric pressure and 50 °C for 10 minutes. Subsequently, a small amount of isobutanol was added to stop the polymerization. After polymerization, the reactants were added to a 1 L acetone / methanol (3 / 1) mixed solvent containing a small amount of hydrochloric acid to precipitate the polymer. After washing with this solvent, the polymer was dried under reduced pressure at 130 °C for 10 hours to obtain 0.413 g of ethylene-benzonorbornadiene copolymer. The polymerization activity was 84.96 kg / mmol·hr. The limiting viscosity [η] of the obtained ethylene-benzonorbornadiene copolymer (constituent (A): 68 mol% ethylene, constituent (B): 32 mol% benzonorbornadiene) was 0.33 (dL / g), Mw was 88,000 (g / mol), and Mw / Mn was 6.90. The glass transition temperature obtained by DSC was 112°C, and the ratio of racemic to meso structures obtained by 13C-NMR was 0.26. Furthermore, the racemic / meso ratio was calculated based on the case of the C: ethylene and BNBD polymer. Additionally, the proportion of the B-chain in the constituent unit (B) determined by 13C-NMR was 0.0, indicating poor solubility relative to methylcyclohexane (solubility relative to methylcyclohexane: B). However, it exhibited good solubility relative to toluene (solubility relative to toluene: A). Furthermore, the membrane formability was good in some areas (membrane formability: B). The results are shown in Table 1.

[0139] (Comparative Example 1) In a 500 mL glass reactor that had undergone sufficient nitrogen replacement, 240 mL of a cyclohexane / hexane (9 / 1) mixed solution and 10.0 g of tetracyclododecene were added, and the liquid and gas phases were saturated with ethylene at a flow rate of 50 L / hr and hydrogen at a flow rate of 3.0 L / hr. 19.8 mg (0.1 mmol) of TIBAL was added. Subsequently, 0.00025 mmol of dimethylmethylene bisindenylzirconium dichloride was added, and 0.001 mmol of borate compound (1) was added, and polymerization was started.

[0140] Ethylene was continuously supplied at 50 L / hr and hydrogen at 3.0 L / hr. Polymerization was carried out at atmospheric pressure and 50 °C for 10 minutes. A small amount of isobutanol was added to stop the polymerization. After polymerization, the reactants were added to a 1 L acetone / methanol (3 / 1) mixed solvent containing a small amount of hydrochloric acid to precipitate the polymer. After washing with this solvent, the polymer was dried under reduced pressure at 130 °C for 10 hours to obtain 1.83 g of ethylene-tetracyclododecene copolymer. The polymerization activity was 43.82 kg / mmol·hr. The limiting viscosity [η] of the obtained ethylene-tetracyclododecene copolymer (constituent unit (A): 64 mol% ethylene, constituent unit (B): 36 mol% tetracyclododecene) was 0.50 (dL / g), Mw was 97,200 (g / mol), and Mw / Mn was 2.47. The glass transition temperature obtained by DSC was 148 °C, and the ratio of racemic to meso structure obtained by 13C-NMR was 0.00. Furthermore, the proportion of the B-chain within the constituent unit (B) determined by 13C-NMR was 0.0, indicating poor solubility relative to methylcyclohexane (solubility relative to methylcyclohexane: C). Additionally, it showed poor solubility relative to toluene (solubility relative to toluene: C). Furthermore, it exhibited poor film formation (film formation: C). The results are shown in Table 1.

[0141] (Comparative Example 2) In a 500 mL glass reactor that had undergone sufficient nitrogen replacement, 175 mL of a mixed solution of cyclohexane / hexane in a 9 / 1 ratio, 4.0 g of tetracyclododecene, and 5.0 g of benzonorbornene were added, and the liquid and gas phases were saturated with ethylene at a flow rate of 51 L / hr and hydrogen at a flow rate of 2 L / hr. 148.5 mg (0.75 mmol) of TIBAL (triisobutylaluminum) was added. Subsequently, 0.0015 mmol of dimethylmethylene bisindenylzirconium dichloride and 0.006 mmol of borate compound (1) were added, and the polymerization reaction was initiated.

[0142] Ethylene was continuously supplied at 51 L / hr and hydrogen at 2 L / hr. Polymerization was carried out at atmospheric pressure and 50 °C for 10 minutes. A small amount of isobutanol was added to stop the polymerization. After polymerization, the reactants were added to a 1 L acetone / methanol (3 / 1) mixed solvent containing a small amount of hydrochloric acid to precipitate the polymer. After washing with this solvent, the polymer was dried under reduced pressure at 130 °C for 10 hours to obtain 0.814 g of ethylene-tetracyclododecene-benzonorbornene copolymer. The polymerization activity was 3.26 kg / mmol·hr. The limiting viscosity [η] of the obtained ethylene-tetracyclododecene-benzonorbornene copolymer (constituent unit (A): 62 mol% ethylene, constituent unit (B): 21 mol% tetracyclododecene, 17 mol% benzonorbornene was 0.50 (dL / g), Mw was 99,200 (g / mol), and Mw / Mn was 2.80. The glass transition temperature, determined using a differential scanning calorimeter (DSC), was 137°C. The racemic / meta-race structure ratio, determined by 13C-NMR, was 0.00. Furthermore, the racemic / meta-race structure ratio was calculated based on the case of the polymer of ethylene, TD, and BNBD. Additionally, the proportion of the chain of constituent unit (B) within constituent unit (B), determined by 13C-NMR, was 0.0. The solubility was poor relative to methylcyclohexane (solubility relative to methylcyclohexane: C). It was also poor relative to toluene (solubility relative to toluene: C). The membrane formation was poor (membrane formation: C). The results are shown in Table 1.

[0143] [Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Comparative Example 1 Example 10 Example 11 Example 12 Example 13 Example 14 Comparative Example 2 Derivation of constituent unit (B) Cyclic olefins with NB backbone TD TD BNBD BNBD TD TD TD TD TD TD TD / BNBD TD TD TD BNBD TD / BNBD Tg (°C) 153 151 106 152 145 158 176 173 154 148 163 188 150 203 112 137 Limiting viscosity [η] (dL / g) 0.92 0.45 0.20 0.72 0.58 0.51 0.20 1.44 2.03 0.50 0.40 1.05 0.36 0.30 0.33 0.50 Mw (g / mol) 217,000 124,000 34,300 310,000 84,800 112,000 35,800 450,000 634,000 97,200 95,500 320,000 62,200 67,200 88,000 99,200 Mw / Mn 2.43 2.07 1.76 1.84 4.75 4.38 2.19 3.55 2.33 2.47 2.90 2.17 2.05 3.03 6.90 2.80 structural regularity (Exo-racemic structure / meso-racemic structure) 0.89 0.72 0.79 0.89 0.64 0.54 1.00 1.00 1.00 0.00 0.50 1.00 0.14 1.00 0.26 0.00 Solubility relative to methylcyclohexane A A A A A A A A A C A A B A B C Solubility relative to toluene A A A A B A A B A C A B B B A C The chain (mol%) of the constituent unit (B) 1.0 1.9 2.2 4.0 0.5 2.0 1.2 2.6 1.7 0.0 3.2 3.7 1.4 5.1 0.0 0.0 Formability (pressing) A A A A A A B A A C A A B C B C

[0144] In each embodiment, the coexistence of racemic and meso compounds results in high solubility relative to methylcyclohexane and toluene. On the other hand, in each comparative example, the solubility relative to methylcyclohexane and toluene remains low.

[0145] This application claims priority based on Japanese Patent Application No. 2021-106711 filed on June 28, 2021 and Japanese Patent Application No. 2022-006837 filed on January 20, 2022, the entire disclosure of which is incorporated herein by reference.

Claims

1. A cyclic olefin polymer having a norbornene backbone, wherein the cyclic olefin polymer is a cyclic olefin copolymer and satisfies the following necessary conditions (a), (b-1), and (b-2), wherein the glass transition temperature of the cyclic olefin copolymer, as measured by a differential scanning calorimeter, is 83°C or higher and 169°C or lower, wherein the cyclic olefin copolymer comprises: 40 mol% to 77 mol% of a constituent unit (A) derived from ethylene or propylene; and 23 mol% to 60 mol% of a constituent unit (B) derived from one or more cyclic monomers selected from the group consisting of general formulas [ZI] and [Z-IV]. (In the formula [ZI], u is 0 or 1, v is 0 or a positive integer, w is 0 or 1; R61 to R78 and Ra1 and Rb1 each independently comprise one or more groups selected from hydrogen atoms, halogen atoms, and hydrocarbon groups; R75 to R78 can be bonded to each other to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring may also have double bonds; in addition, R75 and R76, or R77 and R78 may also form alkylene rings) (In the general formula [Z-IV], x is an integer greater than or equal to 0; R111 to R118 are each independently selected from hydrogen atoms, halogen atoms, and hydrocarbon groups; R121 to R124 are each independently selected from hydrogen atoms, halogen atoms, and hydrocarbon groups, and two adjacent groups may also be bonded to each other to form a monocyclic or polycyclic aromatic ring) The total of the constituent unit (A) and the constituent unit (B) is 100 mol%, (necessary condition (a)) The cyclic olefin polymer comprises a chain olefin (A) and a cyclic olefin (B) having a norbornene backbone, and the ratio of meso to racemic structures (racemic structure / meso structure) in the chain of the constituent unit (B)-the constituent unit (A)-the constituent unit (B) as determined by 13C-NMR is 0.01 to 100; (necessary condition (b-1)) the proportion of the chain of the constituent unit (B)-the constituent unit (B) in the constituent unit (B) as determined by 13C-NMR is 0.3 mol% or more; (necessary condition (b-2)) the proportion of the chain of the constituent unit (B)-the constituent unit (B) in the constituent unit (B) as determined by 13C-NMR is 10 mol% or less.

2. The cyclic olefin polymer as claimed in claim 1, wherein the cyclic olefin copolymer comprises 50 mol% to 75 mol% of the constituent unit (A) and 25 mol% to 50 mol% of the constituent unit (B).

3. The cyclic olefin polymer as claimed in claim 1 or claim 2, wherein the limiting viscosity of the cyclic olefin copolymer is 0.1 [dL / g] or more and 5.0 [dL / g] or less.

4. The cyclic olefin polymer as claimed in claim 1 or claim 2, wherein the weight average molecular weight (Mw) of the cyclic olefin copolymer determined by gel permeation chromatography is 1,000 or more and 4,500,000 or less.

5. The cyclic olefin polymer as claimed in claim 1 or claim 2, wherein the molecular weight distribution (Mw / Mn) of the cyclic olefin copolymer determined by gel permeation chromatography is 1.76 or more and 6.90 or less.

6. A cyclic olefin polymer composition comprising any one of claims 1 to 5.

7. The cyclic olefin polymer composition as described in claim 6 is used in optical components, film packaging materials, optical films, or medical components.

8. A molded article comprising a cyclic olefin polymer as described in any one of claims 1 to 5.

9. The molded body as described in claim 8 is an optical component, a film packaging material, an optical film, or a medical component.

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