JP7756719B2 - Cyclic olefin polymer, cyclic olefin polymer composition and molded article - Google Patents

Description

The present invention relates to a cyclic olefin polymer, a cyclic olefin polymer composition, and a molded article.

Cyclic olefin copolymers are used in optical lenses such as imaging lenses, fθ lenses, and pickup lenses. Cyclic olefin copolymers used in molded articles such as optical lenses are required to have properties such as high transparency, excellent dimensional stability, excellent heat resistance, and excellent moisture resistance.

An example of a resin composition containing such a cyclic olefin copolymer is 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.

Patent Document 2 also discloses a method for producing a cyclic olefin copolymer, which comprises copolymerizing an α-olefin and a cyclic olefin in the presence of a catalyst formed from (A) a coordination metal compound of Group IVB of the periodic table, which has as a ligand a multidentate compound in which at least two different cycloalkadienyl groups or their substituents are bonded via a hydrocarbon group, a silylene group, or a substituted silylene group, and (B) an organoaluminum oxy compound.

Furthermore, Patent Document 3 discloses (a) an ethylene-cyclic olefin copolymer obtained by random copolymerization of ethylene and an aromatic-containing norbornene derivative represented by a specific formula.

Patent document 4 also discloses a method for producing an olefin polymer, which includes a contacting step in which a transition metal complex is contacted with an organoaluminum in a proportion of 10,000 moles or less per mole of transition metal atom in the transition metal complex, calculated as the amount of aluminum atoms, and a solvent, and a polymerization step in which an olefin is polymerized in the presence of a solution containing the transition metal complex that has undergone the contacting step and the organoaluminum at a concentration of 0.005 mmol/L or more calculated as aluminum atoms.

Patent document 5 also 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 having no aromatic ring, and a structural unit (C) derived from a cyclic olefin having an aromatic ring.

Patent Document 5 also discloses a cyclic olefin copolymer composition comprising [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-based polymer having a glass transition point of 50°C or lower, 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] measured in accordance with ASTM D542 is within a specific range, and wherein the cyclic olefin copolymer composition contains 5 to 50 parts by weight of [B] per 50 to 95 parts by weight of [A].

Japanese Patent Application Publication No. 10-287713 Japanese Unexamined Patent Publication No. 2-173112 Japanese Patent Application Laid-Open No. 2005-330465 Japanese Patent Application Laid-Open No. 2018-165308 International Publication No. 2008/068897

Walter Kaminsky, Rudiger Engehausen, and Jurgen Kopf, “A Tailor-Made Metallocene for the Copolymerization of Ethene with Bulky Cycloalkenes" Angewandte Chemie International Edition in English Volume 34, Issue 20 p. 2273-2275. 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.

Cyclic olefin copolymers or ring-opening polymers having a norbornene structure are generally known to have low solubility in solvents. According to the inventors' investigations, the inventions described in Patent Documents 1 to 5 above are particularly poorly soluble at or near room temperature in solvents used for coating polymers, such as methylcyclohexane and toluene, making it difficult to obtain a homogeneous solution.

The present invention has been made in consideration of the above circumstances, and aims to provide a cyclic olefin polymer having a norbornene skeleton with improved solubility in solvents.

The present inventors conducted extensive research to solve the above-mentioned problems. As a result, they discovered that a cyclic olefin copolymer having a norbornene structure or a ring-opening polymer having a norbornene skeleton has high solubility in solvents when it has a specific stereoregularity, and completed the present invention. Specifically, the present invention provides the following cyclic olefin polymers, cyclic olefin polymer compositions, and molded articles.

[1]
A cyclic olefin polymer having a norbornene skeleton,
the cyclic olefin polymer is a cyclic olefin copolymer or a cyclic olefin ring-opening polymer,
A cyclic olefin polymer characterized by satisfying the following requirement (a):
(Requirement (a))
The cyclic olefin polymer comprises a structural unit (A) which is a chain olefin and a structural unit (B) which contains a cyclic olefin having a norbornene skeleton,
The ratio of mesostructure to racemostructure (racemostructure/mesostructure) in the structural unit (B)-structural unit (A)-structural unit (B) chain measured by ¹³ C-NMR is 0.01 to 100.
[2]
The cyclic olefin polymer according to the above [1],
the cyclic olefin polymer is a cyclic olefin copolymer,
The cyclic olefin copolymer is
As the structural unit (A), 30 to 80 mol % of a structural unit derived from ethylene or an α-olefin having 3 to 30 carbon atoms,
The structural unit (B) contains 20 to 70 mol % of structural units derived from one or more cyclic monomers selected from the group consisting of the following general formula [Z-I], the following general formula [Z-II], the following general formula [Z-III], and the following general formula [Z-IV]:
(In the above formula [Z-I], u is 0 or 1, v is 0 or a positive integer, and w is 0 or 1. R ⁶¹ to R ⁷⁸ , R ^a1 , and R ^b1 each independently include one or more selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group, and R ⁷⁵ to R ⁷⁸ may be bonded to each other to form a monocycle or a polycycle, and the monocycle or the polycycle may have a double bond. Furthermore, R ⁷⁵ and R ⁷⁶ , or R ⁷⁷ and R ⁷⁸ may be bonded to each other to form an alkylidene group.)
(In the above formula [Z-II], x and d are 0 or an integer of 1 or more, and y and z are 0, 1, or 2. R ⁸¹ to R ⁹⁹ are each independently selected from a hydrogen atom, a halogen atom, and a hydrocarbon group, and the carbon atom to which R ⁸⁹ and R ⁹⁰ are bonded may be bonded directly or via an alkylene group having 1 to 3 carbon atoms to the carbon atom to ^{which R 93 is} bonded or the carbon atom to which R 91 is bonded. Furthermore, when y=z=0, R ⁹⁵ and R ⁹² or R ⁹⁵ and R ⁹⁹ may be bonded to each other to form a monocyclic or polycyclic aromatic ring.)
(In the above formula [Z-III], n and m each independently represent 0, 1, or 2, and q is 1, 2, or 3. R ¹⁸ to R ³¹ each independently represent a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom other than a fluorine atom.)
(In general formula [Z-IV], x is 0 or an integer of 1 or more, R ¹¹¹ to R ¹¹⁸ are each independently selected from a hydrogen atom, a halogen atom, and a hydrocarbon group, and R ¹²¹ to R ¹²⁴ are each independently selected from a hydrogen atom, a halogen atom, and a hydrocarbon group, and two adjacent groups may be bonded to each other to form a monocyclic or polycyclic aromatic ring.)
A cyclic olefin polymer, wherein the total amount of the structural unit (A) and the structural unit (B) is 100 mol %.
[3]
The cyclic olefin polymer according to the above [1] or [2],
A cyclic olefin polymer further comprising the following requirement (b):
(Requirement (b))
The proportion of the structural unit (B)-structural unit (B) chains in the structural unit (B) measured by ¹³ C-NMR is 0.1 mol % or more and 20.0 mol % or less.
[4]
The cyclic olefin polymer according to any one of the above [1] to [3],
The cyclic olefin polymer has a glass transition temperature of 50°C or higher and 250°C or lower, as measured by a differential scanning calorimeter (DSC).
[5]
The cyclic olefin polymer according to any one of the above [1] to [4],
The cyclic olefin polymer has a glass transition temperature of 50°C or higher and 180°C or lower, as measured by a differential scanning calorimeter (DSC).
[6]
The cyclic olefin polymer according to any one of [1] to [5] above,
The cyclic olefin copolymer or the cyclic olefin ring-opening polymer has an intrinsic viscosity of 0.1 [dL/g] or more and 5.0 [dL/g] or less.
[7]
A cyclic olefin polymer composition comprising the cyclic olefin polymer according to any one of [1] to [6] above.
[8]
The cyclic olefin polymer composition according to the above [7],
A cyclic olefin polymer composition used for optical parts, film packaging materials, optical films, or medical parts.
[9]
A molded article comprising the cyclic olefin polymer according to any one of [1] to [6] above.
[10]
The molded article according to the above [9],
The molded article is an optical part, a film packaging material, an optical film, or a medical part.

The cyclic olefin polymer having a norbornene skeleton of the present invention has higher solubility in solvents than conventional cyclic olefin copolymers or ring-opening polymers. Therefore, it can be easily dissolved at or near room temperature in solvents used for coating polymers, such as methylcyclohexane and toluene. Furthermore, because a homogeneous solution containing the cyclic olefin copolymer or ring-opening polymer can be obtained, the resulting molded product, such as a film, is uniform and has excellent mechanical strength and elongation.

The present invention will be described below based on embodiments. In this embodiment, "A to B" indicating a numerical range means A or more and B or less unless otherwise specified. Furthermore, "cyclic olefin polymer" means a copolymer and/or a ring-opening polymer unless otherwise specified.

As described above, the inventors have discovered that conventional cyclic olefin copolymers or ring-opening polymers generally have low solubility in solvents. The inventors conducted extensive research to solve the above problem. As a result, they discovered that cyclic olefin polymers with specific stereoregularity have high solubility in solvents, leading to the completion of the present invention.

That is, the cyclic olefin polymer of this embodiment is as follows:

<Cyclic olefin polymer having a norbornene skeleton>
A cyclic olefin polymer having a norbornene skeleton,
the cyclic olefin polymer is a cyclic olefin copolymer or a cyclic olefin ring-opening polymer,
A cyclic olefin polymer characterized by satisfying the following requirement (a):
(Requirement (a))
The cyclic olefin polymer comprises a chain olefin structural unit (A) and a cyclic olefin structural unit (B) having a norbornene skeleton, and the ratio of mesostructure to racemostructure (racemostructure/mesostructure) in the structural unit (B)-structural unit (A)-structural unit (B) chain, as measured by ^13C -NMR, is 0.01 to 100.

The cyclic olefin polymer having a norbornene skeleton according to this embodiment has a specific stereoregularity, which increases its solubility in solvents. In particular, it can be easily dissolved at or near room temperature in solvents used for coating polymers (e.g., methylcyclohexane, toluene, etc.). This results in a homogeneous solution, which allows for consistent formation of molded articles such as films, resulting in excellent mechanical strength and elongation.

Cyclic olefin copolymers with specific stereoregularity can be dissolved in other solvents, such as toluene, in addition to methylcyclohexane. The solubility parameter (SP value) of a cyclic olefin copolymer varies depending on the constituent components and composition of the chain olefin structural unit (A) and the structural unit (B) containing a cyclic olefin having a norbornene skeleton. Therefore, depending on the SP value, the copolymer may have high solubility in toluene.

First, the specific stereoregularity according to 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 mesostructure in the chain of structural unit (B)-structural unit (A)-structural unit (B) refers to the structure shown as αβm in Figure 5 of Non-Patent Document 2. Furthermore, the racemostructure refers to the structure shown as αβr in the same figure.

In the above general formula (I), m and n represent repeating units. Here, if the norbornene-derived structure is NB and the ethylene-derived structure is E, then in the above example, the bonds are linked as follows: ...NB-E-NB-E-NB-E-... The mesostructure and racemostructure are measured by ^13C -NMR. An example of this bonding pattern is shown below.

Generally, cyclic olefin copolymers having a norbornene skeleton or cyclic olefin ring-opening polymers having a norbornene skeleton synthesized without controlling the stereoregularity are only meso or racemo isomers and have low solubility in solvents.
On the other hand, the cyclic olefin polymer having a norbornene skeleton according to the present embodiment has an overall ratio of the portion occupied by structures in a racemo relationship to the portion occupied by structures in a meso relationship, i.e., the ratio of racemo structures to meso structures [racemo/meso], which represents stereoregularity, of 0.01 to 100 (i.e., racemo: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. Having a racemo/meso ratio within the above range improves solubility in solvents. The stereoregularity can be appropriately adjusted by selecting the catalyst and co-catalyst used in the polymerization, as described below.

The ¹³ C-NMR measurement is not particularly limited as long as it can distinguish between the mesostructure and the racemostructure. Examples of such ¹³ C-NMR measurement include the following. More detailed information on ¹³ C-NMR measurement will be explained later in the section on stereoregularity.
Apparatus: Bruker Biospin AVANCE III Cryo-500 Nuclear Magnetic Resonance Measurement nucleus: ¹³ C
Frequency: 125MHz
Measurement mode: Single pass proton (with reverse gate) decoupling Pulse width: 90 degrees Number of points: 64,000
Measurement range: -55 to 195 ppm (total 250 ppm)
Repeat time: 12 seconds Number of accumulations: 256 Solvent: 1,1,2,2-tetrachloroethane-d2
Concentration: 10%w/v
Temperature: 120℃
Chemical shift standard: tetramethylsilane standard (1,1,2,2-tetrachloroethane-d2: 74.2 ppm)

[Cyclic olefin polymer having a norbornene skeleton]
The cyclic olefin copolymer having a norbornene skeleton (hereinafter also simply referred to as cyclic olefin copolymer) or the cyclic olefin ring-opening polymer having a norbornene skeleton (hereinafter also simply referred to as cyclic olefin ring-opening polymer) according to this embodiment will be described in detail.
The cyclic olefin copolymer and the cyclic olefin ring-opening polymer have a norbornene skeleton and are composed of a structural unit (A) which is a chain olefin and a structural unit (B) which contains a cyclic olefin having a norbornene skeleton.

(Cyclic olefin copolymer)
The cyclic olefin copolymer according to this embodiment preferably contains the following structural unit (A) and structural unit (B), from the viewpoint of further improving the heat resistance and improving the moldability while maintaining a good balance between the transparency and refractive index of the resulting optical component.

Structural unit (A): a structural unit derived from ethylene or an α-olefin having 3 to 30 carbon atoms.
Structural unit (B): A structural unit derived from at least one selected from the group consisting of a structural unit represented by the following general formula (Z-I), a structural unit represented by the following general formula (Z-II), a structural unit represented by the following general formula (Z-III), and a structural unit represented by the following general formula (Z-IV).

In the above formula [Z-I], u is 0 or 1, v is 0 or a positive integer, preferably an integer of 1 or more, more preferably 1 or 2, and even more preferably 1, and w is 0 or 1. R ⁶¹ to R ⁷⁸ , R ^a1 and R ^b1 are each independently selected from a hydrogen atom, a halogen atom and a hydrocarbon group.

In the above formula [Z-II], x and d are 0 or an integer of 1 or more, and y and z are 0, 1, or 2. x is preferably an integer of 1 or more, more preferably 1 or 2, and even more preferably 1. ^{R 81} to R ⁹⁹ are each independently selected from a hydrogen atom, a halogen atom, and a hydrocarbon group. The carbon atom to which R ⁸⁹ and R ⁹⁰ are bonded may be bonded directly to the carbon atom to which R ⁹³ is bonded or the carbon atom to which R ⁹¹ is bonded, or may be bonded via an alkylene group having 1 to 3 carbon atoms. Furthermore, when y = z = 0, R ⁹⁵ and R ⁹² , or R ⁹⁵ and R ⁹⁹ , may be bonded to each other to form a monocyclic or polycyclic aromatic ring.

In the formula [Z-III], n and m are each independently 0, 1, or 2, and q is 1, 2, or 3. R ¹⁸ to R ³¹ are each independently a hydrogen atom, a halogen atom other than fluorine, or a hydrocarbon group having 1 to 20 carbon atoms optionally substituted with a halogen atom other than fluorine. When q = 1, R ²⁸ and R ²⁹ , R ²⁹ and R ³⁰ , and R ³⁰ and R ³¹ may be bonded to each other to form a monocycle or a polycycle. When q = 2 or 3, R ²⁸ and R ²⁸ , R ²⁸ and R ²⁹ , R ²⁹ and R ³⁰ , R ³⁰ and R ³¹ , and R ³¹ and R ³¹ may be bonded to each other to form a monocycle or a polycycle, and the monocycle or polycycle may have a double bond, or the monocycle or polycycle may be an aromatic ring. In the formula [Z-III], n and m are preferably 0 and q is preferably 1, 2 or 3, and in the formula [Z-III], n and m are preferably 0 and q is preferably 1.

In the formula [Z-IV], x is 0 or an integer of at least 1. R ¹¹¹ to R ¹¹⁸ are each independently selected from a hydrogen atom, a halogen atom, and a hydrocarbon group, and R ¹²¹ to R ¹²⁴ are each independently selected from a hydrogen atom, a halogen atom, and a hydrocarbon group, and two adjacent groups may be bonded to each other to form a monocyclic or polycyclic aromatic ring.

By using a cyclic olefin monomer represented by the above formula [Z-I], [Z-II], [Z-III] or [Z-IV] as a copolymerization component, the solubility of the cyclic olefin copolymer in solvents is further improved, resulting in better moldability and improved product yield.

When the total of the structural units (A) and (B) is taken as 100 mol%, the structural unit (A) is preferably 30 to 80 mol%, more preferably 40 to 77 mol%, and even more preferably 50 to 75 mol%, and the structural unit (B) is preferably 20 to 70 mol%, more preferably 23 to 60 mol%, and even more preferably 25 to 50 mol%. By setting the proportions of the structural units (A) and (B) within the above numerical ranges, the solubility of the cyclic olefin copolymer in solvents is further improved, resulting in good moldability and an improved product yield.
The proportion of the olefin-derived structural unit (A) can be measured by ¹³ C-NMR.

In this embodiment, the olefin monomer, which is one of the copolymerization raw materials for the olefin copolymer, undergoes addition polymerization to form the above-mentioned structural unit (A). Specific examples include olefin monomers represented by the following general formula (Ia):

In the above general formula (Ia), R ³⁰⁰ represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 28 carbon atoms.
Examples of olefin monomers represented by the general formula (Ia) include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. Among these, ethylene and propylene are preferred, with ethylene being particularly preferred, from the viewpoint of obtaining optical components having superior heat resistance, mechanical properties, and optical properties. Two or more types of olefin monomers represented by the general formula (Ia) may be used. The olefin monomer represented by the general formula (Ia) preferably does not contain acyclic dienes, from the viewpoint of obtaining optical components having better moldability and optical properties.

Specific examples of cyclic olefin monomers represented by the above formula [Z-I], [Z-II], [Z-III], or [Z-IV] include, for example, bicyclo-2-heptene derivatives (bicyclohept-2-ene derivatives), tricyclo-3-decene derivatives, tricyclo-3-undecene derivatives, tetracyclo-3-dodecene derivatives, pentacyclo-4-pentadecene derivatives, pentacyclopentadecadiene derivatives, pentacyclo-3-pentadecene derivatives, pentacyclo-4-hexadecene derivatives, pentacyclo-3-hexadecene derivatives, and heptane derivatives. Examples of the cyclohexene derivatives include octacyclo-4-heptadecene derivatives, heptacyclo-5-eicosene derivatives, heptacyclo-4-eicosene derivatives, heptacyclo-5-heneicosene derivatives, octacyclo-5-docosene derivatives, nonacyclo-5-pentacosene derivatives, nonacyclo-6-hexacosene derivatives, cyclopentadiene-acenaphthylene adducts, 1,4-methano-1,4,4a,9a-tetrahydrofluorene derivatives, 1,4-methano-1,4,4a,5,10,10a-hexahydroanthracene derivatives, and cycloalkylene derivatives having 3 to 20 carbon atoms.

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

Among the cyclic olefin monomers represented by one or two types selected from the formula [Z-I], [Z-II], [Z-III], or [Z-IV], cyclic olefins represented by one or two types selected from the formula [Z-I] and [Z-IV] are preferred.

As the cyclic olefin monomer represented by the formula [Z-I], it is preferable to use one or more selected from bicyclo[2.2.1]-2-heptene (also called norbornene), tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]-3-dodecene (also called tetracyclododecene), 5-phenyl-bicyclo[2.2.1]hept-2-ene, 5-methyl-bicyclo[2.2.1]hept-2-ene, 5-tolyl-bicyclo[2.2.1]hept-2-ene, and 5-(ethylphenyl)-bicyclo[2.2.1]hept-2-ene, and it is more preferable to use tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]-3-dodecene. These cyclic olefins have the advantage of having a rigid ring structure, which makes it easier to maintain the elastic modulus of the copolymer and optical components. The cyclic olefin monomer represented by the formula [ZI] above preferably does not have a polar group, from the viewpoint of obtaining optical components having better moldability and optical properties.

The copolymer type of the copolymer according to this embodiment is not particularly limited, but examples include random copolymers and block copolymers. In this embodiment, it is preferable to use a random copolymer as the copolymer according to this embodiment, as this copolymer has excellent optical properties such as transparency, refractive index, and birefringence, and can produce high-precision optical components.

Copolymers according to this embodiment include a random copolymer of ethylene and tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]-3-dodecene (hereinafter also referred to as TD), a random copolymer of ethylene and bicyclo[2.2.1]-2-heptene (hereinafter referred to as norbornene or NB), a copolymer of ethylene and 5-phenyl-bicyclo[2.2.1]hept-2-ene, a copolymer of ethylene and 5-methyl-bicyclo[2.2.1]hept-2-ene, a copolymer of ethylene and 5-tolyl-bicyclo[2.2.1]hept-2-ene, a copolymer of ethylene and 5-(ethylphenyl)-bicyclo[2.2.1]hept-2-ene, a copolymer of ethylene and 5-(isopropylphenyl)-bicyclo[2.2.1]hept copolymers of ethylene and 5-(α-naphthyl)-bicyclo[2.2.1]hept-2-ene, copolymers of ethylene and 1,4-methano-1,4,4a,9a-tetrahydrofluorene, copolymers of ethylene and 1,4-methano-1,4,4a,5,10,10a-hexahydroanthracene, copolymers of ethylene and 1,4,4a,9a-tetrahydro-1,4-methanofluorene (hereinafter referred to as indene norbornene or IndNB), copolymers of ethylene and 1,4-dihydro-1,4-methanonaphthalene (hereinafter referred to as benzonorbornadiene or BNBD), copolymers of ethylene and tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]-3-dodecene and 1,4-dihydro-1,4-methanonaphthalene, copolymers of ethylene and tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene and 1,4,4a,9a-tetrahydro-1,4-methanofluorene (hereinafter referred to as indene norbornene), a copolymer of ethylene, norbornene and 1,4-dihydro-1,4-methanonaphthalene, a copolymer of ethylene, norbornene and indene norbornene, a copolymer of ethylene, tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]-3-dodecene and norbornene are preferred, and a random copolymer of ethylene and tetracyclo[4.4.0.1 ^2,5 .1 7,10 ]-3-dodecene, a copolymer of ethylene and 1,4-dihydro-1,4-methanonaphthalene, a copolymer of ethylene and tetracyclo[4.4.0.1 2,5 .1 ^7,10 ]-3-dodecene, a copolymer of ethylene and 1,4-dihydro-1,4-methanonaphthalene, a copolymer of ethylene and tetracyclo[4.4.0.1 ^2,5 . Copolymers of ethylene, tetracyclo[4.4.0.1 ^{2,5 .1 7,10} ]-3-dodecene and 1,4-dihydro-1,4-methanonaphthalene, and copolymers of ethylene, tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]-3-dodecene and norbornene are more preferred, and random copolymers of ethylene and tetracyclo[4.4.0.1 ^2,5 .1 ^{7,10 ]-3-dodecene, copolymers of ethylene and 1,4-dihydro-1,4-methanonaphthalene, and copolymers of ethylene, tetracyclo[4.4.0.1 2,5 .1 7,10} ]-3-dodecene and 1,4-dihydro-1,4-methanonaphthalene are even more preferred.

The copolymers of this embodiment may be used alone or in combination of two or more types.

The copolymer according to this embodiment can be produced by appropriately selecting the conditions according to the methods described in, for example, JP-A-60-168708, JP-A-61-120816, JP-A-61-115912, JP-A-61-115916, JP-A-61-271308, JP-A-61-272216, JP-A-62-252406, JP-A-62-252407, JP-A-2018-145349, International Publication No. 2015/122415, JP-A-2007-063409, and JP-A-2-173112.

(Cyclic olefin ring-opening polymer)
The cyclic olefin ring-opening polymer according to this embodiment is a cyclic olefin ring-opening polymer having a norbornene skeleton. From the viewpoint of further improving heat resistance and improving moldability while maintaining a good balance between the transparency and refractive index of the resulting optical component, it is preferable for the polymer to have a structure derived from at least one selected from the group consisting of a structural unit represented by the general formula (Z-I), a structural unit represented by the general formula (Z-II), and a structural unit represented by the general formula (Z-IV). However, excluding u=v=0 in the general formula (Z-I), x=0 in the general formula (Z-II), and x=0 in the general formula (Z-IV). The carbon-carbon bond formed by ring-opening of the carbon-carbon double bond in the general formulas (Z-I), (Z-II), and (Z-IV) corresponds to the structural unit (A), and the portion other than the structural unit (A) corresponds to the structural unit (B).

In other words, it is preferable that the ring-opening polymer has structural units derived from structural units similar to those of the copolymerization components.

{stereoregularity}
The stereoregularity according to this embodiment is measured by ¹³ C-NMR. The ¹³ C-NMR measurement is not particularly limited as long as it can distinguish between a mesostructure and a racemostructure. An example of specific measurement conditions is as described above.
Here, the positions of ¹³ C-NMR signals indicating the mesostructure and racemostructure differ depending on the polymer (copolymer, ring-opening polymer). The positions of ¹³ C-NMR signals and the method for measuring the signals will be described below for several embodiments.

(A: Polymer of ethylene and TD)
A cyclic olefin polymer having ethylene and a structure represented by the above formula [Z-I], where u = 0, v = 1, and the formula [Z-I] does not have an aromatic ring (i.e., a polymer of ethylene and TD).
In the ¹³ C-NMR spectrum,
-Integrated value of the signal in the range of 38.7 to 39.7 ppm (X _A )
Integrated value of the signal in the range of 40.3 to 41.2 ppm (Y _A )
In the above formula, the stereoregularity is defined as X _A /Y _A , and this ratio is 0.01 or more and 100 or less, preferably 0.1 or more and 10.0 or less, more preferably 0.2 or more and 5.0 or less, even more preferably 0.3 or more and 3.0 or less, still more preferably 0.4 or more and 1.5 or less, even more preferably 0.4 or more and 1.2 or less, still more preferably 0.5 or more and 1.0 or less, and most preferably 0.5 or more and 0.9 or less.
A: In the case of a polymer of ethylene and TD, only one peak appears within the range, so it is taken as the integral value of the signal.

(B: Polymer of ethylene and NB)
A cyclic olefin polymer having ethylene and a structural unit represented by the above formula [Z-I], where u = v = 0 and the formula [Z-I] does not have an aromatic ring (i.e., a polymer of ethylene and NB).
In the ¹³ C-NMR spectrum,
The sum of the integral values of the signals in the range of 44.6 to 45.6 ppm (X _B )
The sum of the integral values of the signals in the range of 45.6 to 46.0 ppm (Y _B )
In the formula, the stereoregularity is defined as _XB / _YB , and this ratio is 0.01 or more and 100 or less, preferably 0.01 or more and 50.0 or less, further preferably 0.05 or more and 5.0 or less, more preferably 0.25 or more and 4.0 or less, and most preferably 0.3 or more and 3.0 or less.
B: In the case of a polymer of ethylene and NB, multiple peaks appear within the range, so the sum of the integrated values of the signals is used.

(C: Polymer of ethylene and BNBD)
A cyclic olefin polymer having ethylene and a structural unit represented by the formula [Z-III] (that is, a polymer of ethylene and BNBD).
In the ¹³ C-NMR spectrum,
The value (X _C −Z) obtained by subtracting the integral value (Z) of the signal in the range of 30.1 to 30.8 ppm from the integral value (X _C ) of the signal in the range of 30.8 to 31.3 ppm.
The integral value of the signal in the range of 31.3 to 31.8 ppm (Y _C )
In the above formula, the stereoregularity is defined as (X _C −Z)/Y _C , and this ratio is 0.01 or more and 100 or less, preferably 0.01 or more and 10.0 or less. It is more preferably 0.05 or more and 5.0 or less, and even more preferably 0.1 or more and 1.0 or less. It is most preferably 0.3 or more and 1.0 or less. 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 in the range of 30.8 to 31.3 ppm, which partly includes a signal corresponding to BNBD-ethylene n-BNBE- (n = 2 or more).

(D: Polymer of ethylene, TD and BNBD)
A cyclic olefin polymer having ethylene, a structure represented by the formula [Z-I] above, in which u = 0, v = 1 and the structure does not have an aromatic ring, and a structural unit represented by the formula [Z-III] above (i.e., a polymer of ethylene, TD, and BNBD).
In the ¹³ C-NMR spectrum,
The integral value of the signal in the range of 38.7 to 39.7 ppm (X _D )
The integral value of the signal in the range of 40.3 to 41.2 ppm (Y _D )
In the formula, the ratio of _XD / _YD is 0.01 or more and 100 or less, preferably 0.01 or more and 10.0 or less, further preferably 0.05 or more and 5.0 or less, more preferably 0.1 or more and 1.0 or less, and most preferably 0.3 or more and 1.0 or less.

In addition, in the ¹³ C-NMR spectrum,
Integrated value of the signal in the range of 43.6 to 43.8 ppm (M _D )
Integrated value of the signal in the range of 44.5 to 45.0 ppm (N _D )
In the formula, the ratio of M _D /N _D is 0.01 or more and 100 or less, preferably 0.01 or more and 10.0 or less, further preferably 0.05 or more and 5.0 or less, more preferably 0.1 or more and 1.0 or less, and most preferably 0.3 or more and 1.0 or less.
In the case of a polymer of D: ethylene, TD, and BNBD, peaks of TD-ethylene-TD and BNBD-ethylene-BNBD appear within the range, so _XD and _YD are defined as the integral values of the TD-ethylene-TD signal, M _D and _ND are defined as the integral values of BNBD-ethylene-BNBD, and the stereoregularity is defined as _XD / _YD + _MD / _ND . The ratio of this stereoregularity= _XD / _YD + _MD / _ND is preferably 0.01 or more and 100 or less, more preferably 0.01 or more and 10.0 or less, even more preferably 0.05 or more and 5.0 or less, still more preferably 0.1 or more and 1.0 or less, and most preferably 0.3 or more and 1.0 or less.

The cyclic olefin polymer according to this embodiment preferably satisfies the following requirement (b).
(Requirement (b))
The proportion of the structural unit (B)-structural unit (B) chains in the structural unit (B) measured by ¹³ C-NMR is 0.1 mol % or more and 20.0 mol % or less.
Here, when signals are detected in the range of 51.2 to 55.5 ppm, the proportion of the structural unit (B)-structural unit (B) chains in the structural unit (B) as measured by ¹³ C-NMR is: in the ¹³ C-NMR spectrum: the sum (P) of the integral values of the signals detected in the range of 51.2 to 55.5 ppm
The sum of the integral values of the signals detected in the range of 54.0 to 54.6 ppm (Q)
It can be calculated by subtracting (Q) from (P) and dividing the result (P-Q) by (P).
In this case, the proportion of the structural unit (B)-structural unit (B) chains in the structural units (B), as measured by the ^C -NMR, is preferably 0.1 mol% or more and 20 mol% or less, more preferably 0.3 mol% or more and 10 mol% or less, even more preferably 0.6 mol% or more and 5.0 mol% or less, even more preferably 0.8 mol% or more and 4.5 mol% or less, and even more preferably 1.0 mol% or more and 3.6 mol% or less. This corresponds to the content of chains of cyclic olefin compounds having a norbornene skeleton, for example, corresponding to chains of TD and TD. When these are within the above ranges, aggregation is suppressed and the solubility of the polymer is further increased.

Furthermore, when signals are detected in the range of 40.0 to 50.0 ppm, the proportion of the structural unit (B)-structural unit (B) chain in the structural unit (B) measured by ¹³ C-NMR is: the sum (T) of the integral values of the signals detected in the range of 40.0 to 50.0 ppm in the ¹³ C-NMR spectrum
The sum of the integral values of the signals detected in the range of 45.0 to 46.0 ppm (U)
The value (U/T) obtained by dividing (U) by (T) using the formula (1) can be multiplied by 2.5, multiplied by the composition ratio of BNBD, and then divided by 100 to calculate the value.
In this case, the proportion of the structural unit (B)-structural unit (B) chain, as measured by the ^C -NMR, in the structural unit (B) is preferably 0.1 mol% or more and 20 mol% or less, more preferably 0.3 mol% or more and 10 mol% or less, even more preferably 0.6 mol% or more and 5.0 mol% or less, even more preferably 0.8 mol% or more and 4.5 mol% or less, and even more preferably 1.0 mol% or more and 3.6 mol% or less. This corresponds to the content of a chain of cyclic olefin compounds having a norbornene skeleton, for example, a chain of BNBD and BNBD. When these are within the above ranges, aggregation is suppressed and the solubility of the polymer is further increased.

Here, when signals are detected in both the range of 40.0 to 50.0 ppm and the range of 51.2 to 55.5 ppm, the proportion of the structural unit (B)-structural unit (B) chain measured by ^13C -NMR in the structural unit (B) can be calculated by adding up the proportions of the structural unit (B) calculated by the above-mentioned methods.
At this time, the proportion of the structural unit (B)-structural unit (B) chain, as measured by the ^C -NMR, in the structural unit (B) is preferably 0.1 mol% or more and 20 mol% or less, more preferably 0.3 mol% or more and 10 mol% or less, even more preferably 0.6 mol% or more and 5.0 mol% or less, even more preferably 0.8 mol% or more and 4.5 mol% or less, and even more preferably 1.0 mol% or more and 3.6 mol% or less. This corresponds to the content of chains of cyclic olefin compounds having a norbornene skeleton, and corresponds to, for example, the total of chains of TD and TD and chains of BNBD and BNBD. When these are within the above ranges, aggregation is suppressed and the solubility of the polymer is further increased.

The lower limit of the glass transition temperature (Tg) of the cyclic olefin polymer according to this embodiment is preferably 50°C or higher, more preferably 83°C or higher, and particularly preferably 110°C or higher.
The upper limit of Tg is preferably 250°C or less, more preferably 200°C or less, even more preferably 180°C or less, still more preferably 169°C or less, still more preferably 165°C or less, and particularly preferably 160°C or less.
When the cyclic olefin polymer according to the present embodiment is a cyclic olefin copolymer having the structural unit (A) and the structural unit (B), by having a Tg of at least the lower limit, the solubility in a solvent can be improved without excessively increasing the crystallinity of the cyclic olefin copolymer. On the other hand, by having a Tg of at most the upper limit, aggregation can be suppressed, and the solubility of the polymer can be further increased.
Furthermore, when the Tg is within the above range, sufficient heat resistance can be obtained and good moldability can be achieved when used in parts requiring heat resistance. Generally, the Tg of a cyclic olefin polymer varies depending on the composition of the structural units (A) and (B), and Tg tends to increase as the content of the structural units (B) increases. However, even with the same composition, the Tg tends to be higher as the number of structural unit (B) chains increases, although the reason is unclear. Such a Tg can be obtained by setting the proportion of structural unit (B) chains (structural unit (B)-structural unit (B) chains) derived from one or more cyclic monomers selected from the group consisting of the formulas [Z-I], [Z-II], [Z-III], and [Z-IV] to 0.1 mol % or more and 20.0 mol % or less of all the structural units (B) contained in the cyclic olefin copolymer.

The glass transition temperature can be measured using a differential scanning calorimeter (DSC). Specific measurement conditions include, for example, using a Hitachi High-Tech Science DSC-7020, raising the temperature from room temperature to 250°C at a heating rate of 10°C/min under a nitrogen atmosphere, holding the temperature for 5 minutes, and then lowering the temperature to -20°C at a heating rate of 10°C/min, holding the temperature for 5 minutes. The glass transition temperature (Tg) of the cyclic olefin polymer can then be determined from the endothermic curve obtained when the temperature is raised to 300°C at a heating rate of 10°C/min.

The molecular weight of the cyclic olefin polymer according to the present embodiment is not particularly limited. When the intrinsic viscosity [η][dL/g] is used as an alternative index of molecular weight, the value of [η][dL/g] measured in accordance with ASTM J1601 is preferably 0.1 or more and 5.0 or less, more preferably 0.2 or more and 3.0 or less, and most preferably 0.2 or more and 2.0 or less.
When the cyclic olefin polymer according to the present embodiment is a cyclic olefin copolymer having the structural unit (A) and the structural unit (B), the weight average molecular weight (Mw) determined by gel permeation chromatography (GPC) is preferably in the range of 1,000≦Mw≦4,500,000, preferably 3,000≦Mw≦3,000,000, more preferably 5,000≦Mw≦2,000,000, even more preferably 10,000≦Mw≦1,000,000, and most preferably 30,000≦Mw≦500,000.
When the intrinsic viscosity or weight average molecular weight (Mw) is equal to or greater than the lower limit, the solubility in a solvent or the mechanical strength of a molded article can be improved, whereas when the intrinsic viscosity is equal to or less than the upper limit, the moldability can be improved.

Furthermore, the cyclic olefin polymer according to 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.
When the cyclic olefin polymer according to this embodiment satisfies the above-mentioned numerical ranges for Tg and Mw, it is possible to simultaneously improve the solubility in solvents and the mechanical strength of the molded article.

The density of the cyclic olefin polymer according to this embodiment, as measured in water at 23°C by the underwater displacement method according to JIS K7112, is preferably 1000 kg/m ³ or more and 1200 kg/m ³ or less, more preferably 1020 kg/m ³ or more and 1100 kg/m ³ or less, even more preferably 1040 kg/m ³ or more and 1080 kg/m ³ or less, even more preferably 1050 kg/m ³ or more and 1070 kg/m ³ or less, and even more preferably 1055 kg/m ³ or more and 1065 kg/m ³ or less.
When the density value is within the above range, the heat resistance of the resulting optical component can be further improved while maintaining a good balance between the transparency and refractive index.
The test piece can be obtained, for example, by sandwiching the cyclic olefin polymer according to this embodiment between ultra-heat-resistant polyimide films (product name: Upilex, manufactured by Ube Industries, Ltd.) and vacuum press-molding the film using a 0.1 mm spacer under conditions of 260°C, 10 MPa, and 3 minutes.

(Other ingredients)
The cyclic olefin polymer according to the present embodiment may contain, as necessary, hydrophilic agents, stabilizers, weather stabilizers, heat stabilizers, antioxidants, metal deactivators, hydrochloric acid absorbers, antistatic agents, flame retardants, slip agents, antiblocking agents, antifogging agents, lubricants, natural oils, synthetic oils, waxes, organic or inorganic fillers, and the like, in appropriate amounts within a range that does not impair the object of the present embodiment.

The cyclic olefin polymer composition according to this embodiment preferably further contains a hydrophilic agent, which can prevent the deterioration of various properties of the molded article under high-temperature and high-humidity conditions.
The hydrophilic agent is preferably a fatty acid ester of a fatty acid and a polyhydric alcohol, more preferably a fatty acid ester of a fatty acid and a polyhydric alcohol having one or more ether groups.

Examples of fatty acid esters include monoglycerin fatty acid esters, diglycerin fatty acid esters, triglycerin fatty acid esters, pentaerythritol monostearate, pentaerythritol distearate, and pentaerythritol tristearate.
The fatty acid ester of a fatty acid and a polyhydric alcohol having one or more ether groups is an ester of a fatty acid and a polyhydric alcohol having one or more ether groups. Note that the ether group of the polyhydric alcohol does not include the ether group in the ether group.
Examples of polyhydric alcohols having one or more ether groups include monoglycerin, diglycerin, triglycerin, tetraglycerin, and sorbitan.
In this embodiment, the fatty acid ester preferably includes a monoglycerin fatty acid ester, a diglycerin fatty acid ester, or a triglycerin fatty acid ester. The diglycerin fatty acid ester is obtained by esterifying at least one of the four hydroxy groups contained in diglycerin with a fatty acid.

Fatty acids include saturated fatty acids such as butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, capric acid, lauric acid, myristic acid, palmitic acid, and stearic acid; monounsaturated fatty acids such as crotonic acid, myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, gadoleic acid, and eicosenoic acid; diunsaturated fatty acids such as linoleic acid, eicosadienoic acid, and docosadienoic acid; triunsaturated fatty acids such as linolenic acid, pinolenic acid, eleostearic acid, and eicosatrienoic acid; and tetraunsaturated fatty acids such as stearidonic acid, arachidonic acid, and eicosatetraenoic acid.

Examples of diglycerin fatty acid esters include saturated diglycerin fatty acid esters such as diglycerin monocaprylate, diglycerin dicaprylate, diglycerin monocaprate, diglycerin dicaprate, diglycerin monolaurate, diglycerin dilaurate, diglycerin monomyristate, diglycerin dimyristate, diglycerin monopalmitate, diglycerin dipalmitate, diglycerin monostearate, diglycerin distearate, diglycerin monobehenate, and diglycerin dibehenate; and unsaturated diglycerin fatty acid esters such as diglycerin monooleate and diglycerin dioleate; and these may be used alone or in combination of two or more.
In this embodiment, the diglycerin fatty acid ester is preferably an ester of diglycerin and a saturated or unsaturated fatty acid having 12 to 18 carbon atoms selected from the above.

From the perspective of the effects of this embodiment, it is preferable to contain a diglycerin unsaturated fatty acid ester as the main component, and it is even more preferable to contain diglycerin monooleate as the main component. The diglycerin skeleton is hydrophilic, and the fatty acid improves compatibility with the resin, so transparency is maintained and excellent resistance to moist heat is achieved.

The cyclic olefin polymer composition according to this embodiment may contain at least one diglycerol fatty acid ester. Preferred embodiments of the at least one diglycerol fatty acid ester include a monoester alone or a combination of a monoester and a diester.

Triglycerin fatty acid esters are esters of fatty acids and triglycerin.
The triglycerin fatty acid ester according to this embodiment is obtained by esterifying at least one of three hydroxy groups contained in triglycerin with a fatty acid.

Examples of triglycerin fatty acid esters include triglycerin monocaprylate, triglycerin dicaprylate, triglycerin tricaprylate, triglycerin monocaprate, triglycerin dicaprate, triglycerin tricaprate, triglycerin monolaurate, triglycerin dilaurate, triglycerin trilaurate, triglycerin monomyristate, triglycerin dimyristate, triglycerin trimyristate, triglycerin monopalmitate, and triglycerin dipalmitate. triglycerin saturated fatty acid esters such as triglycerin tripalmirate, triglycerin monostearate, triglycerin distearate, triglycerin tristearate, triglycerin monobehenate, triglycerin dibehenate, and triglycerin tribehenate; triglycerin unsaturated fatty acid esters such as triglycerin monooleate, triglycerin dioleate, and triglycerin trioleate; and the like. One or more selected from these may be used in combination.
The triglycerin fatty acid ester according to the present embodiment preferably contains an ester of triglycerin and a saturated or unsaturated fatty acid having from 8 to 24 carbon atoms, and more preferably contains an ester of triglycerin and a saturated or unsaturated fatty acid having from 12 to 18 carbon atoms.

Examples of the triglycerin fatty acid ester according to this embodiment include a monoester alone, a mixture of a monoester and a diester, and a mixture of a monoester, a diester, and a triester.
As such triglycerin fatty acid esters, for example, compounds described in JP-A Nos. 2006-232714, 2002-275308, and 10-165152 can be used.
Examples of commercially available hydrophilic agents according to this embodiment include Rikemal DO-100 (manufactured by Riken Vitamin Co., Ltd.) and Exepar PE-MS (manufactured by Kao Corporation).
In the composition as the cyclic olefin polymer according to this embodiment, the lower limit of the content of the hydrophilic agent is preferably 0.05 parts by mass or more, more preferably 0.4 parts by mass or more, per 100 parts by mass of the cyclic olefin polymer composition, and the upper limit of the content of the hydrophilic agent is preferably 3.0 parts by mass or less, more preferably 2.5 parts by mass or less, and even more preferably 1.2 parts by mass or less, per 100 parts by mass of the cyclic olefin polymer composition.

Known antioxidants can be used. Specifically, hindered phenol compounds, sulfur-based antioxidants, lactone-based antioxidants, organic phosphite compounds, organic phosphonite compounds, or combinations of these can be used.

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, which can be used alone or in combination of two or more. The amount of lubricant used is not particularly limited, but can be, for example, 0.01 to 3 parts by weight, and preferably 0.01 to 2 parts by weight, per 100 parts by weight of the olefin polymer.

As a slip agent, it is preferable to use amides of saturated or unsaturated fatty acids such as lauric acid, palmitic acid, oleic acid, stearic acid, erucic acid, and hebenic acid, or bisamides of these saturated or unsaturated fatty acids. Of these, erucic acid amide and ethylene bisstearamide are particularly preferred. These fatty acids can typically be blended in an amount of 0.01 to 5 parts by mass per 100 parts by mass of the cyclic olefin polymer.

Antiblocking agents include finely divided silica, finely divided aluminum oxide, finely divided clay, powdered or liquid silicone resin, tetrafluoroethylene resin, and finely divided crosslinked resin powder (e.g., crosslinked acrylic or methacrylic resin powder). Of these, finely divided silica and finely divided crosslinked resin powder are preferred.

The cyclic olefin copolymer having a norbornene skeleton and the cyclic olefin ring-opening polymer having a norbornene skeleton according to the present embodiment can be used in various forms, such as lens, sphere, rod, plate, column, cylinder, tube, fiber, film, or sheet. Among these, they are preferably used in optical components, films, and medical components. Examples of optical components include optical lenses such as eyeglass lenses, fθ lenses, pickup lenses, imaging lenses, sensor lenses, digital camera lenses, projector lenses, optical disc pickup lenses, and in-vehicle camera lenses, as well as prisms, light guide plates, and XR devices. Examples of films include retardation films for displays, visibility-improving films for displays, touch sensor films, solar cell base film substrates, circuit boards, high-frequency application substrates, substrates, films, or sheets for liquid crystal displays and solar cells, tablet packaging sheets (PTP), shrink films, easily tearable food packaging films, and film capacitors. Examples of medical parts include pre-filled syringes, plastic vials, infusion bags, blood analysis cells, catheter members, pill bottles, test containers, sterilization sheets, bioplates, and biochips.
Cyclic olefin copolymers and cyclic olefin ring-opening polymers have high solubility in solvents, and therefore can be easily dissolved at or near room temperature in solvents (e.g., methylcyclohexane, toluene, etc.) that are particularly used for coating polymers. Therefore, a homogeneous solution can be obtained, and when formed into a molded product such as a film, it is uniform and has excellent mechanical strength and elongation.

The molded article according to this embodiment can be obtained by molding a composition containing a cyclic olefin polymer into a predetermined shape. The method for molding a composition containing a cyclic olefin polymer to obtain a molded article is not particularly limited, and known methods can be used. Depending on the intended use and shape, applicable methods include extrusion molding, injection molding, compression molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, vacuum molding, powder slush molding, calendar molding, and foam molding. Among these, injection molding and extrusion molding are preferred from the standpoint of moldability and productivity. Furthermore, molding conditions are appropriately selected depending on the intended use or molding method. For example, the composition temperature during injection molding is typically selected from the range of 150°C to 400°C, preferably 200°C to 350°C, and more preferably 230°C to 330°C.

Cyclic olefin copolymers and cyclic olefin ring-opening polymers may be used in the preparation of coating agents, or may be mixed in a solvent during the preparation of the coating agent.

Solvents for preparing coating agents include, but are not limited to, 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, isopropyl alcohol, butanol, pentanol, hexanol, propanediol, and phenol; ketone solvents such as acetone, methyl isobutyl ketone, methyl ethyl ketone, pentanone, hexanone, isophorone, and acetophenone; cellosolves such as methyl cellosolve and ethyl cellosolve; 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. These may be used alone or in combination.

When used as a coating agent, the coating method is not particularly limited and can be performed by any known method. For example, it can be applied by methods such as die coating, flow coating, spray coating, bar coating, gravure coating, gravure reverse coating, kiss reverse coating, microgravure coating, roll coating, blade coating, rod coating, roll doctor coating, air knife coating, comma roll coating, reverse roll coating, transfer roll coating, kiss roll coating, curtain coating, and dip coating, and then dried by an appropriate method such as natural drying or forced drying with heat to obtain a coating film.

<Method of producing cyclic olefin polymer>
The cyclic olefin polymer according to this embodiment can be obtained by, for example, a method of melt-kneading the cyclic olefin polymer and other components added as needed using a known kneading device such as an extruder or a Banbury mixer; a method of dissolving the cyclic olefin polymer and other components added as needed in a common solvent and then evaporating the solvent; or a method of adding a solution of the cyclic olefin polymer and other components added as needed to a poor solvent to cause precipitation.

Next, the obtained 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. By carrying out the annealing treatment, the molecules of the cyclic olefin polymer in the molded body are relaxed, and the free volume is reduced. Therefore, even if the heat treatment is carried out, a change in specific gravity (a change in volume) is unlikely to occur.
Here, if the annealing conditions are too strict, the molded body will deform and will not return to its original shape, so it is preferable to perform the annealing under the above conditions within a range in which the molded body does not deform. In other words, it is preferable to perform the annealing at a temperature and for a time that will not cause deformation of the molded body.

During polymerization, the stereoregularity (ratio of racemo structure and meso structure) of the cyclic olefin polymer of this embodiment can be adjusted by selecting the catalyst and co-catalyst. The catalyst and co-catalyst are described in detail below.

[catalyst]
The catalyst according to this embodiment (hereinafter also referred to as the main catalyst) is not particularly limited as long as it can adjust the ratio of the racemo structure and meso structure of the cyclic olefin polymer.Specific examples of such main catalysts include half-metallocene titanium compounds, zirconium compounds, and hafnium compounds, and metallocene titanium compounds, zirconium compounds, and hafnium compounds.Among these, half-metallocene titanium compounds, zirconium compounds, and hafnium compounds having a cyclopentadienyl group or a pyrazolate group, and metallocene titanium compounds, zirconium compounds, and hafnium compounds having fluorene are particularly preferred.With these main catalysts, the ratio of the racemo structure and meso structure can be easily adjusted.

Specific examples of the above-mentioned main catalyst include 3,5-bismethylethyl-1-pyrazolate-t-butylcyclopentadiene titanium dichloride (paragraphs 0385 to 0388 of JP 2019-172954 A), bis-t-butylketimide cyclopentadienyl titanium dichloride (paragraphs 0003 to 0004 of JP 2018-150273 A), dimethylmethylenefluorenylcyclopentadiene zirconium dimethyl, diphenylmethylenefluorenylcyclopentanyl zirconium dimethyl (paragraphs 0088 to 0109 of JP 2019-172954 A), and dimethylmethylenebisindenylzirconium dichloride (paragraphs 0089 to 0109 of JP 2019-172954 A). Examples of such diphenylmethyleneindenylcyclopentanylzirconium dichloride include diphenylmethyleneindenylcyclopentanylzirconium dichloride (WO 2014/185253, paragraphs 0092 to 0093), 3,5-bis-t-butyl-1-pyrazolate-t-butylcyclopentadiene titanium dichloride, 3,5-bis-t-butyl-1-pyrazolate-indenyl titanium dichloride, 3-(4-methoxyphenyl)-5-(4-t-butylphenyl)-1-pyrazolate-t-butylcyclopentadiene titanium dichloride, and 3,5-diphenyl-1-pyrazolate-t-butylcyclopentadiene titanium dichloride.

[Cocatalyst]
The co-catalyst according to this embodiment is not particularly limited as long as it can improve the catalytic activity of the main catalyst. Examples of such co-catalysts include ionic compounds, with aluminum compounds or boron compounds being particularly preferred. Examples include trialkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, and mixtures thereof; triphenylcarbenium tetrakis(pentafluorophenyl)borate; and N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, with borate compounds having a pentafluorophenyl group being particularly preferred. This co-catalyst allows for more optimal control of stereoregularity.

Specific examples of such cocatalysts include triphenylcarbenium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, MMAO (modified methylaluminoxane), and PMAO (polymethylaluminoxane).

A preferred combination of the main catalyst and co-catalyst according to this embodiment is one or more selected from half-metallocene-based titanium compounds, zirconium compounds, and hafnium compounds having a cyclopentadienyl group or a pyrazolate group, or metallocene-based titanium compounds, zirconium compounds, and hafnium compounds having fluorene, as the main catalyst, and a borate compound having a pentafluorophenyl group as the co-catalyst.
Specific examples of preferred combinations of the main catalyst and the co-catalyst include the following combinations.
Main catalyst: 3,5-bismethylethyl-1-pyrazolate-t-butylcyclopentadienyltitanium dichloride, bis-t-butylketimide cyclopentadienyltitanium diethyl, dimethylmethylenefluorenylcyclopentadienylzirconium dimethyl, diphenylmethylenefluorenylcyclopentanylzirconium dimethyl, dimethylmethylenebisindenylzirconium dichloride, diphenylmethyleneindenylcyclopentanyl di titanium dioxide, 3,5-bis-t-butyl-1-pyrazolate-t-butylcyclopentadiene titanium dichloride, 3,5-bis-t-butyl-1-pyrazolate-indenyl titanium dichloride, 3-(4-methoxyphenyl)-5-(4-t-butylphenyl)-1-pyrazolate-t-butylcyclopentadiene titanium dichloride, 3,5-diphenyl-1-pyrazolate-t-butylcyclopentadiene titanium dichloride. Co-catalysts: triphenylcarbenium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate. Here, the main catalyst and the co-catalyst may be used alone or in combination of two or more.
By using the above combination of the main catalyst and the co-catalyst, the solubility of the cyclic olefin polymer can be made more favorable. Although the mechanism behind this is not entirely clear, it is thought that by using the above co-catalyst as the co-catalyst, the proportion of meso-isomers in the cyclic olefin polymer can be reduced.

The method for producing a cyclic olefin polymer according to this embodiment is characterized by copolymerizing an olefin and a cyclic olefin in the presence of the above-mentioned main catalyst and co-catalyst.

In the method for producing a cyclic olefin polymer according to this embodiment, a copolymer may be produced by copolymerizing two or more types of olefins with a cyclic olefin.
The use of each component constituting the olefin polymerization catalyst of the present invention and the order of addition to the polymerization vessel may be selected arbitrarily, but examples include the following. Hereinafter, the main catalyst (A), co-catalyst (B), carrier (C), and organic compound component (D) may be referred to as "components (A) to (D)," respectively. (1) A method of adding component (A) alone to a polymerization vessel. (2) A method of adding components (A) and (B) to a polymerization vessel in any order. (3) A method of adding a catalyst component in which component (A) is supported on component (C), and component (B), to a polymerization vessel in any order. (4) A method of adding a catalyst component in which component (B) is supported on component (C), and component (A), to a polymerization vessel in any order. (5) A method of adding a catalyst component in which component (A) and component (B) are supported on component (C), to a polymerization vessel.

In each of the above methods, component (D) may be added at any stage.
In each of the above methods, at least two of the catalyst components may be contacted in advance.
In the above methods (4) and (5) in which component (B) is supported, unsupported component (B) may be added in any order, if necessary. In this case, the components (B) may be the same or different. Furthermore, the solid catalyst component in which component (A) is supported on component (C) and the solid catalyst component in which components (A) and (B) are supported on component (C) may be prepolymerized with an olefin, or the prepolymerized solid catalyst component may have further catalyst components supported thereon.

Copolymerization of olefins and cyclic olefins can be carried out by either liquid-phase polymerization methods such as solution polymerization and suspension polymerization, or gas-phase polymerization methods. 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 ethylene chloride, chlorobenzene, and dichloromethane. These inert hydrocarbon media may be used alone or in combination.

When olefin polymerization is carried out using the above-mentioned olefin polymerization catalyst, the main catalyst (A) is used in an amount of usually 10 ⁻¹² to 10 ⁻² mol, preferably 10 ⁻¹⁰ to 10 ⁻³ mol, per liter of reaction volume.

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

In the production method of this embodiment, the polymerization temperature in the polymerization step is usually −50 to +200° C., preferably 0 to 180° C.; the polymerization pressure is usually atmospheric pressure to 10 MPa gauge pressure, preferably atmospheric pressure to 5 MPa gauge pressure. The polymerization reaction can be carried out in any of a batch system, a semi-continuous system, and a continuous system. Furthermore, the polymerization can be carried out in two or more stages with different reaction conditions.

The molecular weight of the resulting cyclic olefin polymer can be adjusted by adding hydrogen to the polymerization system, changing the polymerization temperature, or by adjusting the amount of co-catalyst (B) used. If hydrogen is added, the appropriate amount is approximately 0.001 to 5,000 NL per kg of copolymer produced.

Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various other configurations can also be adopted.
Furthermore, the present invention is not limited to the above-described embodiment, and modifications and improvements within the scope of achieving the object of the present invention are included in the present invention.

The present embodiment will be described in detail below with reference to examples. Note that the present embodiment is not limited to the descriptions of these examples.

First, we will explain the measurement methods used in the examples.

[ ¹³ C-NMR measurement]
The ¹³ C-NMR measurement was carried out under the following conditions.
Apparatus: AVANCE III cryo-500 nuclear magnetic resonance, manufactured by Bruker Biospin Measurement nucleus: ¹³ C (125 MHz)
Measurement mode: Single pulse proton (with reverse gate) decoupling Pulse width: 90 degrees Number of points: 64,000
Measurement range: -55 to 195 ppm (total 250 ppm)
Repeat time: 12 seconds Number of accumulations: 256 Solvent: 1,1,2,2-tetrachloroethane-d2
Concentration: 10%w/v
Temperature: 120℃
Chemical shift reference: tetramethylsilane reference (1,1,2,2-tetrachloroethane-d2: equivalent to 74.2 ppm)

Under the above conditions, ^13C -NMR measurements were carried out to determine the proportion of the [CO]-[CO] constitutional unit (the total of the [CO]-[CO] structure, [E]-[CO] structure, and [E]-[E] structure was taken as 100 mol%), as well as the proportion of the [CO]-[E]-[CO] racemo structure and the [CO]-[E]-[CO] mesostructure (the total of the [CO]-[E]-[CO] racemo structure and [CO]-[E]n-[CO]n (n≧2) was taken as 100 mol%).
Here, [CO] means a structural unit derived from a cyclic olefin, and [E] means a structural unit derived from ethylene.
Furthermore, if a signal is detected in the range of 51.2 to 55.5 ppm,
The sum of the integrated values of the signals detected in the range of 51.2 to 55.5 ppm (P)
- Signal integral value (Q) in the range of 54.0 to 54.6 ppm
The proportion of linked structural units (B) was calculated by measuring the ratio of linked structural units (B) to linked structural units (B) and dividing the value (P−Q) obtained by subtracting (Q) from (P) by (P).
Alternatively, if a signal is detected in the range of 40.0 to 50.0 ppm,
The sum of the integral values of the signals detected in the range of 40.0 to 50.0 ppm (T)
The sum of the integral values of the signals detected in the range of 45.0 to 46.0 ppm (U)
The ratio of linked structural units (B) was calculated by dividing (U) by (T) (U/T), multiplying the result by 2.5, multiplying it by the composition ratio of BNBD, and then dividing by 100.
Alternatively, when signals are detected in both the range of 40.0 to 50.0 ppm and the range of 51.2 to 55.5 ppm,
The proportion of the chains of the structural unit (B) was calculated by adding up the proportions of the structural unit (B) calculated by the above-mentioned methods.

[Solubility test]
The solubility in methylcyclohexane and toluene was evaluated under the following conditions.
<Solubility in methylcyclohexane>
In the case of the examples and comparative examples using a polymer of ethylene and TD (i.e., Examples 1, 2, 5 to 9, 11 to 13 and Comparative Example 1),
Sample: Cyclic olefin copolymer produced in each of the Examples and Comparative Examples described below Solvent: Methylcyclohexane Solution concentration: 10 wt %
Temperature: 25℃
Solubility evaluation criteria: Dissolved, and the solubility was visually confirmed after leaving it for a day. A: No undissolved polymer, transparent state. B: No undissolved polymer immediately after dissolution, and opaque state after leaving it for a day. C: Undissolved polymer, cloudy state.

In the case of the examples and comparative examples using a polymer of ethylene and BNBD and a polymer of ethylene, TD and BNBD (i.e., Examples 3, 4, 10, 14 and Comparative Example 2),
Sample: Cyclic olefin copolymer produced in each of the Examples and Comparative Examples described below Solvent: Methylcyclohexane Solution concentration: 1 wt %
Temperature: 50℃
Solubility evaluation criteria: Dissolved, and the solubility was visually confirmed after leaving it for a day. A: No undissolved polymer, transparent state. B: No undissolved polymer immediately after dissolution, and opaque state after leaving it for a day. C: Undissolved polymer, cloudy state.

<Solubility in toluene>
Sample: Cyclic olefin copolymer produced in each of the Examples and Comparative Examples described below Solvent: Toluene Solution concentration: 10 wt %
Temperature: 25℃
Solubility evaluation criteria: Dissolved, and the solubility was visually confirmed after leaving it for a day. A: No undissolved polymer, transparent state. B: No undissolved polymer immediately after dissolution, and opaque state after leaving it for a day. C: Undissolved polymer, cloudy state.

[Moldability]
The cyclic olefin copolymer obtained in each Example and Comparative Example was sandwiched between ultra-heat-resistant polyimide films (trade name: Upilex, manufactured by Ube Industries, Ltd.) and vacuum-press molded using a 0.1 mm spacer at 260°C, 10 MPa, and for 3 minutes.
A: No cracks were observed visually, and 80% or more of the area maintained the film shape.
B: Cracks were visually observed, and more than 30% but less than 80% of the film maintained its shape.
C: Cracks were visually observed, and 70% or more of the film area did not maintain its shape.
[density]
The cyclic olefin copolymer obtained in each Example and Comparative Example was sandwiched between ultra-heat-resistant polyimide films (trade name: Upilex, manufactured by Ube Industries, Ltd.) and vacuum-press molded using a 0.1 mm spacer at 260°C, 10 MPa, and 3 minutes to obtain test specimens. The density of these test specimens was measured in water at 23°C in accordance with JIS K7112. The density was measured by the underwater displacement method.

[Intrinsic viscosity [η]]
Using a migration viscometer (manufactured by Rigo Co., Ltd., Type VNR053U), 0.25 to 0.30 g of the cyclic olefin copolymer was dissolved in 25 ml of decalin to prepare a sample. The specific viscosity of the cyclic olefin copolymer was measured at 135°C in accordance with ASTM J1601, and the ratio of this to the concentration was extrapolated to a concentration of 0 to determine the intrinsic viscosity [η] of the cyclic olefin copolymer.
[Weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) of polymer]
The weight average molecular weight (Mw) and number average molecular weight (Mn) of the olefin polymer were determined by gel permeation chromatography (GPC), calculated from a molecular weight distribution curve obtained using a Waters "Alliance GPC 2000" gel permeation chromatograph (high-temperature size exclusion chromatograph), under the following operating conditions:
<Equipment and conditions used>
Measurement equipment: Gel permeation chromatograph Alliance GPC2000 (Waters)
Analysis software: Chromatography Data System Empower (trademark, Waters)
Column: TSKgel GMH6-HT x 2 + TSKgel GMH6-HT x 2
(Inner diameter 7.5 mm x length 30 cm, Tosoh Corporation)
Mobile phase: o-dichlorobenzene [=ODCB] (Wako Pure Chemical Industries, Ltd., special grade reagent)
Detector: Differential refractometer (built into the device)
Column temperature: 140°C
Flow rate: 1.0mL/min
Injection volume: 400μL
Sampling time interval: 1 second Sample concentration: 0.15% (w/v)
Molecular weight calibration: Monodisperse polystyrene (Tosoh Corporation) / molecular weight 495 to 20.6 million

[Glass transition temperature Tg (°C)]
The glass transition temperature (Tg) of the cyclic olefin copolymer was measured under a nitrogen atmosphere using a DSC-7020 manufactured by Hitachi High-Tech Science Corporation. The cyclic olefin copolymer was heated from room temperature to 250°C at a heating rate of 10°C/min and then held at that temperature for 5 minutes. Next, the temperature was lowered to -20°C at a heating rate of 10°C/min and then held at that temperature for 5 minutes. The glass transition temperature (Tg) of the cyclic olefin copolymer was then determined from the endothermic curve when the temperature was raised to 300°C at a heating rate of 10°C/min.

Example 1
A 500 mL glass reactor that had been thoroughly purged with nitrogen was charged with 300 mL of a 9/1 cyclohexane/hexane mixed solution and 2.2 g of tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]-3-dodecene (hereinafter also referred to simply as "tetracyclododecene"; Mw: 160.2 (g/mol)), and the liquid and gas phases were saturated with 90 L/hr of ethylene and 0.24 L/hr of hydrogen. 59.4 mg (0.3 mmol) of TIBAL (triisobutylaluminum) was added. Subsequently, 0.003 mmol of 3,5-bismethylethyl-1-pyrazolate-t-butylcyclopentadienyltitanium dichloride was added, and 0.012 mmol of triphenylcarbenium tetrakis(pentafluorophenyl)borate (hereinafter referred to as borate compound (1), synthesized with reference to JP-A-2018-105273) was added to initiate a polymerization reaction.

Ethylene (90 L/hr) and hydrogen (0.24 L/hr) were continuously supplied, and polymerization was carried out at 50°C under atmospheric pressure for 5 minutes. The polymerization was then terminated by the addition of a small amount of isobutanol. After polymerization was completed, the reaction mixture was added to 1 L of a 3/1 acetone/methanol mixed solvent containing a small amount of hydrochloric acid to precipitate the polymer. After washing with the same solvent, the mixture was dried under reduced pressure at 130°C for 10 hours to obtain 0.346 g of an ethylene-tetracyclododecene copolymer. The polymerization activity was 1.38 kg/mmol-hr, and the resulting ethylene-tetracyclododecene copolymer (structural unit (A): 62 mol% ethylene, structural unit (B): 38 mol% tetracyclododecene) had an intrinsic viscosity [η] of 0.92 (dL/g), an Mw of 217,000 (g/mol), and an Mw/Mn of 2.43. The glass transition temperature measured by differential scanning calorimetry (DSC) was 153°C, and the ratio of racemostructure/mesostructure determined by ^13C -NMR measurement was 0.89. The ratio of racemostructure/mesostructure was based on the calculation method for the above-mentioned A: polymer of ethylene and TD. Furthermore, the ratio of structural unit (B)-structural unit (B) chains to structural unit (B) measured by ^13C -NMR was 1.0, and the solubility in methylcyclohexane was good (Solubility in methylcyclohexane: A). The solubility in toluene was also good (Solubility in toluene: A). The formability of the film was also good (Film formability: A). The density was 1046 (kg/m ³ ). The results are shown in Table 1.

Example 2
A 500 mL glass reactor thoroughly purged with nitrogen was charged with 245 mL of a cyclohexane/hexane (9/1) mixed solution and 5.0 g of tetracyclododecene, and the liquid and gas phases were saturated with ethylene at 50 L/hr. 39.6 mg (0.2 mmol) of TIBAL was added. 0.0005 mmol of bis-t-butylketimidocyclopentadienyltitanium diethyl was added, followed by 0.002 mmol of borate compound (1) to initiate polymerization.

Ethylene was continuously fed at 50 liters/hr, and polymerization was carried out for 10 minutes at 50°C under atmospheric pressure. The polymerization was then terminated by adding a small amount of isobutanol. After polymerization was completed, the reaction mixture was added to 1 liter of a 3/1 acetone/methanol mixed solvent containing a small amount of hydrochloric acid to precipitate the polymer. After washing with the same solvent, the mixture was dried under reduced pressure at 130°C for 10 hours, yielding 0.41 g of an ethylene-tetracyclododecene copolymer. The polymerization activity was 4.91 kg/mmol-hr, and the resulting ethylene-tetracyclododecene copolymer (structural unit (A): ethylene 62 mol%, structural unit (B): tetracyclododecene 38 mol%) had an intrinsic viscosity [η] of 0.45 (dL/g), an Mw of 124,000 (g/mol), and an Mw/Mn of 2.07. The glass transition temperature measured by DSC was 151°C, and the ratio of racemostructure/mesostructure measured by ^13C -NMR was 0.72. The ratio of racemostructure/mesostructure was based on the calculation method for the above-mentioned A: polymer of ethylene and TD. Furthermore, the ratio of structural unit (B)-structural unit (B) chains to structural unit (B) measured by ^13C -NMR was 1.9, and the solubility in methylcyclohexane was good (Solubility in methylcyclohexane: A). The solubility in toluene was also good (Solubility in toluene: A). The formability of the film was also good (Film formability: A). The results are shown in Table 1.

Example 3
A 500 ml glass reactor thoroughly purged with nitrogen was charged with 289 mL of a cyclohexane/hexane (9/1) mixed solution and 20.9 g of benzonorbornadiene (hereinafter also referred to as BNBD; Mw: 142.2 (g/mol)), and the liquid and gas phases were saturated with ethylene at 51 L/hr and hydrogen at 2 L/hr. 59.4 mg (0.3 mmol) of TIBAL was added, followed by the addition of 0.003 mmol of 3,5-bis-1-methylethyl-1-pyrazolate-t-butylcyclopentadienyltitanium dichloride, and then 0.012 mmol of borate compound (1) to initiate polymerization. Ethylene was continuously fed at 51 L/hr and hydrogen at 2 L/hr, and polymerization was carried out at 50°C under atmospheric pressure for 10 minutes. The polymerization was then terminated by the addition of a small amount of isobutanol. After polymerization was complete, the reaction mixture was added to 1 liter of a 3/1 acetone/methanol mixed solvent containing a small amount of hydrochloric acid to precipitate the polymer. After washing with the same solvent, the mixture was dried under reduced pressure at 130°C for 0 hours, yielding 0.658 g of an ethylene-benzonorbornadiene copolymer. The polymerization activity was 6.58 kg/mmol-hr, and the intrinsic viscosity [η] of the resulting ethylene-benzonorbornadiene copolymer (structural unit (A): ethylene 67 mol%, structural unit (B): benzonorbornadiene 33 mol%) was 0.20 (dL/g), Mw was 34,300 (g/mol), and Mw/Mn was 1.76. The glass transition temperature measured by DSC was 106°C, and the racemostructure/mesostructure ratio measured by ^C -NMR was 0.79. The racemostructure/mesostructure ratio was calculated based on the calculation method used for the polymer C of ethylene and BNBD described above. Furthermore, the proportion of structural unit (B)-structural unit (B) chains in structural unit (B) measured by ^13C -NMR was 2.2, and the solubility in methylcyclohexane was good (Solubility in methylcyclohexane: A). The solubility in toluene was good (Solubility in toluene: A). The formability into a film was good (Film formability: A). The results are shown in Table 1.

Example 4
A 500 mL glass reactor that had been thoroughly purged with nitrogen was charged with 300 mL of a cyclohexane/hexane (9/1) mixed solution and 18.0 g of benzonorbornadiene, and the liquid and gas phases were saturated with ethylene at 90 L/hr and hydrogen at 0.24 L/hr. 297.0 mg (1.5 mmol) of TIBAL was added, followed by 0.001 mmol of 3,5-bis-1-methylethyl-1-pyrazolate-t-butylcyclopentadienyltitanium dichloride and 0.004 mmol of borate compound (1), to initiate polymerization.

Ethylene was continuously fed at 90 L/hr and hydrogen at 0.24 L/hr, and polymerization was carried out at normal pressure and 50°C for 3 minutes. The polymerization was then terminated by adding a small amount of isobutanol. After polymerization was completed, the reaction mixture was added to 1 L of a 3/1 acetone/methanol mixed solvent containing a small amount of hydrochloric acid to precipitate the polymer. After washing with the same solvent, the mixture was dried under reduced pressure at 130°C for 10 hours, yielding 4.490 g of an ethylene-benzonorbornadiene copolymer. The polymerization activity was 89.8 kg/mmol-hr, and the resulting ethylene-benzonorbornadiene copolymer (structural unit (A): ethylene 57 mol%, structural unit (B): benzonorbornadiene 43 mol%) had an intrinsic viscosity [η] of 0.72 (dL/g), an Mw of 310,000 (g/mol), and an Mw/Mn of 1.84. The glass transition temperature measured by DSC was 152°C, and the ratio of racemostructure/mesostructure measured by ^13C -NMR was 0.89. The ratio of racemostructure/mesostructure was based on the calculation method for the above-mentioned C: polymer of ethylene and BNBD. Furthermore, the ratio of structural unit (B)-structural unit (B) chains to structural unit (B) measured by ^13C -NMR was 4.0, and the solubility in methylcyclohexane was good (Solubility in methylcyclohexane: A). The solubility in toluene was good (Solubility in toluene: A). The formability of the film was good (Film formability: A). The density was 1060 (kg/m ³ ). The results are shown in Table 1.

Example 5
A 500 mL glass reactor thoroughly purged with nitrogen was charged with 150 mL of a cyclohexane/hexane (9/1) mixed solution and 4.9 g of tetracyclododecene, and the liquid and gas phases were saturated with ethylene at 51 L/hr and hydrogen at 9.96 L/hr. 297.0 mg (1.5 mmol) of TIBAL was added, followed by 0.003 mmol of dimethylmethylenefluorenylcyclopentadienylzirconium dimethyl and 0.012 mmol of borate compound (1), to initiate polymerization.

Ethylene was continuously fed at 51 L/hr and hydrogen at 9.96 L/hr, and polymerization was carried out at 50°C under atmospheric pressure for 5 minutes. The polymerization was then terminated by adding a small amount of isobutanol. After polymerization was completed, the reaction mixture was added to 0.75 L of a 3/1 acetone/methanol mixed solvent containing a small amount of hydrochloric acid to precipitate the polymer. After washing with the same solvent, the mixture was dried under reduced pressure at 130°C for 10 hours, yielding 0.235 g of an ethylene-tetracyclododecene copolymer. The polymerization activity was 0.94 kg/mmol-hr, and the resulting ethylene-tetracyclododecene copolymer (structural unit (A): ethylene 62 mol%, structural unit (B): tetracyclododecene 38 mol%) had an intrinsic viscosity [η] of 0.58 (dL/g), Mw of 84,800 (g/mol), and Mw/Mn of 4.75. The glass transition temperature measured by DSC was 145°C, and the ratio of racemostructure/mesostructure measured by ^13C -NMR was 0.64. The ratio of racemostructure/mesostructure was based on the calculation method for the above-mentioned A: polymer of ethylene and TD. Furthermore, the ratio of structural unit (B)-structural unit (B) chains to structural unit (B) measured by ^13C -NMR was 0.5, and the solubility in methylcyclohexane was good (Solubility in methylcyclohexane: A). Furthermore, the solubility in toluene was good immediately after dissolution, but became opaque after standing for one day (Solubility in toluene: B). Furthermore, the formability of the film was good (Film formability: A). The results are shown in Table 1.

Example 6
A 500 mL glass reactor thoroughly purged with nitrogen was charged with 150 mL of a cyclohexane/hexane (9/1) mixed solution and 9.8 g of tetracyclododecene, and the liquid and gas phases were saturated with ethylene at 90 L/hr and hydrogen at 0.24 L/hr. 198.0 mg (1.0 mmol) of TIBAL was added, followed by 0.002 mmol of diphenylmethylenefluorenylcyclopentanylzirconium dimethyl and 0.008 mmol of borate compound (1), to initiate polymerization.

Ethylene was continuously fed at 90 L/hr and hydrogen at 0.24 L/hr, and polymerization was carried out at 50°C under atmospheric pressure for 10 minutes. The polymerization was then terminated by adding a small amount of isobutanol. After polymerization was completed, the reaction mixture was added to 0.75 L of a 3/1 acetone/methanol mixed solvent containing a small amount of hydrochloric acid to precipitate the polymer. After washing with the same solvent, the mixture was dried under reduced pressure at 130°C for 10 hours, yielding 0.362 g of an ethylene-tetracyclododecene copolymer. The polymerization activity was 1.09 kg/mmol-hr, and the resulting ethylene-tetracyclododecene copolymer (structural unit (A): ethylene 59 mol%, structural unit (B): tetracyclododecene 41 mol%) had an intrinsic viscosity [η] of 0.51 (dL/g), an Mw of 112,000 (g/mol), and an Mw/Mn of 4.38. The glass transition temperature measured by DSC was 158°C, and the ratio of racemostructure/mesostructure measured by ^13C -NMR was 0.54. The ratio of racemostructure/mesostructure was based on the calculation method for the above-mentioned A: polymer of ethylene and TD. Furthermore, the ratio of structural unit (B)-structural unit (B) chains to structural unit (B) measured by ^13C -NMR was 2.0, and the solubility in methylcyclohexane was good (Solubility in methylcyclohexane: A). The solubility in toluene was also good (Solubility in toluene: A). The formability of the film was also good (Film formability: A). The results are shown in Table 1.

Example 7
A 500 mL glass reactor that had been thoroughly purged with nitrogen was charged with 276 mL of a cyclohexane/hexane (9/1) mixed solution and 22.4 g of tetracyclododecene, 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 was added, followed by 0.000125 mmol of 3,5-bis(t-butyl)-1-pyrazolate-t-butylcyclopentadienyltitanium dichloride and 0.004 mmol of borate compound (1), to initiate polymerization.

Ethylene was continuously fed at 90 L/hr and hydrogen at 0.24 L/hr, and polymerization was carried out at 50°C under atmospheric pressure for 10 minutes. The polymerization was then terminated by adding a small amount of isobutanol. After polymerization was completed, the reaction mixture was added to 1.25 L of a 3/1 acetone/methanol mixed solvent containing a small amount of hydrochloric acid to precipitate the polymer. After washing with the same solvent, the mixture was dried under reduced pressure at 130°C for 10 hours, yielding 0.932 g of an ethylene-tetracyclododecene copolymer. The polymerization activity was 44.7 kg/mmol-hr, and the resulting ethylene-tetracyclododecene copolymer (structural unit (A): ethylene 54 mol%, structural unit (B): tetracyclododecene 46 mol%) had an intrinsic viscosity [η] of 0.20 (dL/g), Mw of 35,800 (g/mol), and Mw/Mn of 2.19. The glass transition temperature measured by DSC was 176°C, and the ratio of racemostructure/mesostructure measured by ^13C -NMR was 1.00. The ratio of racemostructure/mesostructure was based on the calculation method for the above-mentioned A: polymer of ethylene and TD. Furthermore, the ratio of structural unit (B)-structural unit (B) chains to structural unit (B) measured by ^13C -NMR was 1.2, and the solubility in methylcyclohexane was good (Solubility in methylcyclohexane: A). The solubility in toluene was also good (Solubility in toluene: A). Furthermore, the formability of the film was partially good (Film formability: B). The results are shown in Table 1.

(Example 8)
A 500 mL glass reactor that had been thoroughly purged with nitrogen was charged with 300 mL of a cyclohexane/hexane (9/1) mixed solution and 2.9 g of tetracyclododecene, and the liquid and gas phases were saturated with ethylene at 90 L/hr. 59.4 mg (0.3 mmol) of TIBAL was added, followed by 0.003 mmol of 3,5-bisphenyl-1-pyrazolate-t-butylcyclopentadienyltitanium dichloride and 0.012 mmol of borate compound (1), to initiate polymerization.

Ethylene was continuously fed at 90 L/hr, and polymerization was carried out at 50°C under atmospheric pressure for 10 minutes. The polymerization was then terminated by adding a small amount of isobutanol. After polymerization was completed, the reaction mixture was added to 1.25 L of a 3/1 acetone/methanol mixed solvent containing a small amount of hydrochloric acid to precipitate the polymer. After washing with the same solvent, the mixture was dried under reduced pressure at 130°C for 10 hours, yielding 0.326 g of an ethylene-tetracyclododecene copolymer. The polymerization activity was 0.65 kg/mmol-hr, and the resulting ethylene-tetracyclododecene copolymer (structural unit (A): ethylene 58 mol%, structural unit (B): tetracyclododecene 42 mol%) had an intrinsic viscosity [η] of 1.44 (dL/g), an Mw of 450,000 (g/mol), and an Mw/Mn of 3.55. The glass transition temperature measured by DSC was 173°C, and the ratio of racemostructure/mesostructure measured by ^13C -NMR was 1.00. The ratio of racemostructure/mesostructure was based on the calculation method for the above-mentioned A: polymer of ethylene and TD. Furthermore, the ratio of structural unit (B)-structural unit (B) chains to structural unit (B) measured by ^13C -NMR was 2.6, and the solubility in methylcyclohexane was good (Solubility in methylcyclohexane: A). Furthermore, the solubility in toluene was good immediately after dissolution, but became opaque after standing for one day (Solubility in toluene: B). Furthermore, the formability of the film was good (Film formability: A). The results are shown in Table 1.

Example 9
A 500 mL glass reactor that had been thoroughly purged with nitrogen was charged with 300 mL of a cyclohexane/hexane (9/1) mixed solution and 1.9 g of tetracyclododecene, and the liquid and gas phases were saturated with ethylene at 90 L/hr. 59.4 mg (0.3 mmol) of TIBAL was added, followed by 0.003 mmol of 3,5-bisphenyl-1-pyrazolate-t-butylcyclopentadienyltitanium dichloride and 0.012 mmol of borate compound (1), to initiate polymerization.

Ethylene was continuously fed at 90 L/hr, and polymerization was carried out at 50°C under atmospheric pressure for 10 minutes. The polymerization was then terminated by adding a small amount of isobutanol. After polymerization was completed, the reaction mixture was added to 1.25 L of a 3/1 acetone/methanol mixed solvent containing a small amount of hydrochloric acid to precipitate the polymer. After washing with the same solvent, the mixture was dried under reduced pressure at 130°C for 10 hours, yielding 0.545 g of an ethylene-tetracyclododecene copolymer. The polymerization activity was 1.09 kg/mmol-hr, and the resulting ethylene-tetracyclododecene copolymer (structural unit (A): 62 mol% ethylene, structural unit (B): 38 mol% tetracyclododecene) had an intrinsic viscosity [η] of 2.03 (dL/g), an Mw of 634,000 (g/mol), and an Mw/Mn of 2.33. The glass transition temperature measured by DSC was 154°C, and the ratio of racemostructure/mesostructure measured by ^13C -NMR was 1.00. The ratio of racemostructure/mesostructure was based on the calculation method for the above-mentioned A: polymer of ethylene and TD. Furthermore, the ratio of structural unit (B)-structural unit (B) chains to structural unit (B) measured by ^13C -NMR was 1.7, and the solubility in methylcyclohexane was good (Solubility in methylcyclohexane: A). The solubility in toluene was also good (Solubility in toluene: A). The formability of the film was also good (Film formability: A). The results are shown in Table 1.

Example 10
A 500 mL glass reactor that had been thoroughly purged with nitrogen was charged with 300 mL of a 9:1 cyclohexane/hexane mixed solution, 3.3 g of tetracyclododecene, and 5.7 g of benzonorbornadiene, and the liquid and gas phases were saturated with ethylene at 50 L/hr and hydrogen at 0.24 L/hr. 59.4 mg (0.3 mmol) of TIBAL was added. Subsequently, 0.003 mmol of 3,5-bismethylethyl-1-pyrazolate-t-butylcyclopentadienyltitanium dichloride and 0.012 mmol of borate compound (1) were added to initiate the polymerization reaction.

Ethylene (50 L/hr) and hydrogen (0.24 L/hr) were continuously supplied, and polymerization was carried out at 50°C under atmospheric pressure for 10 minutes. The polymerization was then terminated by adding a small amount of isobutanol. After polymerization was completed, the reaction mixture was added to 1 L of a 3/1 acetone/methanol mixed solvent containing a small amount of hydrochloric acid to precipitate the polymer. After washing with the same solvent, the mixture was dried under reduced pressure at 130°C for 10 hours to obtain 1.671 g of an ethylene-tetracyclododecene-benzonorbornadiene copolymer. The polymerization activity was 3.34 kg/mmol-hr, and the resulting ethylene-tetracyclododecene-benzonorbornadiene copolymer (structural unit (A): ethylene 59 mol%, structural unit (B): tetracyclododecene 25 mol%, benzonorbornadiene: 16 mol%) had an intrinsic viscosity [η] of 0.40 (dL/g), an Mw of 95,500 (g/mol), and an Mw/Mn of 2.90. The glass transition temperature measured by differential scanning calorimetry (DSC) was 163°C, and the ratio of racemostructure/mesostructure determined by ^13C -NMR measurement was 0.50. The ratio of racemostructure/mesostructure was based on the calculation method for the above-mentioned A: polymer of ethylene, TD, and BNBD. Furthermore, the ratio of structural unit (B)-structural unit (B) chains to structural unit (B) measured by ^13C -NMR was 3.2, and the solubility in methylcyclohexane was good (Solubility in methylcyclohexane: A). The solubility in toluene was also good (Solubility in toluene: A). Furthermore, the formability of the film was good (Film formability: A). The density was 1057 (kg/m ³ ). The results are shown in Table 1.

Example 11
A 500 mL glass reactor that had been thoroughly purged with nitrogen was charged with 250 mL of a cyclohexane/hexane (9/1) mixed solution, 5 g of tetracyclododecene, and 331 mg (1.50 mmol) of BHT, and the liquid and gas phases were saturated with ethylene at 50 L/hr. Thereafter, 1.5 mmol of methylaluminoxane (calculated as aluminum atoms) was added, followed by 0.0030 mmol of 3,5-bismethylethyl-1-pyrazolate-t-butylcyclopentadienyltitanium dichloride and 0.012 mmol of borate compound (1), to initiate the polymerization reaction.

Ethylene was continuously supplied at 50 L/hr, and polymerization was carried out at 50°C under atmospheric pressure for 10 minutes. The polymerization was then terminated by the addition of a small amount of isobutanol. After polymerization was completed, the reaction mixture was added to 1 L of a 3/1 acetone/methanol mixed solvent containing a small amount of hydrochloric acid to precipitate the polymer. After washing with the same solvent, the mixture was dried under reduced pressure at 130°C for 10 hours, yielding 1.292 g of ethylene-tetracyclododecene copolymer. The polymerization activity was 2.58 kg/mmol-Ti hr, and the resulting ethylene-tetracyclododecene copolymer (structural unit (A): 55 mol% ethylene, structural unit (B): 45 mol% tetracyclododecene) had an intrinsic viscosity [η] of 1.05 (dL/g), an Mw of 320,000 (g/mol), and an Mw/Mn of 2.17. The glass transition temperature measured by differential scanning calorimetry (DSC) was 188°C, and the ratio of racemostructure/mesostructure determined by ^13C -NMR measurement was 1.00. The ratio of racemostructure/mesostructure was based on the calculation method for the above-mentioned A: polymer of ethylene and TD. Furthermore, the ratio of structural unit (B)-structural unit (B) chains to structural unit (B) measured by 13C-NMR was ^3.7 , and the solubility in methylcyclohexane was good (Solubility in methylcyclohexane: A). Furthermore, the solubility in toluene was good immediately after dissolution, but became opaque after standing for one day (Solubility in toluene: B). Furthermore, the formability of the film was good (Film formability: A). The results are shown in Table 1.

Example 12
A 500 mL glass reactor thoroughly purged with nitrogen was charged with 245 mL of a 9:1 cyclohexane/hexane mixed solution and 5.0 g of tetracyclododecene, and the liquid and gas phases were saturated with ethylene at 50 L/hr. 39.6 mg (0.2 mmol) of TIBAL was added. Subsequently, 0.0005 mmol of diphenylmethyleneindenylcyclopentanylzirconium dichloride and 0.002 mmol of borate compound (1) were added to initiate the polymerization reaction.

Ethylene was continuously supplied at 50 liters/hr, and polymerization was carried out at 50°C under normal pressure for 10 minutes. The polymerization was then terminated by adding a small amount of isobutanol. After polymerization was completed, the reaction mixture was added to 1 liter of a 3/1 acetone/methanol mixed solvent containing a small amount of hydrochloric acid to precipitate the polymer. After washing with the same solvent, the mixture was dried under reduced pressure at 130°C for 10 hours to obtain 1.1 g of an ethylene-tetracyclododecene copolymer. The polymerization activity was 13.18 kg/mmol-hr, and the resulting ethylene-tetracyclododecene copolymer (structural unit (A): 62 mol% ethylene, structural unit (B): 38 mol% tetracyclododecene) had an intrinsic viscosity [η] of 0.36 (dL/g), an Mw of 62,200 (g/mol), and an Mw/Mn of 2.05. The glass transition temperature measured by differential scanning calorimetry (DSC) was 150°C, and the ratio of racemostructure/mesostructure determined by ^13C -NMR was 0.14. The ratio of racemostructure/mesostructure was based on the calculation method for the above-mentioned A: polymer of ethylene and TD. Furthermore, the ratio of structural unit (B)-structural unit (B) chains to structural unit (B) measured by ^13C -NMR was 1.4. The solubility in methylcyclohexane was good immediately after dissolution, but became opaque after standing for one day (Solubility in methylcyclohexane: B). The solubility in toluene was good immediately after dissolution, but became opaque after standing for one day (Solubility in toluene: B). Furthermore, the formability of the film was partially good (Film formability: B). The results are shown in Table 1.

Example 13
A 500 mL glass reactor that had been thoroughly purged with nitrogen was charged with 300 mL of a 9:1 cyclohexane/hexane mixed solution and 11.4 g of tetracyclododecene, 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 was added. Subsequently, 0.003 mmol of 3,5-bismethylethyl-1-pyrazolate-t-butylcyclopentadienyltitanium dichloride and 0.012 mmol of a borate compound were added to initiate the polymerization reaction.

Ethylene (90 L/hr) and hydrogen (0.24 L/hr) were continuously supplied, and polymerization was carried out at 50°C under atmospheric pressure for 10 minutes. The polymerization was then terminated by the addition of a small amount of isobutanol. After polymerization was completed, the reaction mixture was added to 1 L of a 3/1 acetone/methanol mixed solvent containing a small amount of hydrochloric acid to precipitate the polymer. After washing with the same solvent, the mixture was dried under reduced pressure at 130°C for 10 hours to obtain 1.483 g of an ethylene-tetracyclododecene copolymer. The polymerization activity was 2.97 kg/mmol-hr, and the resulting ethylene-tetracyclododecene copolymer (structural unit (A): ethylene 51 mol%, structural unit (B): tetracyclododecene 49 mol%) had an intrinsic viscosity [η] of 0.30 (dL/g), an Mw of 67,200 (g/mol), and an Mw/Mn of 3.03. The glass transition temperature measured by differential scanning calorimetry (DSC) was 203°C, and the ratio of racemostructure/mesostructure determined by ^13C -NMR measurement was 1.00. The ratio of racemostructure/mesostructure was based on the calculation method for the above-mentioned A: polymer of ethylene and TD. Furthermore, the ratio of structural unit (B)-structural unit (B) chains to structural unit (B) measured by ^13C -NMR was 5.1, and the solubility in methylcyclohexane was good (Solubility in methylcyclohexane: A). Furthermore, the solubility in toluene was good immediately after dissolution, but became opaque after standing for one day (Solubility in toluene: B). Furthermore, the formability of the film was poor (Film formability: C). The results are shown in Table 1.

Example 14
A 500 mL glass reactor thoroughly purged with nitrogen was charged with 300 mL of a 9/1 cyclohexane/hexane mixture and 3.0 g of benzonorbornadiene, and the liquid and gas phases were saturated with ethylene at 50 L/hr and hydrogen at 6.0 L/hr. 9.9 mg (0.5 mmol) of TIBAL was added, followed by 0.0005 mmol of diphenylmethyleneindenylcyclopentanylzirconium dichloride and 0.002 mmol of borate compound (1), to initiate polymerization.

Ethylene was continuously fed at 50 L/hr and hydrogen at 6.0 L/hr, and polymerization was carried out at 50°C under atmospheric pressure for 10 minutes. The polymerization was then terminated by adding a small amount of isobutanol. After polymerization was completed, the reaction mixture was added to 1 L of a 3/1 acetone/methanol mixed solvent containing a small amount of hydrochloric acid to precipitate the polymer. After washing with the same solvent, the mixture was dried under reduced pressure at 130°C for 10 hours, yielding 0.413 g of an ethylene-benzonorbornadiene copolymer. The polymerization activity was 84.96 kg/mmol-hr, and the resulting ethylene-benzonorbornadiene copolymer (structural unit (A): ethylene 68 mol%, structural unit (B): benzonorbornadiene 32 mol%) had an intrinsic viscosity [η] of 0.33 (dL/g), an Mw of 88,000 (g/mol), and an Mw/Mn of 6.90. The glass transition temperature measured by DSC was 112°C, and the ratio of racemostructure/mesostructure measured by ^13C -NMR was 0.26. The ratio of racemostructure/mesostructure was based on the calculation method for the above-mentioned C: polymer of ethylene and BNBD. Furthermore, the ratio of structural unit (B)-structural unit (B) chains to structural unit (B) measured by ^13C -NMR was 0.0, and the solubility in methylcyclohexane was poor (Solubility in methylcyclohexane: B). Furthermore, the solubility in toluene was good (Solubility in toluene: A). Furthermore, the formability of the film was partially good (Film formability: B). The results are shown in Table 1.

(Comparative Example 1)
A 500 mL glass reactor thoroughly purged with nitrogen was charged with 240 mL of a 9/1 cyclohexane/hexane mixed solution and 10.0 g of tetracyclododecene, and the liquid and gas phases were saturated with ethylene at 50 L/hr and hydrogen at 3.0 L/hr. 19.8 mg (0.1 mmol) of TIBAL was added. Subsequently, 0.00025 mmol of dimethylmethylenebisindenylzirconium dichloride was added, followed by 0.001 mmol of borate compound (1), to initiate polymerization.

Ethylene was continuously fed at 50 L/hr and hydrogen at 3.0 L/hr. Polymerization was carried out at 50°C under atmospheric pressure for 10 minutes, after which the polymerization was terminated by the addition of a small amount of isobutanol. After polymerization was completed, the reaction mixture was added to 1 L of a 3/1 acetone/methanol mixed solvent containing a small amount of hydrochloric acid to precipitate the polymer. After washing with the same solvent, the mixture was dried under reduced pressure at 130°C for 10 hours, yielding 1.83 g of ethylene-tetracyclododecene copolymer. The polymerization activity was 43.82 kg/mmol-hr, and the resulting ethylene-tetracyclododecene copolymer (structural unit (A): 64 mol% ethylene, structural unit (B): 36 mol% tetracyclododecene) had an intrinsic viscosity [η] of 0.50 (dL/g), Mw of 97,200 (g/mol), and Mw/Mn of 2.47. The glass transition temperature measured by DSC was 148°C, and the racemostructure/mesostructure ratio measured by ^13C -NMR was 0.00. Furthermore, the ratio of structural unit (B)-structural unit (B) chains to structural unit (B) measured by ^13C -NMR was 0.0, and the solubility in methylcyclohexane was poor (Solubility in methylcyclohexane: C). Furthermore, the solubility in toluene was poor (Solubility in toluene: C). Furthermore, the formability of the film was poor (Film formability: C). The results are shown in Table 1.

(Comparative Example 2)
A 500 mL glass reactor thoroughly purged with nitrogen was charged with 175 mL of a 9:1 cyclohexane/hexane mixed solution, 4.0 g of tetracyclododecene, and 5.0 g of benzonorbornadiene, and the liquid and gas phases were saturated with ethylene at 51 L/hr and hydrogen at 2 L/hr. 148.5 mg (0.75 mmol) of TIBAL (triisobutylaluminum) was added. Subsequently, 0.0015 mmol of dimethylmethylenebisindenylzirconium dichloride and 0.006 mmol of borate compound (1) were added to initiate the polymerization reaction.

Ethylene (51 L/hr) and hydrogen (2 L/hr) were continuously supplied, and polymerization was carried out at 50°C under atmospheric pressure for 10 minutes. The polymerization was then terminated by the addition of a small amount of isobutanol. After polymerization was completed, the reaction mixture was added to 1 L of a 3/1 acetone/methanol mixed solvent containing a small amount of hydrochloric acid, resulting in a polymer precipitation. After washing with the same solvent, the mixture was dried under reduced pressure at 130°C for 10 hours, yielding 0.814 g of an ethylene-tetracyclododecene-benzonorbornadiene copolymer. The polymerization activity was 3.26 kg/mmol-hr, and the resulting ethylene-tetracyclododecene-benzonorbornadiene copolymer (structural unit (A): ethylene 62 mol%, structural unit (B): tetracyclododecene 21 mol%, benzonorbornadiene: 17 mol%) had an intrinsic viscosity [η] of 0.50 (dL/g), an Mw of 99,200 (g/mol), and an Mw/Mn of 2.80. The glass transition temperature measured by differential scanning calorimetry (DSC) was 137°C, and the ratio of racemostructure/mesostructure determined by ^13C -NMR measurement was 0.00. The ratio of racemostructure/mesostructure was based on the calculation method for the above-mentioned A: polymer of ethylene, TD, and BNBD. Furthermore, the ratio of structural unit (B)-structural unit (B) chains to structural unit (B) measured by ^13C -NMR was 0.0, and the solubility in methylcyclohexane was poor (Solubility in methylcyclohexane: C). Furthermore, the solubility in toluene was poor (Solubility in toluene: C). The formability of the film was poor (Film formability: C). The results are shown in Table 1.

In each example, the coexistence of the racemo structure and meso structure resulted in high solubility in methylcyclohexane and toluene. On the other hand, in each comparative example, solubility in methylcyclohexane and toluene remained low.

This application claims priority based on Japanese Patent Application No. 2021-106711, filed June 28, 2021, and Japanese Patent Application No. 2022-006837, filed January 20, 2022, the disclosures of which are incorporated herein in their entireties.

Claims (12)

A cyclic olefin polymer having a norbornene skeleton,
the cyclic olefin polymer is a cyclic olefin copolymer,
It is characterized by satisfying the following requirement (a):
(Requirement (a))
The cyclic olefin polymer comprises a structural unit (A) which is a chain olefin and a structural unit (B) which contains a cyclic olefin having a norbornene skeleton,
the ratio of mesostructure to racemostructure in the structural unit (B)-structural unit (A)-structural unit (B) chain (racemostructure/mesostructure) measured by ^13C -NMR is 0.01 to 100; the cyclic olefin copolymer comprises, as the structural unit (A), a structural unit derived from ethylene, and , as the structural unit (B) , a structural unit derived from a cyclic monomer represented by the following general formula [Z-IV] :
the proportion of the structural units derived from ethylene is 50 to 75 mol %, with the total of the structural units (A) and (B) being 100 mol %,
the proportion of the structural unit (B) is 25 to 50 mol %, with the total of the structural unit (A) and the structural unit (B) being 100 mol %,
(In general formula [Z-IV], x is 0 or an integer of 1 or more, R ¹¹¹ to R ¹¹⁸ are each independently selected from a hydrogen atom, a halogen atom, and a hydrocarbon group, and R ¹²¹ to R ¹²⁴ are each independently selected from a hydrogen atom, a halogen atom, and a hydrocarbon group, and two adjacent groups may be bonded to each other to form a monocyclic or polycyclic aromatic ring. )
Furthermore, the following requirement (b) is satisfied:
A cyclic olefin polymer, characterized in that the glass transition temperature of the cyclic olefin copolymer measured by a differential scanning calorimeter (DSC) is 169°C or lower .
(Requirement (b))
The proportion of the structural unit (B)-structural unit (B) chains in the structural unit (B) measured by ¹³ C-NMR is 0.0 mol % or more and 10 mol % or less. The cyclic olefin polymer according to claim 1,
The cyclic olefin polymer further comprises, as the structural unit (B), a structural unit derived from one or more cyclic monomers selected from the group consisting of the following general formulas [Z-I], [Z-II], and [Z-III]:
(In the above formula [Z-I], 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 selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group; R ⁷⁵ ~R ⁷⁸ may be bonded to each other to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring may have a double bond. ⁷⁵ and R ⁷⁶ With or R ⁷⁷ and R ⁷⁸ and may form an alkylidene group.)
(In the above formula [Z-II], x and d are integers of 0 or 1 or more, and y and z are 0, 1, or 2. R ⁸¹ ~R ⁹⁹ are each independently selected from a hydrogen atom, a halogen atom, and a hydrocarbon group; R ⁸⁹ and R ⁹⁰ and a carbon atom to which R ⁹³ or the carbon atom to which R ⁹¹ may be bonded directly or via an alkylene group having 1 to 3 carbon atoms. ⁹⁵ and R ⁹² or R ⁹⁵ and R ⁹⁹ may be bonded to each other to form a monocyclic or polycyclic aromatic ring.
(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 are each independently a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom other than a fluorine atom. The cyclic olefin polymer according to claim 1 or 2,
The cyclic olefin polymer has a glass transition temperature of 50°C or higher as measured by a differential scanning calorimeter (DSC). The cyclic olefin polymer according to claim 1 or 2,
A cyclic olefin polymer comprising, as the structural unit (B), a structural unit derived from the general formula [Z-I] and a structural unit derived from the general formula [Z-IV]. The cyclic olefin polymer according to claim 1 or 2,
The cyclic olefin copolymer may be a copolymer of ethylene and 1,4-dihydro-1,4-methanonaphthalene, a copolymer of ethylene and tetracyclo[4.4.0.1 ^2,5 ．１ ^{7, 10} a copolymer of ethylene, norbornene and 1,4-dihydro-1,4-methanonaphthalene; The cyclic olefin polymer according to claim 1 or 2,
The cyclic olefin copolymer has an intrinsic viscosity of 0.1 [dL/g] or more and 5.0 [dL/g] or less. The cyclic olefin polymer according to claim 1 or 2,
The cyclic olefin copolymer has a weight average molecular weight (Mw) of 1,000 or more and 4,500,000 or less as determined by gel permeation chromatography (GPC). The cyclic olefin polymer according to claim 1 or 2,
The cyclic olefin polymer has a molecular weight distribution (Mw/Mn) of 1.76 or more and 6.90 or less as determined by gel permeation chromatography (GPC). A cyclic olefin polymer composition comprising the cyclic olefin polymer of claim 1 or 2. The cyclic olefin polymer composition according to claim 9 ,
A cyclic olefin polymer composition used for optical parts, film packaging materials, optical films, or medical parts. A molded article comprising the cyclic olefin polymer of claim 1 or 2. The molded article according to claim 11 ,
The molded article is an optical part, a film packaging material, an optical film, or a medical part.