Cyclic olefin polymers, cyclic olefin polymer compositions and molded articles

Abstract

A cyclic olefin polymer having 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 requirement (a). Requirement (a): The cyclic olefin polymer is composed of structural units (A) as chain olefins and structural units (B) containing cyclic olefins having a norbornene backbone, through… 13 The ratio of meso-racemic structures to racemic structures (racemic structure / meso-racemic structure) in the chain of the above-mentioned structural unit (B)-the above-mentioned structural unit (A)-the above-mentioned structural unit (B) determined by C-NMR is 0.01 to 100.

Description

Technical Field

[0001] This invention relates to cyclic olefin polymers, cyclic olefin polymer compositions, and molded articles. Background Technology

[0002] Cyclic olefin copolymers are used in optical lenses such as camera lenses, fθ lenses, and pickup lenses. Cyclic olefin copolymers used in such molded 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 are copolymerized with cyclic olefins in the presence of a catalyst formed by a coordination metal compound of group IVB of the periodic table (A) and an organoaluminooxy compound (B), wherein the coordination metal compound of group IVB of the periodic table (A) is a polydentate coordination compound formed by combining at least two different cycloalkadienyl groups or their substitutes via a hydrocarbon group or a methylene silyl group or a substituted methylene silyl group as a ligand.

[0005] In addition, Patent Document 3 discloses an ethylene-cyclic olefin copolymer, which is formed by random copolymerization of (a) ethylene with 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 aforementioned transition metal complex (converted to aluminum atoms), are contacted with a solvent; 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 aforementioned contacting step and containing organoaluminum at a concentration of 0.005 mmol / L or more (converted to aluminum atoms).

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

[0008] In addition, Patent Document 5 discloses a cyclic olefin copolymer composition, characterized in that it comprises [A] a cyclic olefin polymer selected from a specific structure and having a softening temperature of 120 to 300°C, and [B] a cyclic olefin polymer with a glass transition point of 50°C or less, wherein 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 ASTM D542 is below a specific range, and [B] is contained in an amount of 5 to 50 parts by weight relative to 50 to 95 parts by weight of [A].

[0009] Existing technical documents

[0010] Patent documents

[0011] Patent Document 1: Japanese Patent Application Publication No. 10-287713

[0012] Patent Document 2: Japanese Patent Application Publication No. 2-173112

[0013] Patent Document 3: Japanese Patent Application Publication No. 2005-330465

[0014] Patent Document 4: Japanese Patent Application Publication No. 2018-165308

[0015] Patent Document 5: International Publication No. 2008 / 068897

[0016] Non-patent literature

[0017] 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, Vol. 34, No. 20, pp. 2273-2275;

[0018] 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

[0019] The problem that the invention aims to solve

[0020] It is known that cyclic olefin copolymers or ring-opening polymers with a norbornene structure generally have low solubility in solvents. According to the research of the inventors, in the inventions described in the aforementioned Patent Documents 1 to 5, it has been clarified that solvents such as methylcyclohexane and toluene, which are difficult to dissolve in polymer coatings, especially at or near room temperature, cannot produce homogeneous solutions.

[0021] The present invention was 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.

[0022] Methods for solving problems

[0023] The inventors conducted repeated and in-depth research to solve the aforementioned problems. As a result, they discovered that cyclic olefin copolymers having a norbornene structure or ring-opening polymers having a norbornene backbone exhibit higher solubility in solvents if they possess specific stereoregularity, thus completing the present invention. Specifically, according to the present invention, a cyclic olefin polymer, a cyclic olefin polymer composition, and a molded article are provided as shown below. [1]

[0025] A cyclic olefin polymer, which is a cyclic olefin polymer having a norbornene backbone, characterized in that...

[0026] The above-mentioned cyclic olefin polymer is a cyclic olefin copolymer or a cyclic olefin ring-opening polymer, and satisfies the following requirement (a).

[0027] (Requirement (a))

[0028] This cyclic olefin polymer is composed of structural units (A) that are chain olefins and structural units (B) that contain cyclic olefins with a norbornene backbone.

[0029] pass 13 The ratio of racemic to exoracemic structures in the chain of the above-mentioned structural unit (B)-the above-mentioned structural unit (A)-the above-mentioned structural unit (B) determined by C-NMR is 0.01 to 100. [2]

[0031] The cyclic olefin polymer described above [1] is a cyclic olefin copolymer.

[0032] The above-mentioned cyclic olefin copolymer comprises 30-80 mol% of the above-mentioned structural unit (A) and 20-70 mol% of the above-mentioned structural unit (B).

[0033] The aforementioned structural unit (A) is a structural unit derived from ethylene or an α-olefin with 3 to 30 carbon atoms.

[0034] The aforementioned structural unit (B) is a structural unit derived from one or more cyclic monomers selected from the group consisting of the following general formulas [ZI], [Z-II], [Z-III], and [Z-IV].

[0035] [Chemistry 1]

[0036]

[0037] (In the above formula [ZI], u is 0 or 1, v is 0 or a positive integer, and w is 0 or 1. R) 61 ~R 78 and R a1 and R b1 Each independently contains one or more elements selected from the group consisting of hydrogen atoms, halogen atoms, and hydrocarbon groups, R 75 ~R 78 They can combine to form single or multiple rings, and these single or multiple rings can have double bonds. Additionally, R... 75 With R 76 、or R 77 With R 78 It can form alkylidene groups.

[0038] [Chemistry 2]

[0039]

[0040] (In the above formula [Z-II], x and d are integers greater than or equal to 0 or 1, and y and z are 0, 1, or 2. R) 81 ~R99 Each is independently selected from hydrogen atoms, halogen atoms, and hydrocarbon groups, R 89 and R 90 The carbon atom that is bonded to R 93 The bonded carbon atom or R 91 The bonded carbon atoms can be directly bonded or bonded via alkylene groups having 1 to 3 carbon atoms. Additionally, when y = z = 0, R... 95 With R 92 Or R 95 With R 99 They can combine to form monocyclic or polycyclic aromatic rings.

[0041] [Chemistry 3]

[0042]

[0043] (In the above formula [Z-III], n and m are each independently 0, 1, or 2, and q is 1, 2, or 3. R) 18 ~R 31 Each group consists independently of a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group with 1 to 20 carbon atoms that can be substituted by a halogen atom other than a fluorine atom.

[0044] [Chemistry 4]

[0045]

[0046] (In the general formula [Z-IV], x is an integer greater than or equal to 0 or 1, R) 111 ~R 118 Each is independently selected from hydrogen atoms, halogen atoms, and hydrocarbon groups. R 121 ~R 124 Each group is independently selected from hydrogen atoms, halogen atoms, and hydrocarbon groups; two adjacent groups can combine to form monocyclic or polycyclic aromatic rings.

[0047] The total of the above structural unit (A) and the above structural unit (B) is 100 mol%. [3]

[0049] The cyclic olefin polymers as described in [1] or [2] above are characterized by further satisfying the following requirement (b).

[0050] (Requirement (b))

[0051] pass 13 The proportion of the chain of the above-mentioned structural unit (B) in the structural unit (B) as determined by C-NMR is more than 0.1 mol% and less than 20.0 mol%. [4]

[0053] The cyclic olefin polymers described in any one of [1] to [3] above have a glass transition temperature of 50°C or more and 250°C or less, as determined by differential scanning calorimetry (DSC). [5]

[0055] The cyclic olefin polymers described in any one of [1] to [4] above have a glass transition temperature of 50°C or more and 180°C or less, as determined by differential scanning calorimetry (DSC). [6]

[0057] The cyclic olefin polymer as described in any one of [1] to [5] above, wherein the intrinsic viscosity of the cyclic olefin copolymer or the cyclic olefin ring-opening polymer is 0.1 [dL / g] or more and 5.0 [dL / g] or less. [7]

[0059] A cyclic olefin polymer composition comprising any one of the cyclic olefin polymers described in [1] to [6] above. [8]

[0061] The cyclic olefin polymer composition described above [7] is used for optical components, film packaging materials, optical films or medical components. [9]

[0063] A molded body comprising any one of the cyclic olefin polymers described in any one of [1] to [6] above.

[10]

[0065] The molded body described above [9] is an optical component, a film packaging material, an optical film, or a medical component.

[0066] Invention Effects

[0067] If the cyclic olefin polymer of the present invention has a norbornene backbone, it exhibits higher solvent solubility compared to conventional cyclic olefin copolymers or ring-opening polymers. Therefore, it can readily dissolve in solvents such as methylcyclohexane and toluene used in 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 molded articles such as films, resulting in excellent mechanical strength and elongation. Detailed Implementation

[0068] The present invention will now be described based on embodiments. It should be noted that, in this embodiment, unless otherwise specified, "A to B" indicating a numerical range means A or more and B or less. Furthermore, unless otherwise specified, "cyclic olefin polymer" means copolymer and / or ring-opening polymer.

[0069] As described above, based on the inventors' understanding, it is known that conventional cyclic olefin copolymers or ring-opening polymers generally have low solvent solubility. The inventors conducted repeated and in-depth research to solve the above-mentioned problem. As a result, it was discovered that cyclic olefin polymers with specific stereoregularity exhibit higher solvent solubility, thus completing the present invention.

[0070] That is, the cyclic olefin polymer of this embodiment is as follows.

[0071] <Cyclic olefin polymers with norbornene backbone>

[0072] A cyclic olefin polymer, which is a cyclic olefin polymer having a norbornene backbone, characterized in that...

[0073] The above-mentioned cyclic olefin polymer is a cyclic olefin copolymer or a cyclic olefin ring-opening polymer, and satisfies the following requirement (a).

[0074] (Requirement (a))

[0075] This cyclic olefin polymer is composed of structural units (A) that are chain olefins and cyclic olefin structural units (B) that have a norbornene backbone. 13 The ratio of racemic to exoracemic structures in the chain of the above-mentioned structural unit (B)-the above-mentioned structural unit (A)-the above-mentioned structural unit (B) determined by C-NMR is 0.01 to 100.

[0076] If the polymer is a cyclic olefin polymer with a norbornene backbone as described in this embodiment, its solubility in solvents is increased due to its specific stereoregularity. In particular, it can be readily dissolved in solvents (e.g., methylcyclohexane, toluene, etc.) used when coating the polymer at or near room temperature. Therefore, since a homogeneous solution can be obtained, there is no inhomogeneity when forming molded articles such as films, resulting in excellent mechanical strength and elongation.

[0077] Cyclic olefin copolymers with specific stereoregularity can be dissolved in solvents other than methylcyclohexane, such as toluene. The solubility parameter (SP value) of cyclic olefin copolymers varies depending on the composition of the structural unit (A) which is a chain olefin and the structural unit (B) which contains a cyclic olefin with a norbornene backbone. Therefore, depending on the difference in SP value, the solubility in toluene solvent is sometimes also high.

[0078] First, the specific stereoregularity of 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 the above-mentioned structural unit (B)-structural unit (A)-structural 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 the same figure.

[0079] [Chemistry 5]

[0080]

[0081] In the above general formula (I), m and n represent repeating units. Here, if the structure derived from norbornene is denoted as NB and the structure derived from ethylene is denoted as E, then in the above example, the connection is ... -NB-E -NB-E -NB-E - ... . The above meso and racemic structures can be obtained through ... 13 It is determined by C-NMR. An example of its binding mode is shown below.

[0082] [Chemistry 6]

[0083]

[0084] Typically, cyclic olefin copolymers with a norbornene skeleton or ring-opening polymers with a norbornene skeleton synthesized without controlling stereoregularity are either meso compounds or racemic compounds, and have low solubility in solvents.

[0085] On the other hand, regarding the cyclic olefin polymer with a norbornene backbone of this embodiment, 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 racemic to meso structures representing stereoregularity [racemic / meso], is generally 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, and even more preferably 0.5 to 0.9. By having the racemic / meso ratio within the above range, the solubility in solvents is improved. The stereoregularity described above can be appropriately adjusted by selecting the catalyst and co-catalyst used in polymerization, as described later.

[0086] about 13 There are no particular limitations to C-NMR measurements, as long as they can distinguish between meso and racemic structures. 13C-NMR measurements, for example, can be illustrated below. For more details... 13 C-NMR measurements will be explained in the section on stereoregularity later.

[0087] Apparatus: Burker Biospin AVANCE IIIcryo-500 MRI scanner

[0088] Measurement nucleus: 13 C

[0089] Frequency: 125MHz

[0090] Measurement mode: Single-pulse proton (with reverse grid) decoupling

[0091] Pulse width: 90 degrees

[0092] Points accumulated: 64000

[0093] Measurement range: -55 to 195 ppm (total 250 ppm)

[0094] Repeat time: 12 seconds

[0095] Total number of times: 256

[0096] Solvent: 1,1,2,2-Tetrachloroethane-d2

[0097] Concentration: 10% w / v

[0098] Temperature: 120℃

[0099] Chemical shift standard: tetramethylsilyl quasi-(1,1,2,2-tetrachloroethane-d2: equivalent to 74.2 ppm)

[0100] [Cyclic olefin polymers with a norbornene backbone]

[0101] The cyclic olefin copolymers having a norbornene backbone (hereinafter also referred to as cyclic olefin copolymers) or cyclic olefin ring-opening polymers having a norbornene backbone (hereinafter also referred to as cyclic olefin ring-opening polymers) of this embodiment will be described in detail.

[0102] Cyclic olefin copolymers and cyclic olefin ring-opening polymers are composed of structural units (A) having a norbornene backbone and being chain olefins, and structural units (B) containing cyclic olefins having a norbornene backbone.

[0103] (Cyclic olefin copolymer)

[0104] From the viewpoint of being able to maintain a good balance between the transparency and refractive index of the obtained optical components and further improve heat resistance or moldability, the cyclic olefin copolymer of this embodiment preferably has the following structural unit (A) and structural unit (B).

[0105] Structural unit (A): Structural unit derived from ethylene or α-olefins with 3 to 30 carbon atoms.

[0106] Structural unit (B): Derived from at least one structural unit selected from the group consisting of structural units represented by the following general formula (ZI), structural units represented by the following general formula (Z-II), structural units represented by the following general formula (Z-III), and structural units represented by the following general formula (Z-IV).

[0107] [Chemistry 7]

[0108]

[0109] In the above formula [ZI], u is 0 or 1, v is 0 or a positive integer, preferably an integer greater than or equal to 1, more preferably 1 or 2, and even more preferably 1, w is 0 or 1. R 61 ~R 78 and R a1 and R b1 Each is independently selected from hydrogen atoms, halogen atoms, and hydrocarbon groups.

[0110] [Chemistry 8]

[0111]

[0112] In the above formula [Z-II], x and d are integers of 0 or 1 or higher, and y and z are 0, 1, or 2. X is preferably an integer of 1 or higher, more preferably 1 or 2, and even more preferably 1. R 81 ~R 99 Each is independently selected from hydrogen atoms, halogen atoms, and hydrocarbon groups. R 89 and R 90 The carbon atom that is bonded to R 93 The bonded carbon atom or R 91 The bonded carbon atoms can be directly bonded or bonded via alkylene groups having 1 to 3 carbon atoms. Additionally, when y = z = 0, R... 95 With R 92 Or R 95 With R 99 They can combine with each other to form monocyclic or polycyclic aromatic compounds.

[0113] [Chemistry 9]

[0114]

[0115] In the above [Z-III] formula, n and m are each independently 0, 1, or 2, and q is 1, 2, or 3. R 18 ~R 31 Each is independently a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group with 1 to 20 carbon atoms that can be substituted by a halogen atom other than a fluorine atom. Additionally, when q = 1, R 28 With R 29 R 29 With R 30 R 30 With R 31 They can combine to form single or multiple rings. Additionally, when q = 2 or 3, R... 28 With R 28 R 28 With R 29 R 29 With R 30 R 30 With R 31 R 31 With R 31 They can combine to form monocyclic or polycyclic rings, which may have double bonds and may be aromatic rings. In formula [Z-III], n and m are preferably 0 and q is 1, 2 or 3. In formula [Z-III], n and m are more preferably 0 and q is 1.

[0116] [Chemistry 10]

[0117]

[0118] In the above [Z-IV] formula, x is an integer greater than or equal to 1 or 0. Additionally, R... 111 ~R 118 Each is independently selected from hydrogen atoms, halogen atoms, and hydrocarbon groups, R 121 ~R 124 Each group is independently selected from hydrogen atoms, halogen atoms, and hydrocarbon groups. Two adjacent groups can combine with each other to form monocyclic or polycyclic aromatic rings.

[0119] By using cyclic olefin monomers represented by the above-mentioned [ZI] formula, [Z-II] formula, [Z-III] formula or [Z-IV] formula as copolymer components, the solubility of cyclic olefin copolymers in solvents is further improved, thereby improving moldability and increasing the yield of finished products.

[0120] When the total percentage of structural unit (A) and structural unit (B) is set to 100 mol%, structural unit (A) is preferably 30–80 mol%, more preferably 40–77 mol%, and even more preferably 50–75 mol%, and structural unit (B) is preferably 20–70 mol%, more preferably 23–60 mol%, and even more preferably 25–50 mol%. By setting the ratio of structural unit (A) and structural unit (B) within the above-mentioned range, the solubility of the cyclic olefin copolymer in solvents is further improved, thereby improving its moldability and increasing the yield of the finished product.

[0121] The proportion of structural units (A) derived from olefins can be determined by... 13 The determination was performed using C-NMR.

[0122] In this embodiment, the olefin monomer, which is one of the copolymerization raw materials for the olefin copolymer, is an olefin monomer that forms the above-mentioned structural unit (A) through addition polymerization. Specifically, for example, an olefin monomer represented by the following general formula (Ia) can be exemplified.

[0123] [Chemistry 11]

[0124]

[0125] In the above general formula (Ia), R 300 A straight-chain or branched hydrocarbon group representing 1 to 28 hydrogen or carbon atoms.

[0126] Examples of olefin monomers represented by the above 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, and 1-eicosene. From the viewpoint of obtaining optical components with superior heat resistance, mechanical properties, and optical properties, ethylene and propylene are preferred, with ethylene being particularly preferred. Two or more olefin monomers represented by the above general formula (Ia) may be used. From the viewpoint of obtaining optical components with superior formability and optical properties, the olefin monomer represented by the above general formula (Ia) preferably does not have acyclic dienes.

[0127] Specific examples of cyclic olefin monomers represented by the above-described [ZI], [Z-II], [Z-III], or [Z-IV] formulas 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, and pentacyclo-3-hexadecene derivatives. Alkene 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 cycloalkylene derivatives with 3 to 20 carbon atoms.

[0128] The weight-average molecular weight of the cyclic olefin monomer represented by the above-described [ZI], [Z-II], [Z-III], or [Z-IV] formulas 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.

[0129] Furthermore, when the cyclic olefin polymer contains one or more cyclic olefin monomers selected from the group consisting of general formulas [ZI], [Z-II], [Z-III] and [Z-IV], it is preferable that at least one of these cyclic olefin monomers has a weight-average molecular weight of 100 g / mol or more and 500 g / mol or less.

[0130] The monomers are selected from one or two of the cyclic olefin monomers represented by the [ZI], [Z-II], [Z-III] and [Z-IV] formulas, preferably cyclic olefins represented by one or two of the [ZI] and [Z-IV] formulas.

[0131] As the cyclic olefin monomer represented by the above [ZI] formula, it is preferable to use a monomer selected from bicyclo[2.2.1]-2-heptene (also known as norbornene), tetracyclo[4.4.0.1]-2-heptene, etc. 2,5 .1 7,10One or more of the following: 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, preferably tetracyclo[4.4.0.1]hept-2-ene. 2,5 .1 7,10 ]-3-Dodecene. These cyclic olefins have a rigid ring structure, thus having the advantage of easily maintaining the elastic modulus of the copolymer and optical components. As cyclic olefin monomers represented by the above [ZI] formula, from the viewpoint of obtaining optical components with better formability and optical properties, it is preferable that they do not have polar groups.

[0132] The copolymer type of the copolymer in this embodiment is not particularly limited; for example, random copolymers and block copolymers can be cited. In this embodiment, considering the possibility of obtaining optical components with excellent optical properties such as transparency, refractive index, and birefringence, and high precision, random copolymers are preferably used as the copolymer in this embodiment.

[0133] The copolymer used in this embodiment is preferably ethylene and tetracyclo[4.4.0.1]. 2,5 .1 7,10 Random copolymers of 1-3-dodecene (hereinafter 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, copolymers of ethylene and 5-(ethylphenyl)-bicyclo[2.2.1]hept-2-ene, copolymers of ethylene and 5-(isopropylphenyl)-bicyclo[2.2.1]hept-2-ene -2-ene copolymers, 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 benzonorbornediene or BNBD), copolymers of ethylene with tetracyclo[4.4.0.1]hept-2-ene. 2,5 .1 7,10 A copolymer of 3-dodecene and 1,4-dihydro-1,4-methylnaphthalene, and ethylene with tetracyclo[4.4.0.1] 2,5 .1 7,10Copolymers of 1,4,4a,9a-tetrahydro-1,4-methyl-bridged fluorene (hereinafter referred to as indobornene), copolymers of ethylene with norbornene with 1,4-dihydro-1,4-methyl-bridged naphthalene, copolymers of ethylene with norbornene with indobornene, and copolymers of ethylene with tetracyclo[4.4.0.1] 2,5 .1 7,10 A copolymer of 3-dodecene and norbornene, more preferably ethylene and tetracyclo[4.4.0.1] 2,5 .1 7,10 Random copolymers of 3-dodecene, copolymers of ethylene and 1,4-dihydro-1,4-methylnaphthalene, and copolymers of ethylene and tetracyclo[4.4.0.1] 2,5 .1 7,10 A copolymer of 3-dodecene and 1,4-dihydro-1,4-methylnaphthalene, and ethylene with tetracyclo[4.4.0.1] 2,5 .1 7,10 A copolymer of 3-dodecene and norbornene, more preferably ethylene and tetracyclo[4.4.0.1] 2,5 .1 7,10 Random copolymers of 3-dodecene, copolymers of ethylene and 1,4-dihydro-1,4-methylnaphthalene, and copolymers of ethylene and tetracyclo[4.4.0.1] 2,5 .1 7,10 A copolymer of 3-dodecene and 1,4-dihydro-1,4-methylnaphthalene.

[0134] The copolymers in this embodiment can be used alone or in combination of two or more.

[0135] The copolymer of this embodiment can be manufactured, for example, by selecting suitable conditions according to the methods of 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 Publishers No. 2015 / 122415, Japanese Patent Application Publication No. 2007-063409, and Japanese Patent Application Publication No. 2-173112.

[0136] (Ring-opening polymers of cyclic olefins)

[0137] The cyclic olefin ring-opening polymer of this embodiment is a cyclic olefin ring-opening polymer having a norbornene backbone. From the viewpoint of being able to maintain a good balance between the transparency and refractive index of the obtained optical component and further improve heat resistance or moldability, it is preferable to have a structure derived from at least one of the structural units selected from the group consisting of the structural units represented by the above general formula (ZI), the above general formula (Z-II), and the above general formula (Z-IV). However, u=v=0 in the above general formula (ZI), x=0 in the above general formula (Z-II), and x=0 in the above general formula (Z-IV) are excluded. The carbon-carbon bonds formed by the ring-opening of carbon-carbon double bonds in the above general formulas (ZI), (Z-II), and (Z-IV) correspond to structural unit (A), and the parts other than those corresponding to structural unit (A) correspond to structural unit (B).

[0138] That is, the ring-opening polymer preferably has structural units derived from the same structural units as the copolymer component.

[0139] {Stage regularity}

[0140] The structural regularity of this embodiment is achieved through 13 The determination was performed using C-NMR. 13 There are no particular limitations to C-NMR measurements as long as they can distinguish between meso and racemic structures. An example of specific measurement conditions is described above.

[0141] Here, the meso-racemic structure and the exo-racemic structure are shown. 13 The location of the C-NMR signal varies depending on the polymer (polymer, ring-opening polymer). Some implementation methods are described below. 13 The location of C-NMR signals and the method for measuring the signals.

[0142] (A: The case of polymers of ethylene and TD)

[0143] As a cyclic olefin polymer, it has ethylene and the structure represented by the above [ZI] formula, 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).

[0144] against 13 C-NMR spectrum,

[0145] • The integral value (X) of the signal in the range of 38.7–39.7 ppm A )

[0146] • The integral value (Y) of the signal in the range of 40.3 to 41.2 ppm A )

[0147] Defined as stereoregularity = XA / Y A The ratio is 0.01 to 100, preferably 0.1 to 10.0, more preferably 0.2 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, and most preferably 0.5 to 0.9.

[0148] A: In the case of the polymer of ethylene and TD, only one peak appears in the range, so it is set as the integral value of the signal.

[0149] (B: The case of polymers of ethylene and NB)

[0150] As a cyclic olefin polymer, it has ethylene and the structural unit represented by the above [ZI] formula, u=v=0, and the [ZI] formula does not have an aromatic ring (i.e., the case of a polymer of ethylene and NB).

[0151] against 13 C-NMR spectrum,

[0152] The total integral value of the signal in the range of 44.6 to 45.6 ppm (X B )

[0153] The total integral value of the signal in the range of 45.6 to 46.0 ppm (Y) B )

[0154] Defined as stereoregularity = X B / Y B The ratio is 0.01 to 100, preferably 0.01 to 50.0, more preferably 0.05 to 5.0, more preferably 0.25 to 4.0, and most preferably 0.3 to 3.0.

[0155] B: In the case of the polymer of ethylene and NB, multiple peaks appear in the range, so they are set as the sum of the integral values ​​of the signal.

[0156] (C: The case of polymers of ethylene and BNBD)

[0157] As a cyclic olefin polymer, it has the case of ethylene and the structural unit represented by the above [Z-III] formula (i.e., the case of a polymer of ethylene and BNBD).

[0158] against 13 C-NMR spectrum,

[0159] • The integral value (X) of the signal in the range of 30.8–31.3 ppm CThe value (X) is obtained by subtracting the integral value (Z) of the signal in the range of 30.1 to 30.8 ppm. C -Z)

[0160] • The integral value (Y) of the signal in the range of 31.3 to 31.8 ppm C )

[0161] Defined as stereoregularity = (X C -Z) / Y C The ratio is 0.01 to 100, preferably 0.01 to 10.0. More preferably 0.05 to 5.0, more preferably 0.1 to 1.0. Most preferably 0.3 to 1.0. This value is obtained by subtracting the integral value (Z) of the signal in the range of 30.1 to 30.8 ppm from the peak containing a portion of the signal equivalent to BNBD-ethylene n-BNBE- (n=2 or more).

[0162] (D: The case of polymers of ethylene, TD and BNBD)

[0163] As a cyclic olefin polymer, it includes the following cases: ethylene, the structure represented by the above [ZI] formula where u=0, v=1 and there is no aromatic ring, and the structural unit represented by the above [Z-III] formula (i.e., the case of a polymer of ethylene, TD and BNBD).

[0164] against 13 C-NMR spectrum,

[0165] • The integral value (X) of the signal in the range of 38.7–39.7 ppm D )

[0166] • The integral value (Y) of the signal in the range of 40.3 to 41.2 ppm D )

[0167] X D / Y D The ratio is 0.01 to 100, preferably 0.01 to 10.0, more preferably 0.05 to 5.0, more preferably 0.1 to 1.0, and most preferably 0.3 to 1.0.

[0168] In addition, regarding 13 C-NMR spectrum,

[0169] • The integral value (M) of the signal in the range of 43.6 to 43.8 ppm D )

[0170] • The integral value (N) of the signal in the range of 44.5 to 45.0 ppmD )

[0171] M D / N D The ratio is 0.01 to 100, preferably 0.01 to 10.0, more preferably 0.05 to 5.0, more preferably 0.1 to 1.0, and most preferably 0.3 to 1.0.

[0172] D: In the case of polymers of ethylene, TD, and BNBD, peaks of TD-ethylene-TD and BNBD-ethylene-BNBD will appear in the range, therefore X D Y D Let M be the integral value of the TD-ethylene-TD signal. D N D Let the integral value of BNBD-ethylene-BNBD be defined as stereoregularity = X. D / Y D +M D / N D The stereoregularity = X D / Y D +M D / N D The ratio is preferably 0.01 to 100, more preferably 0.01 to 10.0, even more preferably 0.05 to 5.0, even more preferably 0.1 to 1.0, and most preferably 0.3 to 1.0.

[0173] The cyclic olefin polymer of this embodiment preferably satisfies the following requirement (b).

[0174] (Requirement (b))

[0175] pass 13 The proportion of the chain of the above-mentioned structural unit (B) in the structural unit (B) as determined by C-NMR is more than 0.1 mol% and less than 20.0 mol%.

[0176] Here, when a signal is detected in the range of 51.2–55.5 ppm, by… 13 The proportion of the chain of the above-mentioned structural unit (B) in structural unit (B) as determined by C-NMR can be obtained by using... 13 C-NMR spectrum

[0177] • Total integral value (P) of signals detected in the range of 51.2–55.5 ppm

[0178] • Total integral value (Q) of the signal detected in the range of 54.0–54.6 ppm

[0179] The value of (PQ), obtained by subtracting (Q) from (P), is then divided by (P) to calculate the result.

[0180] At this time, the above-mentioned passage 13 The proportion of the chain of the aforementioned structural unit (B) as determined by C-NMR is preferably 0.1 mol% to 20 mol% or less, more preferably 0.3 mol% to 10 mol% or less, even more preferably 0.6 mol% to 5.0 mol% or less, even more preferably 0.8 mol% to 4.5 mol% or less, and even more preferably 1.0 mol% to 3.6 mol% or less. This corresponds to the content of chains formed by cyclic olefin compounds having a norbornene backbone, for example, chains formed by TD and TD. By having them within the above range, aggregation is suppressed, and the solubility of the polymer becomes higher.

[0181] Additionally, when a signal is detected in the range of 40.0–50.0 ppm, by… 13 The proportion of the chain of the above-mentioned structural unit (B) in structural unit (B) as determined by C-NMR can be obtained by using... 13 C-NMR spectrum

[0182] • Total integral value (T) of signals detected in the range of 40.0–50.0 ppm

[0183] • Total integral value (U) of signals detected in the range of 45.0–46.0 ppm

[0184] The (U / T) value obtained by dividing (U) by (T) is multiplied by 2.5, then multiplied by the composition ratio of BNBD and divided by 100 to calculate.

[0185] At this time, the above-mentioned passage 13 The proportion of the chain of the aforementioned structural unit (B) as determined by C-NMR is preferably 0.1 mol% to 20 mol% or less, more preferably 0.3 mol% to 10 mol% or less, even more preferably 0.6 mol% to 5.0 mol% or less, even more preferably 0.8 mol% to 4.5 mol% or less, and even more preferably 1.0 mol% to 3.6 mol% or less. This corresponds to the content of chains formed by cyclic olefin compounds having a norbornene backbone, such as chains formed by BNBD and BNBD. By having them within the above range, aggregation is suppressed, and the solubility of the polymer becomes higher.

[0186] Here, when signals are detected in both the 40.0–50.0 ppm range and the 51.2–55.5 ppm range, by… 13 The proportion of the chain of the above-mentioned structural unit (B) in the structural unit (B) as determined by C-NMR can be calculated by summing the proportions in the structural unit (B) calculated separately using the above method.

[0187] At this time, the above-mentioned passage 13 The proportion of the chain of the aforementioned structural unit (B) as determined by C-NMR is preferably 0.1 mol% to 20 mol% or less, more preferably 0.3 mol% to 10 mol% or less, even more preferably 0.6 mol% to 5.0 mol% or less, even more preferably 0.8 mol% to 4.5 mol% or less, and even more preferably 1.0 mol% to 3.6 mol% or less. This corresponds to the content of chains formed by cyclic olefin compounds having a norbornene skeleton, for example, the total amount of chains formed by TD and BNBD. By having them within the above range, aggregation is suppressed, and the solubility of the polymer becomes higher.

[0188] The lower limit of the glass transition temperature (Tg) of the cyclic olefin polymer in this embodiment is preferably 50°C or higher, more preferably 83°C or higher, and particularly preferably 110°C or higher.

[0189] In addition, the upper limit of Tg is preferably below 250°C, more preferably below 200°C, even more preferably below 180°C, even more preferably below 169°C, even more preferably below 165°C, and particularly preferably below 160°C.

[0190] In this embodiment, when the cyclic olefin polymer is a cyclic olefin copolymer having the aforementioned structural unit (A) and the aforementioned structural unit (B), by having Tg at or above the aforementioned lower limit value, 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 value, aggregation can be suppressed, thereby increasing the polymer's solubility.

[0191] Furthermore, if the Tg is within the aforementioned range, sufficient heat resistance and good moldability can be obtained when used as a component requiring heat resistance. Generally, the Tg of cyclic olefin polymers varies depending on the composition of structural unit (A) and structural unit (B), and Tg tends to increase with increasing content of structural unit (B). However, even with the same composition, Tg tends to become higher when the number of chains of structural unit (B) increases, for reasons unknown. Such a Tg can be obtained by making the proportion of the chains of structural unit (B) derived from one or more cyclic monomers selected from the group consisting of [ZI], [Z-II], [Z-III], and [Z-IV] in the total structural unit (B) contained in the cyclic olefin copolymer, for example, between 0.1 mol% and 20.0 mol%.

[0192] The glass transition temperature can be determined using a differential scanning calorimeter (DSC). For specific measurement conditions, for example, using a Hitachi Advanced Scientific Corporation DSC-7020, the temperature is increased from room temperature to 250°C at a rate of 10°C / min under a nitrogen atmosphere, 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 heating to 300°C at a rate of 10°C / min.

[0193] The molecular weight of the cyclic olefin polymer in this embodiment is not particularly limited. When using intrinsic 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 to 5.0 or less, more preferably 0.2 to 3.0 or less, and most preferably 0.2 to 2.0 or less.

[0194] In this embodiment, when the cyclic olefin polymer is a cyclic olefin copolymer having the aforementioned structural unit (A) and the aforementioned structural unit (B), the weight-average molecular weight (Mw) determined by gel permeation chromatography (GPC) is in the range of 1,000 ≤ Mw ≤ 4,500,000, preferably in the range of 3,000 ≤ Mw ≤ 3,000,000, more preferably in the range of 5,000 ≤ Mw ≤ 2,000,000, even more preferably in the range of 10,000 ≤ Mw ≤ 1,000,000, and most preferably in the range of 30,000 ≤ Mw ≤ 500,000.

[0195] If the intrinsic viscosity and weight-average molecular weight (Mw) are above the lower limit mentioned above, the solubility in the solvent or the mechanical strength of the molded article can be improved. Conversely, if the intrinsic viscosity is below the upper limit mentioned above, the moldability can be improved.

[0196] In addition, the cyclic olefin polymer of 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.

[0197] The cyclic olefin polymer of this embodiment simultaneously satisfies the above-mentioned numerical ranges of Tg and Mw, thereby simultaneously improving the solubility in solvents and the mechanical strength of the molded article.

[0198] Regarding the density of the cyclic olefin polymer in this embodiment, the density value measured in water at 23°C using the water displacement method based on JIS K7112 is preferably 1000 kg / m³. 3 Above 1200 [kg / m 3 Below that, more preferably 1020 [kg / m] 3 Above 1100 [kg / m 3 Below that, a further preferred value is 1040 [kg / m³]. 3 The above 1080 [kg / m 3 Below that, 1050 [kg / m] is further preferred. 3 The above 1070 [kg / m 3 Below that, a further preferred value is 1055 kg / m³. 3 The above 1065 [kg / m 3 ]the following.

[0199] If the density value is within the above range, the transparency and refractive index performance of the obtained optical component can be well maintained, and the heat resistance can be further improved.

[0200] It should be noted that the test piece can be obtained, for example, as follows: the cyclic olefin polymer of this embodiment is sandwiched in an ultra-heat resistant polyimide film (trade name: Upilex, manufactured by Ube Industries Co., Ltd.), using a 0.1 mm spacer, and vacuum-pressed at 260°C, 10 MPa, and 3 minutes.

[0201] (Other ingredients)

[0202] The cyclic olefin polymer of this embodiment may be combined 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 impairing the purpose of this embodiment, and the proportions of these combinations shall be appropriate.

[0203] The cyclic olefin polymer composition of this embodiment preferably further comprises a hydrophilic agent. By including a hydrophilic agent, it is possible to suppress the deterioration of various properties of the molded article under high temperature and high humidity conditions.

[0204] As a hydrophilic agent, fatty acid esters of fatty acids and polyols are preferred. More preferably, fatty acid esters of fatty acids and polyols having one or more ether groups are preferred.

[0205] Examples of fatty acid esters include monoglyceride fatty acid esters, diglyceride fatty acid esters, triglyceride fatty acid esters, pentaerythritol monostearate, pentaerythritol distearate, and pentaerythritol tristearate.

[0206] Fatty acid esters of fatty acids and polyols having one or more ether groups are defined as esters of fatty acids and polyols having one or more ether groups. It should be noted that the ether group in a polyol does not include the ether group itself.

[0207] Examples of polyols having one or more ether groups include monoglycerides, diglycerides, triglycerides, tetraglycerides, and sorbitol.

[0208] In this embodiment, the fatty acid ester preferably includes monoglyceride, diglyceride, and triglyceride fatty acid esters. The diglyceride fatty acid ester is a substance formed by esterification of at least one of the four hydroxyl groups in diglyceride with a fatty acid.

[0209] Examples of fatty acids 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 crotonic acid, myristoleic acid, palmitoleic acid, cis-6-hexadecenoic acid, oleic acid, transoleic acid, codoleic acid, and eicosapentaenoic acid; diunsaturated fatty acids such as linoleic acid, eicosadienoic acid, and docosahexaenoic acid; triunsaturated fatty acids such as linolenic acid, terpineic acid, tung oil acid, and eicosatrienoic acid; and tetraunsaturated fatty acids such as octadecanoic acid, arachidonic acid, and eicosatrienoic acid.

[0210] 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 monostearate, diglyceride monobehenate, diglyceride dibehenate, and other diglyceride saturated fatty acid esters; diglyceride monooleate, diglyceride dioleate, and other diglyceride unsaturated fatty acid esters; etc., and one or more of these may be used.

[0211] 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-mentioned 12 to 18 carbon atoms.

[0212] It should be noted that, 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. The diglyceride skeleton is hydrophilic, and the fatty acids improve the compatibility with the resin, thus maintaining transparency and providing excellent resistance to damp heat.

[0213] The cyclic olefin polymer composition of this embodiment may contain at least one diglyceride fatty acid ester. Preferably, at least one diglyceride fatty acid ester may be a single monoester or a combination of a monoester and a diester.

[0214] Triglyceride fatty acid esters are esters of fatty acids and triglycerides.

[0215] The triglyceride fatty acid ester in this embodiment is a substance formed by esterification of at least one of the three hydroxyl groups contained in triglycerides with fatty acids.

[0216] Examples of triglyceride fatty acid esters 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 monobehenate, triglyceride dibehenate, triglyceride tribehenate, etc., saturated triglyceride fatty acid esters; triglyceride monooleate, triglyceride dioleate, triglyceride trioleate, etc., unsaturated triglyceride fatty acid esters; etc., and one or more of these may be used.

[0217] The triglyceride fatty acid ester of this embodiment preferably comprises an ester containing triglyceride and a saturated or unsaturated fatty acid with 8 to 24 carbon atoms, and more preferably an ester containing triglyceride and a saturated or unsaturated fatty acid with 12 to 18 carbon atoms.

[0218] Examples of triglyceride fatty acid esters in this embodiment include single monoesters, mixtures of monoesters and diesters, or mixtures of monoesters, diesters, and triesters.

[0219] As such triglyceride fatty acid esters, compounds described in, for example, Japanese Patent Application Publication No. 2006-232714, Japanese Patent Application Publication No. 2002-275308, and Japanese Patent Application Publication No. Hei 10-165152 can be used.

[0220] Commercially available hydrophilic agents used in this embodiment include, for example, RIKEMAL DO-100 (manufactured by Riken Vitamin Co., Ltd.) and EXCEPARL PE-MS (manufactured by Kao Corporation).

[0221] In the cyclic olefin polymer composition of 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. Furthermore, the upper limit of the hydrophilic agent content relative to 100 parts by weight of the 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.

[0222] As antioxidants, well-known antioxidants can be used. Specifically, hindered phenolic compounds, sulfur-based antioxidants, lactone-based antioxidants, organophosphites, organophosphonites, or combinations thereof can be used.

[0223] Examples of lubricants 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.

[0224] As a slip agent, amides of saturated or unsaturated fatty acids such as lauric acid, palmitic acid, oleic acid, stearic acid, erucic acid, and behenic acid, or diamides of these saturated or unsaturated fatty acids, are preferred. Among these, erucamide and ethylene bis-stearamide 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.

[0225] 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 resin powder, methacrylic resin powder, etc.). Among these, micronized silica and micronized cross-linked resin powder are preferred.

[0226] The cyclic olefin copolymers with a norbornene backbone and the ring-opening polymers with a norbornene backbone of this embodiment can be used in a variety of forms, such as lens shapes, spherical shapes, rod shapes, plate shapes, cylindrical shapes, tubular shapes, fibrous shapes, film shapes, or sheet shapes. They are preferably used in optical components, films, and medical components. Examples of optical components include eyeglass lenses, fθ lenses, pickup lenses, camera lenses, sensor lenses, digital camera lenses, projector lenses, optical disc pickup lenses, automotive camera lenses, prisms, light guide plates, and XR devices. Examples of films include phase retardation films for displays, visibility-enhancing films for displays, touch sensor films, base films for solar cells, circuit boards, high-frequency substrates, substrates for liquid crystal displays or solar cells, films or sheets, tablet packaging sheets (PTP), shrink films, easy-tear films for food packaging, and film capacitors. Examples of medical components include pre-installed syringes, plastic vials, infusion bags, blood analysis pools, catheter components, tablet bottles, examination containers, sterile tablets, bioplates, and biochips.

[0227] Cyclic olefin copolymers and ring-opening polymers of cyclic olefins exhibit high solubility in solvents, and are therefore readily soluble in solvents (e.g., methylcyclohexane, toluene, etc.) used in coating polymers, especially at or near room temperature. This results in homogeneous solutions, preventing unevenness when forming molded articles such as films, and providing excellent mechanical strength and elongation.

[0228] The molded article of this embodiment can be obtained by molding a composition containing a cyclic olefin polymer into a predetermined shape. The method for molding the composition containing the cyclic olefin polymer to obtain the molded article is not particularly limited, and known methods can be used. Depending on the application and shape, methods such as extrusion molding, injection molding, compression molding, blow molding, blow molding, extrusion blow molding, injection blow molding, compression molding, vacuum molding, powder slush molding, calendering, and foam molding can be applied. From the viewpoint of formability and productivity, injection molding and extrusion molding are preferred. Furthermore, the molding conditions can be appropriately selected according to the intended use or molding method. For example, the composition temperature during injection molding is typically 150°C to 400°C, preferably 200°C to 350°C, and more preferably within the range of 230°C to 330°C.

[0229] Cyclic olefin copolymers and cyclic olefin ring-opening polymers can be used to prepare coating agents, which can be mixed in a solvent during the preparation of the coating agent.

[0230] The solvent used to prepare the coating agent is not particularly limited. 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. They can be used individually or in combination of two or more.

[0231] When preparing a coating agent, there are no particular restrictions on the coating method, and it can be carried out by known methods. For example, after coating by methods such as mold coating, flow coating, spray coating, bar coating, gravure coating, gravure reverse coating, contact reverse coating, micro-gravure coating, roller coating, doctor blade coating, bar coating, roller knife coating, air knife coating, corner wheel coating, reverse roller coating, transfer roller coating, wet roller coating, curtain coating, and dip coating, the coating film is obtained by drying by suitable methods such as natural drying or forced drying by heat.

[0232] <Methods for manufacturing cyclic olefin polymers>

[0233] The cyclic olefin polymer of this embodiment can be obtained, for example, by the following methods: a method of melt-blending the cyclic olefin polymer and other components to be added as needed using a known mixing apparatus such as an extruder and a Bamberley internal mixer; a method of dissolving the cyclic olefin polymer and other components to be added as needed in a common solvent and then evaporating the solvent; a method of 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.

[0234] Next, the resulting molded body is annealed for 2 to 8 hours, for example, in 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. Through the above annealing treatment, the molecules of the cyclic olefin polymer in the molded body are relaxed, and the free volume is reduced. Therefore, even if heat treatment is performed, it is not easy to cause a change in specific gravity (volume change).

[0235] Here, if the annealing conditions are made more stringent, the molded body will deform and cannot be restored. Therefore, it is preferable to perform the annealing under the above conditions and within a range that does not cause deformation of the molded body. That is, it is preferable to perform the annealing at a temperature and time that will not cause deformation of the molded body.

[0236] During polymerization, for the cyclic olefin polymer of this embodiment, the stereoregularity (ratio of racemic to meso structures) can be adjusted by selecting the catalyst and co-catalyst. The catalyst and co-catalyst will be described in detail below.

[0237] [catalyst]

[0238] The catalyst in this embodiment (hereinafter also referred to as the main catalyst) is not particularly limited as long as the ratio of the racemic structure to the meso structure of the cyclic olefin polymer can be adjusted. Specific examples of such main catalysts include semi-metallocene titanium compounds, zirconium compounds, and hafnium compounds, as well as metallocene titanium compounds, zirconium compounds, and hafnium compounds. Among these, semi-metallocene titanium compounds, zirconium compounds, and hafnium compounds having cyclopentadienyl or pyrazolate groups, and metallocene titanium compounds, zirconium compounds, and hafnium compounds having fluorene are particularly preferred. When using these main catalysts, the ratio of the racemic structure to the meso structure can be easily adjusted.

[0239] Specific examples of the aforementioned main catalysts include 3,5-dimethylethyl-1-pyrazol-tert-butylcyclopentadiene titanium dichloride (Japanese Patent Application Laid-Open No. 2019-172954, paragraphs 0385-0388), bis-tert-butyl ketone imine cyclopentadiene titanium dichloride (Japanese Patent Application Laid-Open No. 2018-150273, paragraphs 0003-0004), dimethylmethylenefluorenylcyclopentadiene dimethylzirconium, diphenylmethylenefluorenylcyclopentadiene dimethylzirconium (Japanese Patent Application Laid-Open No. 2019-172954, paragraphs 0088-0109), and dimethylmethylenebisindenyl dichloride. Zirconium chloride (Japanese Patent Application Publication No. 2019-172954, paragraphs 0081-0087), diphenylmethylene indene cyclopentyl dichloride (International Publication No. 2014 / 185253, paragraphs 0092-0093), 3,5-bis-tert-butyl-1-pyrazolite-tert-butylcyclopentadiene titanium dichloride, 3,5-bis-tert-butyl-1-pyrazolite-indene titanium dichloride, 3-(4-methoxyphenyl)-5-(4-tert-butylphenyl)-1-pyrazolite-tert-butylcyclopentadiene titanium dichloride, 3,5-diphenyl-1-pyrazolite-tert-butylcyclopentadiene titanium dichloride, etc.

[0240] [Cocatalyst]

[0241] The cocatalyst in this embodiment is not particularly limited as long as it can improve the catalytic activity of the main catalyst. Examples of such cocatalysts include ionic compounds, with aluminum or boron compounds being particularly preferred. Examples include trialkylaluminum such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, and mixtures thereof; triphenylcarbium tetra(pentafluorophenyl)borate and N,N-dimethylphenylammonium tetra(pentafluorophenyl)borate, with borate compounds containing pentafluorophenyl groups being particularly preferred. When using this cocatalyst, stereoregularity can be more appropriately controlled.

[0242] Specific examples of such cocatalysts include triphenylcarbamonite tetra(pentafluorophenyl)borate, N,N-dimethylphenylammonium tetra(pentafluorophenyl)borate, MMAO (modified methylaluminoxane), and PMAO (polymethylaluminoxane).

[0243] The combination of the main catalyst and the co-catalyst in this embodiment is preferably a combination of one or more of the following: semi-metallocene titanium compounds, zirconium compounds and hafnium compounds having cyclopentadienyl or pyrazolite groups, and metallocene titanium compounds, zirconium compounds and hafnium compounds having fluorene, as the main catalyst and a borate compound having pentafluorophenyl as the co-catalyst.

[0244] Specific examples of preferred combinations of main catalyst and co-catalyst include the following combinations.

[0245] • Main catalysts: 3,5-bismethylethyl-1-pyrazolite-tert-butylcyclopentadienyl titanium dichloride, bis-tert-butylacyl ketone imine cyclopentadienyl titanium diethyl, dimethylmethylenefluorenylcyclopentadienyl dimethylzirconium, diphenylmethylenefluorenylcyclopentadienyl dimethylzirconium, dimethylmethylenebisindylzirconium dichloride, diphenylmethyleneindylcyclopentadienylzirconium dichloride, 3,5-bis-tert-butyl-1-pyrazolite-tert-butylcyclopentadienyl titanium dichloride, 3,5-bis-tert-butyl-1-pyrazolite-indyl titanium dichloride, 3-(4-methoxyphenyl)-5-(4-tert-butylphenyl)-1-pyrazolite-tert-butylcyclopentadienyl titanium dichloride, 3,5-diphenyl-1-pyrazolite-tert-butylcyclopentadienyl titanium dichloride

[0246] • Catalysts: Triphenylcarbamonite tetra(pentafluorophenyl)borate, N,N-dimethylphenylammonium tetra(pentafluorophenyl)borate

[0247] Here, one type of main catalyst and two or more types of co-catalyst can be used.

[0248] By using a combination of primary and co-catalysts as described above, the solubility of cyclic olefin polymers can be improved. While the mechanism is not necessarily clear, it is believed that by using the aforementioned co-catalyst, the proportion of racemic compounds in the cyclic olefin polymer can be reduced.

[0249] 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 aforementioned main catalyst and co-catalyst.

[0250] In the method for manufacturing cyclic olefin polymers according to this embodiment, copolymers can be manufactured by copolymerizing two or more olefins with cyclic olefins.

[0251] The method of using each component of the olefin polymerization catalyst constituting the present invention during polymerization and the order of addition to the polymerization vessel can be arbitrarily selected, and the following methods can be exemplified. Hereinafter, the main catalyst (A), co-catalyst (B), support (C), and organic compound component (D) may be referred to as "component (A) to (D)". (1) A method of adding component (A) alone to the polymerization vessel. (2) A method of adding component (A) and component (B) to the polymerization vessel in any order. (3) A method of adding a catalyst component obtained by supporting component (A) on component (C) and component (B) in any order to the polymerization vessel. (4) A method of adding a catalyst component obtained by supporting component (B) on component (C) and component (A) in any order to the polymerization vessel. (5) A method of adding a catalyst component obtained by supporting component (A) and component (B) on component (C) to the polymerization vessel.

[0252] In all the methods described above, component (D) can be added at any stage.

[0253] In each of the above methods, at least two of the catalyst components can be pre-contacted.

[0254] In the methods described in (4) and (5) above, where component (B) is supported, unsupported component (B) can be added in any order as needed. In this case, component (B) can be the same or different. Furthermore, for solid catalyst components obtained by supporting component (A) on component (C), and solid catalyst components obtained by supporting components (A) and (B) on component (C), olefins can be prepolymerized, or catalyst components can be further supported on the prepolymerized solid catalyst components.

[0255] The copolymerization of olefins with cyclic olefins can be carried out through either liquid-phase polymerization (such as solution polymerization or 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 used in combination.

[0256] When using the catalyst for olefin polymerization as described above to carry out olefin polymerization, the main catalyst (A) is typically 10 relative to 1 liter of reaction volume. -12 ~10 -2 Moore, preferred to become 10 -10 ~10 -3 Use it in moles.

[0257] When using a support (C), the main catalyst (A) to the support (C) 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.

[0258] In the manufacturing method of this embodiment, the polymerization temperature in the aforementioned polymerization process is typically -50 to +200°C, preferably 0 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 by any of the batch, semi-continuous, or continuous methods. Furthermore, the polymerization can also be carried out in two or more steps with different reaction conditions.

[0259] The molecular weight of the resulting 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 approximately 0.001 to 5,000 NL relative to 1 kg of copolymer produced.

[0260] The embodiments of the present invention have been described above, but these are merely examples of the present invention, and various other configurations may also be adopted.

[0261] Furthermore, the present invention is not limited to the foregoing embodiments, and variations and improvements within the scope of achieving the purpose of the present invention are also included in the present invention.

[0262] Example

[0263] Hereinafter, this embodiment will be described in detail with reference to examples and the like. It should be noted that this embodiment is not limited in any way by the description in these examples.

[0264] First, the measurement methods used in the examples will be described.

[0265] [ 13 [C-NMR determination]

[0266] 13 C-NMR measurements were performed under the following conditions.

[0267] Device: AVANCE IIIcryo-500 MRI scanner manufactured by Burker Biospin

[0268] Measurement nucleus: 13 C(125MHz)

[0269] Measurement mode: Single-pulse proton (with reverse grid) decoupling

[0270] Pulse width: 90 degrees

[0271] Points accumulated: 64000

[0272] Measurement range: -55 to 195 ppm (total 250 ppm)

[0273] Repeat time: 12 seconds

[0274] Total number of times: 256

[0275] Solvent: 1,1,2,2-Tetrachloroethane-d2

[0276] Concentration: 10% w / v

[0277] Temperature: 120℃

[0278] Chemical shift standard: tetramethylsilyl quasi-(1,1,2,2-tetrachloroethane-d2: equivalent to 74.2 ppm)

[0279] Under the above conditions 13 C-NMR measurements were used to determine the proportion of [CO]-[CO] structural units (the total of [CO]-[CO], [E]-[CO] and [E]-[E] structures was set to 100 mol%), as well as 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%).

[0280] It should be noted that [CO] refers to the structural unit derived from cyclic olefins, and [E] refers to the structural unit derived from ethylene.

[0281] Furthermore, when a signal was detected in the range of 51.2–55.5 ppm, the following was measured:

[0282] • Total integral value (P) of signals detected in the range of 51.2–55.5 ppm

[0283] • The integral value (Q) of the signal in the range of 54.0–54.6 ppm.

[0284] The value of (PQ) obtained by subtracting (Q) from (P) is then divided by (P), thereby calculating the chain ratio of structural unit (B).

[0285] Alternatively, if a signal is detected in the range of 40.0–50.0 ppm, use:

[0286] • Total integral value (T) of signals detected in the range of 40.0–50.0 ppm

[0287] • Total integral value (U) of signals detected in the range of 45.0–46.0 ppm

[0288] The (U / T) value obtained by dividing (U) by (T) is multiplied by 2.5, then multiplied by the composition ratio of BNBD and divided by 100 to calculate the chain ratio of structural unit (B).

[0289] Alternatively, if signals are detected in both the 40.0–50.0 ppm range and the 51.2–55.5 ppm range,

[0290] The proportions of each element in the structural unit (B) calculated using the methods described above are summed to calculate the chain proportion of the structural unit (B).

[0291] [Solubility Test]

[0292] The solubility of methylcyclohexane and toluene should be evaluated under the following conditions.

[0293] <Solubility of methylcyclohexane>

[0294] • Examples and comparative examples using polymers of ethylene and TD (i.e., Examples 1, 2, 5-9, 11-13 and Comparative Example 1)

[0295] Samples: cyclic olefin copolymers manufactured in the examples and comparative examples described below.

[0296] Solvent: Methylcyclohexane

[0297] Solution concentration: 10 wt%

[0298] Temperature: 25℃

[0299] Solubility evaluation criteria: visually confirmed solubility after standing for one day.

[0300] A: There is no polymer dissolution residue; it is transparent.

[0301] B: There is no polymer residue immediately after dissolution; it becomes opaque after standing for a day.

[0302] C: There are residual dissolved polymers, resulting in a cloudy appearance.

[0303] • Examples and comparative examples (i.e., Examples 3, 4, 10, 14 and Comparative Example 2) that used polymers of ethylene and BNBD, as well as polymers of ethylene, TD and BNBD.

[0304] Samples: cyclic olefin copolymers manufactured in the examples and comparative examples described below.

[0305] Solvent: Methylcyclohexane

[0306] Solution concentration: 1 wt%

[0307] Temperature: 50℃

[0308] Solubility evaluation criteria: visually confirmed solubility after standing for one day.

[0309] A: There is no polymer dissolution residue; it is transparent.

[0310] B: There is no polymer residue immediately after dissolution; it becomes opaque after standing for a day.

[0311] C: There are residual dissolved polymers, resulting in a cloudy appearance.

[0312] <Regarding the solubility of toluene>

[0313] Samples: cyclic olefin copolymers manufactured in the examples and comparative examples described below.

[0314] Solvent: Toluene

[0315] Solution concentration: 10 wt%

[0316] Temperature: 25℃

[0317] Solubility evaluation criteria: visually confirmed solubility after standing for one day.

[0318] A: There is no polymer dissolution residue; it is transparent.

[0319] B: There is no polymer residue immediately after dissolution; it becomes opaque after standing for a day.

[0320] C: There are residual dissolved polymers, resulting in a cloudy appearance.

[0321] [Moldability]

[0322] The cyclic olefin copolymers obtained in each example and comparative example were sandwiched in 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 0.1 mm spacers.

[0323] A: No cracks were observed visually, and the membrane shape was maintained over 80% of the area.

[0324] B: Cracks were visually observed, and the area of ​​cracks greater than 30% and less than 80% maintained the membrane shape.

[0325] C: Cracks were visually observed, and more than 70% of the area did not maintain the membrane shape.

[0326] [density]

[0327] The cyclic olefin copolymers obtained in each example and comparative example were sandwiched within an ultra-heat-resistant polyimide film (trade name: Upilex, manufactured by Ube Industries, Inc.) using 0.1 mm spacers, and vacuum-pressed at 260°C, 10 MPa, and 3 minutes to obtain test pieces. The density of these test pieces was determined in water at 23°C based on JIS K7112. It should be noted that the density was determined by a water displacement method.

[0328] Intrinsic viscosity [η]

[0329] A mobile viscometer (manufactured by Clutch Company, type VNR053U) was used, and a solution obtained by dissolving 0.25–0.30 g of cyclic olefin copolymer in 25 ml of decahydronaphthalene was used as the sample. 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 obtain the intrinsic viscosity [η] of the cyclic olefin copolymer.

[0330] [Polymer weight-average molecular weight (Mw), molecular weight distribution (Mw / Mn)]

[0331] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the olefin polymers were determined using gel permeation chromatography (GPC). The values ​​were calculated from molecular weight distribution curves obtained using a Waters Alliance GPC 2000 gel permeation chromatograph (high-temperature size exclusion chromatography), under the following operating conditions:

[0332] <Apparatus and Conditions for Use>

[0333] Apparatus used: Gel permeation chromatograph, Alliance GPC 2000 (Waters Corporation)

[0334] Analysis software: Empower (trademark, Waters Corporation) chromatography data system

[0335] Chromatographic column: TSKgel GMH6-HT×2 + TSKgel GMH6-HT×2 (inner diameter 7.5mm × length 30cm, Tosoh Corporation)

[0336] Mobile phase: o-dichlorobenzene [=ODCB] (Wako Purified Pharmaceuticals, Grade A Reagent)

[0337] Detector: Differential refractometer (built into the device)

[0338] Column temperature: 140℃

[0339] Flow rate: 1.0 mL / min

[0340] Injection volume: 400 μL

[0341] Sampling time interval: 1 second

[0342] Sample concentration: 0.15% (w / v)

[0343] Molecular weight correction: Monodisperse polystyrene (Tosoh Corporation) / Molecular weight 495 to 20.6 million

[0344] [Glass transition temperature Tg (°C)]

[0345] The glass transition temperature (Tg) of the cyclic olefin copolymer was determined using a DSC-7020 (manufactured by Hitachi Advanced Scientific Corporation) under a nitrogen atmosphere. The cyclic olefin copolymer was heated from room temperature to 250°C at a heating rate of 10°C / min and held for 5 minutes. Then, it was cooled 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 copolymer was then determined from the endothermic curve obtained when the temperature was increased to 300°C at a heating rate of 10°C / min.

[0346] (Example 1)

[0347] A 500 mL glass reactor, fully purged with nitrogen, was filled with 300 mL of a 9 / 1 mixture of cyclohexane and hexane, and tetracyclohexane [4.4.0.1]. 2,5 .1 7,10 2.2 g of 3-dodecene (hereinafter also referred to as "tetracyclododecene". Mw: 160.2 (g / mol)) was added, and 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-pyrazol-tert-butylcyclopentadienyl titanium dichloride was added, and 0.012 mmol of triphenylcarbium tetra(pentafluorophenyl)borate (hereinafter referred to as borate compound (1). Synthesized according to Japanese Patent Application Publication No. 2018-105273) was added to start the polymerization reaction.

[0348] Ethylene was continuously supplied at 90 L / hr and hydrogen at 0.24 L / hr. Polymerization was carried out at 50 °C for 5 minutes under normal pressure, followed by the addition of a small amount of isobutanol 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 the same 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 intrinsic viscosity [η] of the obtained ethylene-tetracyclododecene copolymer (structural unit (A): 62 mol% ethylene, structural 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 by differential scanning calorimetry (DSC), was 153 °C. 13 The ratio of racemic to meso structures determined by C-NMR was 0.89. It should be noted that this ratio was calculated based on the method described above for the polymer of A: ethylene and TD. Furthermore, through... 13 C-NMR analysis showed that the proportion of the chain of structural unit (B) in structural unit (B) within structural unit (B) was 1.0. It exhibits good solubility in methylcyclohexane (solubility in methylcyclohexane: A). Additionally, it shows good solubility in toluene (solubility in toluene: A). Furthermore, the membrane exhibits good formability (membrane formability: A). The density is 1046 (kg / m³). 3 The results are shown in Table 1.

[0349] (Example 2)

[0350] A 500 mL glass reactor, fully purged with nitrogen, was loaded with 245 mL of a cyclohexane / hexane (9 / 1) mixture and 5.0 g of tetracyclododecene. The liquid and gas phases were saturated with ethylene at a flow rate of 50 L / hr. 39.6 mg (0.2 mmol) of TIBAL was added. 0.0005 mmol of bis-tert-butyl ketone imine cyclopentadienyl diethyltitanium and 0.002 mmol of borate compound (1) were added to initiate polymerization.

[0351] Ethylene was continuously supplied at a rate of 50 L / hr, and polymerization was carried out at 50 °C for 10 minutes under normal pressure. Then, 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 the same 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. The intrinsic viscosity [η] of the obtained ethylene-tetracyclododecene copolymer (structural unit (A): 62 mol% ethylene, structural 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, determined by DSC, was 151 °C. 13 The ratio of racemic to meso structures obtained by C-NMR was 0.72. It should be noted that this ratio was calculated based on the method described above for the polymer of A: ethylene and TD. Furthermore, through... 13 The C-NMR analysis showed that the proportion of the chain of structural unit (B)-structural unit (B) in structural unit (B) was 1.9, and the membrane exhibited good solubility for methylcyclohexane (solubility for methylcyclohexane: A). Additionally, it showed good solubility for toluene (solubility for toluene: A). Furthermore, the membrane exhibited good formability (membrane formability: A). The results are shown in Table 1.

[0352] (Example 3)

[0353] In a 500 mL glass reactor that had been fully purged with nitrogen, 289 mL of a cyclohexane / hexane (9 / 1) mixture and 20.9 g of benzonorbornene (hereinafter also known as BNBD. Mw: 142.2 (g / mol)) 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 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-pyrazol-tert-butylcyclopentadienyl titanium dichloride and 0.012 mmol of borate compound (1), and polymerization was initiated. Polymerization was carried out continuously at a flow rate of 51 L / hr and hydrogen at a flow rate of 2 L / hr under normal pressure and at 50 °C for 10 minutes. Then, 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) mixture containing a small amount of hydrochloric acid to precipitate the polymer. After washing with the same solvent, the product was dried under reduced pressure at 130℃ for 10 hours to obtain 0.658 g of ethylene-benzonorbornene copolymer. The polymerization activity was 6.58 kg / mmol·hr. The intrinsic viscosity [η] of the obtained ethylene-benzonorbornene copolymer (structural unit (A): 67 mol% ethylene, structural unit (B): 33 mol% benzonorbornene) was 0.20 (dL / g), Mw was 34,300 (g / mol), and Mw / Mn was 1.76. The glass transition temperature determined by DSC was 106℃. 13 The ratio of racemic to meso structures obtained by C-NMR was 0.79. It should be noted that this ratio was calculated based on the method described above for the polymer of C: ethylene and BNBD. Furthermore, through... 13 The C-NMR analysis showed that the proportion of the chain of structural unit (B)-structural unit (B) in structural unit (B) was 2.2, and the membrane exhibited good solubility for methylcyclohexane (solubility for methylcyclohexane: A). Additionally, it showed good solubility for toluene (solubility for toluene: A). Furthermore, the membrane exhibited good formability (membrane formability: A). The results are shown in Table 1.

[0354] (Example 4)

[0355] A 500 mL glass reactor, fully purged with nitrogen, was loaded with 300 mL of a cyclohexane / hexane (9 / 1) mixture and 18.0 g of benzonorbornene. 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. 297.0 mg (1.5 mmol) of TIBAL was added, followed by 0.001 mmol of 3,5-bis-1-methylethyl-1-pyrazol-tert-butylcyclopentadienyl titanium dichloride and 0.004 mmol of borate compound (1), and polymerization was initiated.

[0356] Ethylene was continuously supplied at 90 L / hr and hydrogen at 0.24 L / hr, and polymerization was carried out at 50 °C for 3 minutes under normal pressure. 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 the same solvent, the polymer was dried under reduced pressure at 130 °C for 10 hours to obtain 4.490 g of ethylene-benzonorbornene copolymer. The polymerization activity was 89.8 kg / mmol·hr. The intrinsic viscosity [η] of the obtained ethylene-benzonorbornene copolymer (structural unit (A): 57 mol% ethylene, structural unit (B): 43 mol% benzonorbornene) was 0.72 dL / g, Mw was 310,000 g / mol, and Mw / Mn was 1.84. The glass transition temperature, determined by DSC, was 152 °C. 13 The ratio of racemic to meso structures obtained by C-NMR was 0.89. It should be noted that this ratio was calculated based on the method described above for the polymer of C: ethylene and BNBD. Furthermore, through... 13 C-NMR analysis showed that the proportion of the chain of structural unit (B)-structural unit (B) in structural unit (B) was 4.0. It exhibits good solubility in methylcyclohexane (solubility in methylcyclohexane: A). Additionally, it shows good solubility in toluene (solubility in toluene: A). Furthermore, the membrane exhibits good formability (membrane formability: A). The density is 1060 (kg / m³). 3 The results are shown in Table 1.

[0357] (Example 5)

[0358] A 500 mL glass reactor, fully purged with nitrogen, was loaded with 150 mL of a cyclohexane / hexane (9 / 1) mixture and 4.9 g of tetracyclododecene. 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 dimethylmethylenefluorenylcyclopentadienyldimethylzirconium and 0.012 mmol of borate compound (1), and polymerization was initiated.

[0359] The polymerization was carried out continuously at 50°C for 5 minutes under normal pressure, with ethylene supplied at 51 L / hr and hydrogen at 9.96 L / hr. A small amount of isobutanol was then added to stop the polymerization. After polymerization, the reactants were added to 0.75 L of an acetone / methanol (3 / 1) mixture containing a small amount of hydrochloric acid to precipitate the polymer. After washing with the same 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 intrinsic viscosity [η] of the obtained ethylene-tetracyclododecene copolymer (structural unit (A): 62 mol% ethylene, structural 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, determined by DSC, was 145°C. 13 The ratio of racemic to meso structures obtained by C-NMR was 0.64. It should be noted that this ratio was calculated based on the method described above for the polymer of A: ethylene and TD. Furthermore, through... 13 C-NMR analysis revealed that the proportion of the chain of structural unit (B)-structural unit (B) within structural unit (B) was 0.5, indicating good solubility in methylcyclohexane (Solubility in methylcyclohexane: A). However, regarding solubility in toluene, while it was good immediately after dissolution, it 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.

[0360] (Example 6)

[0361] A 500 mL glass reactor, fully purged with nitrogen, was loaded with 150 mL of a cyclohexane / hexane (9 / 1) mixture and 9.8 g of tetracyclododecene. 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 diphenylmethylenefluorenylcyclopentyldimethylzirconium and 0.008 mmol of borate compound (1), and polymerization was initiated.

[0362] Ethylene was continuously supplied at 90 L / hr and hydrogen at 0.24 L / hr, and polymerization was carried out at 50 °C for 10 minutes under normal pressure. Then, 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 the same 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 intrinsic viscosity [η] of the obtained ethylene-tetracyclododecene copolymer (structural unit (A): 59 mol% ethylene, structural 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, determined by DSC, was 158 °C. 13 The ratio of racemic to meso structures obtained by C-NMR was 0.54. It should be noted that this ratio was calculated based on the method described above for the polymer of A: ethylene and TD. Furthermore, through... 13 The C-NMR analysis showed that the proportion of the chain of structural unit (B)-structural unit (B) in structural unit (B) was 2.0, and the membrane exhibited good solubility in methylcyclohexane (solubility in methylcyclohexane: A). Additionally, it showed good solubility in toluene (solubility in toluene: A). Furthermore, the membrane exhibited good formability (membrane formability: A). The results are shown in Table 1.

[0363] (Example 7)

[0364] A 500 mL glass reactor, fully purged with nitrogen, was loaded with 276 mL of a cyclohexane / hexane (9 / 1) mixture and 22.4 g of tetracyclododecene. 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, followed by 0.000125 mmol of 3,5-bis(tert-butyl)-1-pyrazol-tert-butylcyclopentadienyl titanium dichloride and 0.004 mmol of borate compound (1), and polymerization was initiated.

[0365] The polymerization was carried out continuously at 90 L / hr ethylene and 0.24 L / hr hydrogen under normal pressure at 50 °C for 10 minutes. A small amount of isobutanol was then 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 the same 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 intrinsic viscosity [η] of the obtained ethylene-tetracyclododecene copolymer (structural unit (A): 54 mol% ethylene, structural 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, determined by DSC, was 176 °C. 13 The ratio of racemic to meso structures obtained by C-NMR was 1.00. It should be noted that this ratio was calculated based on the method described above for the polymer of A: ethylene and TD. Furthermore, through... 13 The C-NMR analysis showed that the proportion of the chain of structural unit (B)-structural unit (B) in structural unit (B) was 1.2, and the membrane exhibited good solubility for methylcyclohexane (solubility for methylcyclohexane: A). Additionally, it showed good solubility for toluene (solubility for toluene: A). Furthermore, the membrane formation properties were partially good (membrane formation properties: B). The results are shown in Table 1.

[0366] (Example 8)

[0367] A 500 mL glass reactor, fully purged with nitrogen, was loaded with 300 mL of a cyclohexane / hexane (9 / 1) mixture and 2.9 g of tetracyclododecene. The liquid and gas phases were saturated with ethylene at a flow 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-pyrazol-tert-butylcyclopentadienyl titanium dichloride and 0.012 mmol of borate compound (1), and polymerization was initiated.

[0368] Ethylene was continuously supplied at a rate of 90 L / hr, and polymerization was carried out at 50 °C for 10 minutes under normal pressure. The polymerization was then stopped by adding a small amount of isobutanol. 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 the same 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. The intrinsic viscosity [η] of the obtained ethylene-tetracyclododecene copolymer (structural unit (A): 58 mol% ethylene, structural 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, determined by DSC, was 173 °C. 13 The ratio of racemic to meso structures measured by C-NMR was 1.00. It should be noted that this ratio was calculated based on the method described above for the polymer of A: ethylene and TD. Furthermore, through... 13 The proportion of the chain of structural unit (B)-structural unit (B) in structural unit (B) determined by C-NMR was 2.6, and the membrane exhibited good solubility for methylcyclohexane (solubility for methylcyclohexane: A). However, regarding solubility in toluene, although it was good immediately after dissolution, it became opaque after standing for one day (solubility for toluene: B). Furthermore, the membrane exhibited good formability (membrane formability: A). The results are shown in Table 1.

[0369] (Example 9)

[0370] A 500 mL glass reactor, fully purged with nitrogen, was loaded with 300 mL of a cyclohexane / hexane (9 / 1) mixture and 1.9 g of tetracyclododecene. The liquid and gas phases were saturated with ethylene at a flow 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-pyrazol-tert-butylcyclopentadienyl titanium dichloride and 0.012 mmol of borate compound (1), and polymerization was initiated.

[0371] Ethylene was continuously supplied at a rate of 90 L / hr, and polymerization was carried out at 50 °C for 10 minutes under normal pressure. Then, 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 the same 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 intrinsic viscosity [η] of the obtained ethylene-tetracyclododecene copolymer (structural unit (A): 62 mol% ethylene, structural unit (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, determined by DSC, was 154 °C. 13 The ratio of racemic to meso structures measured by C-NMR was 1.00. It should be noted that this ratio was calculated based on the method described above for the polymer of A: ethylene and TD. Furthermore, through... 13 The C-NMR analysis showed that the proportion of the chain of structural unit (B)-structural unit (B) in structural unit (B) was 1.7, and the membrane exhibited good solubility for methylcyclohexane (solubility for methylcyclohexane: A). Additionally, it showed good solubility for toluene (solubility for toluene: A). Furthermore, the membrane exhibited good formability (membrane formability: A). The results are shown in Table 1.

[0372] (Example 10)

[0373] In a 500 mL glass reactor that had been fully purged with nitrogen, 300 mL of a 9 / 1 mixture of cyclohexane and hexane, 3.3 g of tetracyclododecene, and 5.7 g of benzonorbornene were added. The liquid and gas phases were saturated with ethylene at a flow rate of 50 L / hr and hydrogen at a flow rate of 0.24 L / hr. 59.4 mg (0.3 mmol) of TIBAL was added. Then, 0.003 mmol of 3,5-dimethylethyl-1-pyrazol-tert-butylcyclopentadienyl titanium dichloride and 0.012 mmol of borate compound (1) were added to initiate the polymerization reaction.

[0374] The polymerization was carried out continuously at 50 L / hr for ethylene and 0.24 L / hr for hydrogen, under normal pressure and at 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 the same 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 intrinsic viscosity [η] of the obtained ethylene-tetracyclododecene-benzonorbornene copolymer (structural unit (A): 59 mol% ethylene, structural unit (B): 25 mol% tetracyclododecene, 16 mol% benzonorbornene was 0.40 dL / g, Mw was 95,500 g / mol, and Mw / Mn was 2.90. The glass transition temperature, determined by differential scanning calorimetry (DSC), was 163 °C. 13 The ratio of racemic to meso structures determined by C-NMR was 0.50. It should be noted that this ratio was calculated based on the method used for the polymer of A: ethylene, TD, and BNBD. Furthermore, through... 13 C-NMR analysis showed that the proportion of the chain of structural unit (B)-structural unit (B) in structural unit (B) was 3.2%. It exhibits good solubility in methylcyclohexane (solubility in methylcyclohexane: A). It also shows good solubility in toluene (solubility in toluene: A). Furthermore, the membrane exhibits good formability (membrane formability: A). The density is 1057 kg / m³. 3 The results are shown in Table 1.

[0375] (Example 11)

[0376] A 500 mL glass reactor, fully purged with nitrogen, was loaded with 250 mL of a cyclohexane / hexane (9 / 1) mixture, 5 g of tetracyclododecene, and 331 mg (1.50 mmol) of BHT. The liquid and gas phases were saturated with ethylene at a flow rate of 50 L / hr. Then, 1.5 mmol of methylaluminoxane (calculated as aluminum atoms) was added, followed by 0.0030 mmol of 3,5-dimethylethyl-1-pyrazol-tert-butylcyclopentadienyl titanium dichloride and 0.012 mmol of borate compound (1), and the polymerization reaction was initiated.

[0377] Ethylene was continuously supplied at a rate of 50 L / hr. Polymerization was carried out at 50 °C for 10 minutes under normal pressure, followed by the addition of a small amount of isobutanol 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 the same 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 intrinsic viscosity [η] of the obtained ethylene-tetracyclododecene copolymer (structural unit (A): 55 mol% ethylene, structural 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 by differential scanning calorimetry (DSC), was 188 °C. 13 The ratio of racemic to meso structures determined by C-NMR was 1.00. It should be noted that this ratio was calculated based on the method described above for the polymer of A: ethylene and TD. Furthermore, through... 13 The proportion of the B-chain in the structural unit (B) determined by C-NMR was 3.7, indicating good solubility in methylcyclohexane (Solubility in methylcyclohexane: A). However, regarding solubility in toluene, while it was good immediately after dissolution, it 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.

[0378] (Example 12)

[0379] A 500 mL glass reactor, fully purged with nitrogen, was loaded with 245 mL of a 9 / 1 mixture of cyclohexane and hexane, and 5.0 g of tetracyclododecene. The liquid and gas phases were saturated with ethylene at a flow rate of 50 L / hr. 39.6 mg (0.2 mmol) of TIBAL was added. Next, 0.0005 mmol of diphenylmethyleneindenylcyclopentylzirconium dichloride and 0.002 mmol of borate compound (1) were added to initiate the polymerization reaction.

[0380] Ethylene was continuously supplied at a rate of 50 L / hr. Polymerization was carried out at 50 °C for 10 minutes under normal pressure, followed by the addition of a small amount of isobutanol 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 the same 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 intrinsic viscosity [η] of the obtained ethylene-tetracyclododecene copolymer (structural unit (A): 62 mol% ethylene, structural unit (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 by differential scanning calorimetry (DSC), was 150 °C. 13 The ratio of racemic to meso structures determined by C-NMR was 0.14. It should be noted that this ratio was calculated based on the method described above for the polymer of A: ethylene and TD. Furthermore, through... 13 C-NMR analysis showed that the proportion of the (B)-(B) chain in the structural unit (B) was 1.4. Regarding the solubility in methylcyclohexane, although it was good immediately after dissolution, it became opaque after standing for one day (Solubility in methylcyclohexane: B). Similarly, regarding the solubility in toluene, although it was good immediately after dissolution, it became opaque after standing for one day (Solubility in toluene: B). Furthermore, the membrane formability was partially good (Membrane formability: B). The results are shown in Table 1.

[0381] (Example 13)

[0382] A 500 mL glass reactor, fully purged with nitrogen, was charged with 300 mL of a 9 / 1 mixture of cyclohexane and hexane, along with 11.4 g of tetracyclododecene. 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. Next, 0.003 mmol of 3,5-dimethylethyl-1-pyrazol-tert-butylcyclopentadienyl titanium dichloride and 0.012 mmol of a borate compound were added to initiate the polymerization reaction.

[0383] Ethylene was continuously supplied at 90 L / hr and hydrogen at 0.24 L / hr. Polymerization was carried out at 50 °C for 10 minutes under normal pressure, followed by the addition of a small amount of isobutanol 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 the same 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 intrinsic viscosity [η] of the obtained ethylene-tetracyclododecene copolymer (structural unit (A): 51 mol% ethylene, structural 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 by differential scanning calorimetry (DSC), was 203 °C. 13 The ratio of racemic to meso structures determined by C-NMR was 1.00. It should be noted that this ratio was calculated based on the method described above for the polymer of A: ethylene and TD. Furthermore, through... 13 The C-NMR analysis showed that the proportion of the chain of structural unit (B)-structural unit (B) in structural unit (B) was 5.1, indicating good solubility in methylcyclohexane (Solubility in methylcyclohexane: A). However, regarding solubility in toluene, although it was good immediately after dissolution, it became opaque after standing for one day (Solubility in toluene: B). Furthermore, the membrane exhibited poor formability (Membrane formability: C). The results are shown in Table 1.

[0384] (Example 14)

[0385] A 500 mL glass reactor, fully purged with nitrogen, was loaded with 300 mL of a cyclohexane / hexane (9 / 1) mixture and 3.0 g of benzonorbornene. 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), and polymerization was initiated.

[0386] The polymerization was carried out continuously at 50 L / hr for ethylene and 6.0 L / hr for hydrogen, under normal pressure and at 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 the same solvent, the polymer was dried under reduced pressure at 130 °C for 10 hours to obtain 0.413 g of ethylene-benzonorbornene copolymer. The polymerization activity was 84.96 kg / mmol·hr. The intrinsic viscosity [η] of the obtained ethylene-benzonorbornene copolymer (structural unit (A): 68 mol% ethylene, structural unit (B): 32 mol% benzonorbornene) was 0.33 dL / g, Mw was 88,000 g / mol, and Mw / Mn was 6.90. The glass transition temperature, determined by DSC, was 112 °C. 13 The ratio of racemic to meso structures obtained by C-NMR was 0.26. It should be noted that this ratio was calculated based on the method described above for the polymer of C: ethylene and BNBD. Furthermore, through... 13 The C-NMR analysis showed that the proportion of the chain of structural unit (B)-structural unit (B) in structural unit (B) was 0.0, indicating poor solubility in methylcyclohexane (solubility in methylcyclohexane: B). However, it exhibited good solubility in toluene (solubility in toluene: A). Furthermore, the membrane formability was partially good (membrane formability: B). The results are shown in Table 1.

[0387] (Comparative Example 1)

[0388] A 500 mL glass reactor, fully purged with nitrogen, was loaded with 240 mL of a cyclohexane / hexane (9 / 1) mixture and 10.0 g of tetracyclododecene. 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. Then, 0.00025 mmol of dimethylmethylenebisindenylzirconium dichloride and 0.001 mmol of borate compound (1) were added to initiate polymerization.

[0389] Ethylene was continuously supplied at a rate of 50 L / hr and hydrogen at a rate of 3.0 L / hr. Polymerization was carried out at 50 °C for 10 minutes under normal pressure, followed by the addition of a small amount of isobutanol 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 the same 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 intrinsic viscosity [η] of the obtained ethylene-tetracyclododecene copolymer (structural unit (A): 64 mol% ethylene, structural 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 determined by DSC was 148 °C. 13 The ratio of racemic to meso structures obtained by C-NMR was 0.00. Additionally, through... 13 The C-NMR analysis showed that the proportion of the chain of structural unit (B)-structural unit (B) in structural unit (B) was 0.0, indicating poor solubility in methylcyclohexane (solubility in methylcyclohexane: C). Additionally, poor solubility in toluene (solubility in toluene: C). Furthermore, poor membrane formability (membrane formability: C). The results are shown in Table 1.

[0390] (Comparative Example 2)

[0391] A 500 mL glass reactor, fully purged with nitrogen, was loaded with 175 mL of a 9 / 1 mixture of cyclohexane and hexane, 4.0 g of tetracyclododecene, and 5.0 g of benzonorbornene. 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. Then, 0.0015 mmol of dimethylmethylene bisindenylzirconium dichloride and 0.006 mmol of borate compound (1) were added to initiate the polymerization reaction.

[0392] The polymerization was carried out continuously at 51 L / hr for ethylene and 2 L / hr for hydrogen, under normal pressure and at 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 the same 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 intrinsic viscosity [η] of the obtained ethylene-tetracyclododecene-benzonorbornene copolymer (structural unit (A): 62 mol% ethylene, structural 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 by differential scanning calorimetry (DSC), was 137 °C. 13 The ratio of racemic to meso structures determined by C-NMR was 0.00. It should be noted that this ratio was calculated based on the method used for the polymer of A: ethylene, TD, and BNBD. Furthermore, through... 13 The C-NMR analysis showed that the proportion of the chain of structural unit (B)-structural unit (B) in structural unit (B) was 0.0, indicating poor solubility in methylcyclohexane (solubility in methylcyclohexane: C). Additionally, poor solubility in toluene (solubility in toluene: C). Poor membrane formability (membrane formability: C). The results are shown in Table 1.

[0393] [Table 1]

[0394]

[0395] In each embodiment, the coexistence of racemic and meso structures results in high solubility for methylcyclohexane and toluene. On the other hand, in each comparative example, the solubility for methylcyclohexane and toluene is lower.

[0396] 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, which is a cyclic olefin polymer having a norbornene backbone, characterized in that, The cyclic olefin polymer is a cyclic olefin copolymer and satisfies the following requirements (a) and (b). Requirement (a): This cyclic olefin polymer is composed of structural units (A) that are chain olefins and structural units (B) that contain cyclic olefins with a norbornene backbone. pass 13 The ratio of meso-racemic structures to racemic structures in the chain of structural unit (B)-structural unit (A)-structural unit (B) determined by C-NMR, i.e., racemic structure / meso-racemic structure, is 0.01~100. Requirement (b): pass 13 The proportion of the chain of the structural unit (B) in the structural unit (B) as determined by C-NMR is greater than 0.1 mol% and less than 10.0 mol%. The cyclic olefin copolymer contains 50-75 mol% of the structural unit (A), which is a structural unit derived from ethylene.

2. The cyclic olefin polymer according to claim 1, wherein the cyclic olefin copolymer comprises 25-50 mol% of the structural unit (B), The structural unit (B) is a structural unit derived from one or more cyclic monomers selected from the group consisting of the following general formulas [ZI], [Z-II], [Z-III], and [Z-IV]. [Chemistry 1] In the formula [ZI], u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, and R 61 ~R 78 and R a1 and R b1 Each independently contains one or more elements selected from the group consisting of hydrogen atoms, halogen atoms, and hydrocarbon groups, R 75 ~R 78 They can combine to form single or multiple rings, and the single or multiple rings can have double bonds. Additionally, R... 75 With R 76 、or R 77 With R 78 It can form alkylidene groups. [Chemistry 2] In the formula [Z-II], x and d are integers greater than or equal to 0 or 1, y and z are 0, 1, or 2, and R 81 ~R 99 Each is independently selected from hydrogen atoms, halogen atoms, and hydrocarbon groups, R 89 and R 90 The carbon atom that is bonded to R 93 The bonded carbon atom or R 91 The bonded carbon atoms can be directly bonded or bonded via alkylene groups having 1 to 3 carbon atoms. Additionally, when y=z=0, R... 95 With R 92 Or R 95 With R 99 They can combine to form monocyclic or polycyclic aromatic rings. [Chemistry 3] In the aforementioned formula [Z-III], n and m are each independently 0, 1, or 2, q is 1, 2, or 3, and R 18 ~R 31 Each of the following is independently a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group with 1 to 20 carbon atoms that can be substituted by a halogen atom other than a fluorine atom. [Chemistry 4] In the general formula [Z-IV], x is an integer greater than or equal to 0 or 1, and R 111 ~R 118 Each is independently selected from hydrogen atoms, halogen atoms, and hydrocarbon groups, R 121 ~R 124 Each group is independently selected from hydrogen atoms, halogen atoms, and hydrocarbon groups. Two adjacent groups can combine with each other to form monocyclic or polycyclic aromatic rings. The total of the structural unit (A) and the structural unit (B) is 100 mol.

3. The cyclic olefin polymer according to claim 1 or 2, wherein the glass transition temperature of the cyclic olefin copolymer, as determined by differential scanning calorimetry (DSC), is above 50°C and below 250°C.

4. The cyclic olefin polymer according to claim 1 or 2, wherein the glass transition temperature of the cyclic olefin copolymer, as determined by differential scanning calorimetry (DSC), is above 50°C and below 180°C.

5. The cyclic olefin polymer according to claim 1 or 2, wherein the intrinsic viscosity of the cyclic olefin copolymer is 0.1 dL / g or higher and 5.0 dL / g or lower.

6. The cyclic olefin polymer according to claim 1 or 2, wherein the cyclic olefin copolymer is subjected to... 13 The ratio of racemic to exoracemic structures in the chain of structural unit (B)-structural unit (A)-structural unit (B) determined by C-NMR is 0.1 to 10.

0.

7. The cyclic olefin polymer according to claim 1 or 2, wherein the weight-average molecular weight Mw of the cyclic olefin copolymer determined by GPC is 10,000 or more and 1,000,000 or less.

8. A cyclic olefin polymer composition comprising the cyclic olefin polymer according to any one of claims 1 to 7.

9. The cyclic olefin polymer composition according to claim 8, used in optical components, film packaging materials, optical films, or medical components.

10. A molded article comprising the cyclic olefin polymer according to any one of claims 1 to 7.

11. The molded body according to claim 10, wherein it is an optical component, a film packaging material, an optical film, or a medical component.

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