Cyclic olefin-based copolymer, cyclic olefin-based copolymer composition, molded body and optical component

Abstract

Provided are: a cyclic olefin-based copolymer and a cyclic olefin-based copolymer composition capable of improving the balance between moldability and birefringence of a molded body to be obtained; and a molded body and an optical component capable of improving the balance between moldability and birefringence.　The cyclic olefin-based copolymer has a structural unit (A) derived from at least two α-olefins selected from the group consisting of ethylene and C3-C20 α-olefins, and a structural unit (B) derived from a cyclic olefin.

Description

Cyclic olefin copolymers, cyclic olefin copolymer compositions, molded articles, and optical components

[0001] The present invention relates to cyclic olefin copolymers, cyclic olefin copolymer compositions, molded articles, and optical components.

[0002] Glass is widely used as a material for optical components because of its high transparency, high refractive index, and extremely low birefringence. However, glass has the disadvantages of poor moldability and difficulty in weight reduction. Therefore, recently, lightweight polymer materials with excellent moldability have come to be used as materials for optical components. Examples of such polymer materials include polymethyl methacrylate and polycarbonate.

[0003] On the other hand, polymethyl methacrylate is preferable in that it has good transparency and low birefringence, but it has the disadvantage of low heat resistance and poor shape stability, as it is prone to deformation such as warping after molding. Polycarbonate, on the other hand, has better refractive index and heat resistance than polymethyl methacrylate, but it has the disadvantage of high birefringence. In optical components, high birefringence causes large aberrations, which leads to abnormalities in the shape of the focusing spot and a decrease in pickup performance.

[0004] Here, cyclic olefin copolymers have attracted attention as materials with low birefringence and are used in optical lenses such as imaging lenses, fθ lenses, and pickup lenses. An example of technology related to such cyclic olefin copolymers is the one described in Patent Document 1.

[0005] Patent Document 1 describes a cyclic olefin copolymer comprising a constituent unit (A) derived from an olefin monomer represented by a predetermined general formula, and a constituent unit (B) derived from at least one cyclic olefin monomer selected from the group consisting of a cyclic olefin monomer represented by a predetermined general formula and a cyclic olefin monomer represented by a predetermined general formula, wherein when the total content of constituent units (A) and (B) in the cyclic olefin copolymer is 100 mol%, the content of constituent unit (A) is within a specific range, the content of constituent unit (B) is within a specific range, the weight-average molecular weight (Mw) measured by gel permeation chromatography (GPC) is within a specific range, and the glass transition temperature (Tg) is above a predetermined temperature.

[0006] International Publication No. 2023 / 171221

[0007] However, recent studies have requested that the cyclic olefin copolymer described in Patent Document 1 have even lower melt flow characteristics to further improve moldability.

[0008] The present invention provides cyclic olefin copolymers and cyclic olefin copolymer compositions that can improve the balance between moldability and the birefringence of the resulting molded article, as well as molded articles and optical components that can improve the balance between moldability and birefringence.

[0009] According to the present invention, the following cyclic olefin copolymers, cyclic olefin copolymer compositions, molded articles, and optical components are provided.

[0010] 1. A cyclic olefin-based copolymer having a structural unit (A) derived from at least two monomers selected from the group consisting of ethylene and α-olefins having 3 to 20 carbon atoms, and a structural unit (B) derived from a cyclic olefin. 2. The cyclic olefin-based copolymer according to 1., wherein the structural unit (A) has a structural unit (a1) derived from at least one monomer selected from the group consisting of ethylene and propylene, and a structural unit (a2) derived from at least one α-olefin selected from the group consisting of α-olefins having 4 to 20 carbon atoms, the cyclic olefin includes a compound represented by the following formula (B-1), and when the total content of the structural unit (A) and the structural unit (B) in the cyclic olefin-based copolymer is taken as 100 mol%, the content of the structural unit (B) in the cyclic olefin-based copolymer is 40.0 mol% or more. (In the formula (B-1), n is 0 or 1, m is a positive integer, q is 0 or 1, R １ to R １８ and R ａ and R ｂ are each independently a hydrogen atom, a halogen atom, or a hydrocarbon group optionally substituted with a halogen atom, R １５ to R １８ may be bonded to each other to form a monocyclic or polycyclic ring, the monocyclic or polycyclic ring may have a double bond, and R １５ and R １６ , or R １７ and R １８They may form an alkylidene group. However, the monocyclic or polycyclic ring does not contain an aromatic ring. 3. The cyclic olefin copolymer according to 2, wherein when the total content of the constituent unit (a1) and the constituent unit (a2) in the constituent unit (A) is 100 mol%, the content of the constituent unit (a2) is 1.0 mol% or more and 55.0 mol% or less. 4. The cyclic olefin copolymer according to 2 or 3, wherein the constituent unit (a2) includes at least one α-olefin-derived constituent unit selected from the group consisting of linear α-olefins having 4 to 20 carbon atoms. 5. The cyclic olefin copolymer according to 3 or 4, wherein the total of the constituent unit (a1), the constituent unit (a2), and the constituent unit (B) in the cyclic olefin copolymer exceeds 95 mol%. 6. The constituent unit (B) is tetracyclo[4.4.0.1 ２，５ 1. ７，１０1. A cyclic olefin copolymer according to any one of 1 to 5, containing a constituent unit derived from ]-3-dodecene. 7. A cyclic olefin copolymer according to any one of 1 to 6, which is a random addition copolymer. 8. A cyclic olefin copolymer according to any one of 1 to 7, wherein when the total content of constituent unit (A) and constituent unit (B) in the cyclic olefin copolymer is 100 mol%, the content of constituent unit (A) in the cyclic olefin copolymer is 30.0 mol% or more and 80.0 mol or less. 9. A cyclic olefin copolymer according to any one of 1 to 8, wherein when the total content of constituent unit (A) and constituent unit (B) in the cyclic olefin copolymer is 100 mol%, the content of constituent unit (B) in the cyclic olefin copolymer is 70.0 mol% or less. 10. A cyclic olefin copolymer according to any one of 1 to 9, having a glass transition temperature (Tg) of 185.0°C or less. 11. 11. A cyclic olefin copolymer according to any one of 1 to 10, having only one glass transition temperature (Tg) in the range of 185.0°C or less. 12. A cyclic olefin copolymer according to any one of 1 to 11, having a weight-average molecular weight (Mw) of 60,000 or more and 350,000 or less. 13. A cyclic olefin copolymer according to any one of 1 to 12, having a number-average molecular weight (Mn) of 20,000 or more and 200,000 or less. 14. A cyclic olefin copolymer according to any one of 1 to 13, having a molecular weight distribution (Mw / Mn) of 1.50 or more and 3.50 or less. 15. A cyclic olefin copolymer according to any one of 1 to 14, having a complex viscosity (η*) of 1,200,000 Pa·s or less, as measured by the [Method] below. [Method] The cyclic olefin copolymer is sandwiched between ultra-heat-resistant polyimide films, and vacuum press molded using a 1.0 mm spacer at (Tg + 110) °C, 10 MPa, and for 2 minutes to obtain a 1 mm thick test press piece. Next, the test press piece is placed in a jig of a viscoelasticity measuring device, the temperature is raised to 250 °C to make the test press piece tightly attached to the jig, and then the temperature is lowered to the measurement temperature, and the measurement is performed under the following conditions.Deformation mode: Shear; Temperature range: 150°C to 300°C; Heating rate: 2°C / min; Frequency: 1 rad / s; Fixture: Parallel plate 8 mmφ; Environment: N. ２ 16. A cyclic olefin copolymer according to any of 1 to 15, wherein the average value of the phase difference obtained by the following [Method] is less than 10.0 nm. [Method] The cyclic olefin copolymer is sandwiched between super heat-resistant polyimide films and vacuum-press-molded using a 0.1 mm spacer at (Tg + 110) °C, 10 MPa, and for 2 minutes to obtain a test film with a thickness of 0.1 mm. Next, the test film is stretched 1.5 times in the uniaxial direction at a stretching temperature of (Tg + 5 °C), a stretching speed of 3% / min, and a film chuck distance of 30 mm. It is then removed from the chucks and immersed in ice water for 3 minutes to obtain a birefringence measurement film of 80 mm × 15 mm × thickness of 0.1 mm. The region between the film chucks, i.e., the stretched region, of the birefringence measurement film is called the stretched film portion. Next, the phase difference of the stretched portion of the birefringence measuring film is determined at measurement wavelengths of 523 nm, 543 nm, and 575 nm, and the average value of the phase difference at each measurement wavelength is determined. 17. A cyclic olefin copolymer composition comprising a cyclic olefin copolymer as described in any of 1 to 16. 18. A molded article comprising a cyclic olefin copolymer as described in any of 1 to 16, or a cyclic olefin copolymer composition as described in 17. 19. An optical component comprising the molded article as described in 18.

[0011] According to the present invention, it is possible to provide cyclic olefin copolymers and cyclic olefin copolymer compositions that can improve the balance between moldability and the birefringence of the resulting molded article, as well as molded articles and optical components that can improve the balance between moldability and birefringence.

[0012] The present invention will be described below based on embodiments. In these embodiments, unless otherwise specified, "A to B" indicating a numerical range represents A or greater and B or less. Furthermore, each monomer constituting the cyclic olefin copolymer of the present invention may be a monomer obtained from fossil raw materials or a monomer obtained from animal or plant raw materials.

[0013] [Cyclic Olefin Copolymer] First, the cyclic olefin copolymer of this embodiment will be described.

[0014] The cyclic olefin copolymer of this embodiment comprises a constituent unit (A) derived from at least two monomers selected from the group consisting of ethylene and α-olefins having 3 to 20 carbon atoms, and a constituent unit (B) derived from a cyclic olefin.

[0015] (Component Unit (A)) The component unit (A) will be explained below.

[0016] The constituent unit (A) of this embodiment is a constituent unit derived from ethylene and α-olefins having 3 to 20 carbon atoms. Here, the α-olefins having 3 to 20 carbon atoms may be linear or branched, and examples include linear α-olefins having 3 to 20 carbon atoms such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene; and branched α-olefins having 4 to 20 carbon atoms such as 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, and 3-ethyl-1-hexene.

[0017] In the cyclic olefin copolymer of this embodiment, from the viewpoint of further improving the balance between moldability and birefringence, it is preferable that the constituent unit (A) has a constituent unit (a1) derived from at least one monomer selected from the group consisting of ethylene and propylene, and a constituent unit (a2) derived from at least one α-olefin selected from the group consisting of α-olefins having 4 to 20 carbon atoms.

[0018] The α-olefin that provides the constituent unit (a1) preferably contains ethylene.

[0019] The α-olefin having 4 to 20 carbon atoms that provides the constituent unit (a2) is not particularly limited as long as it has 4 to 20 carbon atoms among the linear α-olefins and branched α-olefins described above. However, from the viewpoint of further reducing the birefringence, the number of carbon atoms of the α-olefin is preferably 4 to 18, more preferably 4 to 15, even more preferably 4 to 12, even more preferably 4 to 10, even more preferably 4 to 8, even more preferably 6 to 8, even more preferably 7 to 8, and even more preferably 8. Such linear or branched α-olefins can be used individually or in combination of two or more.

[0020] The α-olefin having 4 to 20 carbon atoms that provides the constituent unit (a2) preferably includes at least one α-olefin-derived constituent unit selected from the group consisting of linear α-olefins having 4 to 20 carbon atoms, more preferably 4 to 18 carbon atoms, even more preferably 4 to 15 carbon atoms, even more preferably 4 to 12 carbon atoms, even more preferably 4 to 10 carbon atoms, even more preferably 4 to 8 carbon atoms, even more preferably 6 to 8 carbon atoms, even more preferably 7 to 8 carbon atoms, and even more preferably 8 carbon atoms, from the viewpoint of further reducing the birefringence.

[0021] When the total content of the above-mentioned constituent units (A) and (B) in the cyclic olefin copolymer of this embodiment is set to 100 mol%, the content of the above-mentioned constituent unit (A) in the cyclic olefin copolymer of this embodiment is preferably 30.0 mol% or more, more preferably 35.0 mol% or more, even more preferably 40.0 mol% or more, even more preferably 45.0 mol% or more, even more preferably 47.5 mol% or more, even more preferably 49.5 mol% or more, even more preferably 51.0 mol% or more, even more preferably 52.0 mol% or more, even more preferably 55.0 mol% or more, and preferably 80.0 mol% or less, more preferably 75.0 mol% or less, even more preferably 70.0 mol% or less, More preferably, the content is 65.0 mol% or less, more preferably 60.0 mol% or less, more preferably 59.0 mol% or less, more preferably 58.5 mol% or less, and more preferably 58.0 mol% or less. Preferably, it is 30.0 mol% to 80.0 mol%, more preferably 35.0 mol% to 75.0 mol%, more preferably 40.0 mol% to 70.0 mol%, more preferably 45.0 mol% to 65.0 mol%, more preferably 47.5 mol% to 60.0 mol%, more preferably 49.5 mol% to 59.0 mol%, more preferably 51.0 mol% to 58.5 mol%, and more preferably 52.0 mol% to 58.0 mol%. By having a content of the above constituent unit (A) above the lower limit, the heat resistance and dimensional stability of the resulting molded article can be improved. Furthermore, by having a content of the above constituent unit (A) below the upper limit, the transparency and other properties of the resulting molded article can be improved.

[0022] In particular, when the cyclic olefin copolymer of this embodiment has ethylene-derived constituent units (a1), the content of ethylene-derived constituent units (a1) when the total content of constituent units (A) and (B) is 100 mol% is preferably more than 20 mol%, more preferably more than 25 mol%, even more preferably more than 30 mol%, and even more preferably more than 32 mol%. This further improves the balance between moldability and birefringence.

[0023] Furthermore, when the total content of the above-mentioned constituent unit (a1) and the above-mentioned constituent unit (a2) in the above-mentioned constituent unit (A) is 100 mol%, the content of the above-mentioned constituent unit (a2) is preferably 1.0 mol% or more, more preferably 2.0 mol% or more, even more preferably 2.5 mol% or more, even more preferably 4.0 mol% or more, even more preferably 4.5 mol% or more, even more preferably 5.5 mol% or more, even more preferably 7.0 mol% or more, even more preferably 8.0 mol% or more, even more preferably 10.0 mol% or more, and preferably 55.0 mol% or less, more preferably 45.0 mol% or less, even more preferably 40.0 mol% or less, even more preferably 35.0 mol% or less, even more preferably The content of the above constituent unit (a2) is 30.0 mol% or less, more preferably 27.5 mol% or less, even more preferably 25.0 mol% or less, even more preferably 23.5 mol% or less, and preferably 1.0 mol% to 55.0 mol% or less, more preferably 2.0 mol% to 45.0 mol%, even more preferably 2.5 mol% to 40.0 mol%, even more preferably 4.0 mol% to 35.0 mol%, even more preferably 4.5 mol% to 30.0 mol%, even more preferably 5.5 mol% to 27.5 mol%, even more preferably 7.0 mol% to 25.0 mol%, even more preferably 8.0 mol% to 23.5 mol%, and even more preferably 10.0 mol% to 23.5 mol%. By having the content of the above constituent unit (a2) within the above range, the moldability and birefringence of the resulting copolymer are better balanced.

[0024] The sum of constituent units (a1), (a2), and (B) in the cyclic olefin copolymer of this embodiment is preferably greater than 95 mol% and 100 mol%, more preferably 96 mol% or more and 100 mol%, 97 mol% or more and 100 mol%, even more preferably 98 mol% or more and 100 mol%, even more preferably 99 mol% or more and 100 mol%, and even more preferably 100 mol%. By having the sum of constituent units (a1), (a2), and (B) within the above range, the moldability and birefringence of the resulting copolymer are better balanced.

[0025] In this embodiment, the content of constituent unit (A) is: １３ It can be measured by C-NMR.

[0026] (Component Unit (B)) The component unit (B) will be explained below.

[0027] The constituent unit (B) of this embodiment is derived from a cyclic olefin. The cyclic olefin is not particularly limited and any known cyclic olefin can be used, but it is preferable that it contains at least one selected from the group consisting of the compound represented by the following formula (B-1), the compound represented by the following formula (C-1), the compound represented by the following formula (C-2), and the compound represented by the following formula (C-3), and more preferably that it contains the compound represented by the following formula (B-1). These cyclic olefins may be used individually or in combination of two or more.

[0028] In other words, the constituent unit (B) of this embodiment preferably includes a constituent unit derived from at least one selected from the group consisting of the compound represented by the following formula (B-1), the compound represented by the following formula (C-1), the compound represented by the following formula (C-2), and the compound represented by the following formula (C-3), and more preferably includes a constituent unit derived from the compound represented by the following formula (B-1). These constituent units may be included individually or in combination of two or more.

[0029]

[0030] In the above formula (B-1), n ​​is 0 or 1, m is 0 or a positive integer (m is preferably a positive integer from the viewpoint of lowering the birefringence), q is 0 or 1, R １ ~R １８ R ａ and R ｂ Each is independently a hydrogen atom, a halogen atom, or a hydrocarbon group which may be substituted with a halogen atom, and R １５ ~R １８ These may be bonded to each other to form a monocycle or polycycle, and the monocycle or polycycle may have a double bond, and R １５ and R１６ And, or R １７ and R １８ They may form an alkylidene group. However, the monocyclic or polycyclic rings do not contain aromatic rings.

[0031]

[0032] In the above formula (C-1), n ​​and q are each independently 0, 1, or 2. n is preferably 0 or 1, and more preferably 0. q is preferably 0 or 1, and more preferably 0. R １ ~R １７ Each of these is independently a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom other than a fluorine atom, and R １０ ~R １７ One of them is a joint, R １５ It is preferable that the bond is R. １ ~R １７ Each of these is preferably an independent hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrogen atom. Also, when q = 0, R １０ and R １１ , R １１ and R １２ , R １２ and R １３ , R １３ and R １４ , R １４ and R １５ , R １５ and R １０ They may be bonded to each other to form a monocycle or polycycle, and when q = 1 or 2, R １０ and R １１ , R １１ and R １７ , R １７ and R １７ , R １７ and R １２ , R １２ and R １３ , R １３ and R １４ , R １４ and R １５ , R １５ and R １６ , R１６ and R １６ , R １６ and R １０ These elements may be bonded to each other to form a monocycle or polycycle, and the monocycle or polycycle may have a double bond, and the monocycle or polycycle may be an aromatic ring.

[0033]

[0034] In the above formula (C-2), n and m are each independently 0, 1, or 2, and q is 1, 2, or 3. m is preferably 0 or 1, and more preferably 1. n is preferably 0 or 1, and more preferably 0. q is preferably 1 or 2, and more preferably 1. R １８ ~R ３１ Each of these is independently a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms that may be substituted with a halogen atom other than a fluorine atom. １８ ~R ３１ Each of these is preferably an independent hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrogen atom. Also, when q = 1, R ２８ and R ２９ , R ２９ and R ３０ , R ３０ and R ３１ They may be bonded to each other to form a monocycle or polycycle, and when q = 2 or 3, R ２８ and R ２８ , R ２８ and R ２９ , R ２９ and R ３０ , R ３０ and R ３１ , R ３１ and R ３１ These elements may be bonded to each other to form a monocycle or polycycle, and the monocycle or polycycle may have a double bond, and the monocycle or polycycle may be an aromatic ring.

[0035]

[0036] In the above formula (C-3), q is 1, 2 or 3, preferably 1 or 2, and more preferably 1. R ３２ to R ３９ are each independently a hydrogen atom, a halogen atom excluding a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom excluding a fluorine atom. R ３２ to R ３９ are each independently preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrogen atom. Further, when q=1, R ３６ and R ３７ , R ３７ and R ３８ , R ３８ and R ３９ may be bonded to each other to form a monocyclic or polycyclic ring, and when q=2 or 3, R ３６ and R ３６ , R ３６ and R ３７ , R ３７ and R ３８ , R ３８ and R ３９ , R ３９ and R ３９ may be bonded to each other to form a monocyclic or polycyclic ring, the monocyclic or polycyclic ring may have a double bond, and the monocyclic or polycyclic ring may be an aromatic ring.

[0037] Further, as the hydrocarbon group having 1 to 20 carbon atoms which can be represented by R ３２ to R ３９ , each independently includes, for example, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, an aromatic hydrocarbon group, and the like. More specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group and an octadecyl group; examples of the cycloalkyl group include a cyclohexyl group and the like; and examples of the aromatic hydrocarbon group include aryl groups such as a phenyl group, a tolyl group, a naphthyl group, an aralkyl group such as a benzyl group and a phenylethyl group, and the like. These hydrocarbon groups may be substituted with a halogen atom excluding a fluorine atom.

[0038] Among these, the cyclic olefin having an aromatic ring according to this embodiment is preferably one having one aromatic ring, for example, at least one selected from benzonorbornane, indenenorbornene, and methylphenylnorbornene is preferred.

[0039] Furthermore, examples of cyclic olefins having aromatic rings according to this embodiment include the compound represented by the following formula (C-1'), the compound represented by the following formula (C-2'), the compound represented by the following formula (C-3'), and so on. These cyclic olefins having aromatic rings may be used individually or in combination of two or more.

[0040]

[0041]

[0042]

[0043] In the above equations (C-1'), (C-2'), and (C-3'), m and n are independently 0, 1, or 2, and R １ ~R ３６ Each of these is independently a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom other than a fluorine atom, and R １０ and R １１ , R １１ and R １２ , R １２ and R １３ , R １３ and R １４ , R ２５ and R ２６ , R ２６ and R ２７ , R ２７ and R ２８ , R ３３ and R ３４ , R ３４ and R ３５ , R ３５ and R ３６ These elements may be bonded to each other to form a monoring, and the monoring may have a double bond.

[0044] Furthermore, in the above formulas (C-1'), (C-2'), and (C-3'), m is preferably 0 or 1, and more preferably 1. n is preferably 0 or 1, and more preferably 0. R １ ~R ３６ Each of these is preferably an independent hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrogen atom.

[0045] Also, the above R １ ~R ３６ Examples of hydrocarbon groups having 1 to 20 carbon atoms that can be represented include, independently, alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 15 carbon atoms, and aromatic hydrocarbon groups. More specifically, alkyl groups include methyl, ethyl, propyl, isopropyl, amyl, hexyl, octyl, decyl, dodecyl, and octadecyl groups; cycloalkyl groups include cyclohexyl groups; and aromatic hydrocarbon groups include aryl or aralkyl groups such as phenyl, tolyl, naphthyl, benzyl, and phenylethyl groups. These hydrocarbon groups may be substituted with halogen atoms other than fluorine atoms.

[0046] The aromatic ring-containing cyclic olefin according to this embodiment preferably includes one aromatic ring, and more preferably includes at least one selected from the group consisting of benzonorbornane, indenenorbornene, and methylphenylnorbornene.

[0047] Among these cyclic olefins, it is preferable that the cyclic olefin contains the compound represented by formula (B-1). That is, it is preferable that the constituent unit (B) contains a constituent unit derived from the compound represented by formula (B-1). Among these constituent units, the constituent unit (B) according to this embodiment is a constituent unit derived from bicyclo[2.2.1]-2-heptene, tetracyclo[4.4.0.1 ２，５ 1. ７，１０ ]-3-dodecene-derived constituent units and hexacyclo[6,6,1,1 ３，６ ,1１０，１３ ,0 ２，７ ,0 ９，１４ Preferably, it contains at least one constituent unit selected from constituent units derived from heptadecene-4, etc., including a constituent unit derived from bicyclo[2.2.1]-2-heptene and tetracyclo[4.4.0.1 ２，５ 1. ７，１０ It is more preferable to include at least one constituent unit selected from the constituent units derived from ]-3-dodecene, and from the viewpoint of achieving both a lower birefringence and a higher refractive index, tetracyclo[4.4.0.1 ２，５ 1. ７，１０ It is even more preferable to include a constituent unit derived from ]-3-dodecene.

[0048] When the total content of the above-mentioned constituent units (A) and (B) in the cyclic olefin copolymer of this embodiment is set to 100 mol%, the content of the above-mentioned constituent unit (B) in the cyclic olefin copolymer of this embodiment is preferably 20.0 mol% or more, more preferably 25.0 mol% or more, even more preferably 30.0 mol% or more, even more preferably 35.0 mol% or more, even more preferably 40.0 mol% or more, even more preferably 40.5 mol% or more, even more preferably 41.0 mol% or more, even more preferably 41.5 mol% or more, even more preferably 42.0 mol% or more, and preferably 70.0 mol% or less, more preferably 65.0 mol% or less, even more preferably 60.0 mol% or less, even more preferably 55.0 mol% or less, even more preferably More preferably 52.5 mol% or less, more preferably 50.5 mol% or less, more preferably 49.0 mol% or less, more preferably 48.0 mol% or less, more preferably 45.0 mol% or less, and more preferably 20.0 mol% to 70.0 mol%, more preferably 25.0 mol% to 65.0 mol%, more preferably 30.0 mol% to 60.0 mol%, more preferably 35.0 mol% to 55.0 mol%, more preferably 40.0 mol% to 52.5 mol%, more preferably 40.5 mol% to 50.5 mol%, more preferably 41.0 mol% to 49.0 mol%, more preferably 41.5 mol% to 48.0 mol%, and more preferably 42.0 mol% to 45.0 mol%. By having the content of the above constituent unit (B) within the above range, the moldability and birefringence of the resulting copolymer will be better balanced.Furthermore, from the viewpoint of achieving a lower birefringence, the content of the above-mentioned constituent unit (B) is preferably 40.0 mol% or more, more preferably 41.0 mol% or more, even more preferably 42.0 mol% or more, even more preferably 43.0 mol% or more, even more preferably 44.0 mol% or more, and preferably 70.0 mol% or less, more preferably 60.0 mol% or less, even more preferably 50.0 mol% or less, even more preferably 45.0 mol% or less, and preferably 40.0 mol% or more and 70.0 mol% or less, more preferably 41.0 mol% or more and 60.0 mol% or less, even more preferably 42.0 mol% or more and 50.0 mol% or less, even more preferably 43.0 mol% or more and 45.0 mol% or less, even more preferably 44.0 mol% or more and 45.0 mol% or less. In this embodiment, the content of constituent unit (B) is. １３ It can be measured by C-NMR.

[0049] The copolymerization type of the cyclic olefin copolymer in this embodiment is not particularly limited, but examples include random copolymers and block copolymers. From the viewpoint of obtaining a molded article with excellent optical properties such as transparency, Abbe number, refractive index and birefringence, as well as moldability, the cyclic olefin copolymer in this embodiment is preferably a random copolymer. Furthermore, the cyclic olefin copolymer in this embodiment may be either a ring-opening copolymer or an addition copolymer, but from the viewpoint of the degree of freedom in polymer design, an addition copolymer is preferred, and a random addition copolymer is more preferred.

[0050] In this embodiment, "ring-opening copolymer" refers to, for example, a ring-opening metathesis polymer of norbornene. On the other hand, "addition copolymer" refers to, for example, a copolymer polymerized by a vinyl addition reaction between ethylene and an α-olefin having 3 to 20 carbon atoms and a cyclic olefin having an unsaturated bond (e.g., norbornene). Taking an addition copolymer as an example in which constituent unit (A) is derived from ethylene and an α-olefin having 3 to 20 carbon atoms, and constituent unit (B) is derived from the compound represented by the above formula (B-1), such an addition copolymer has the following structure.

[0051]

[0052] In equation (I), R ３００ This represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 18 carbon atoms.

[0053]

[0054] In equation (II), n is 0 or 1, m is a positive integer, q is 0 or 1, and R １ ~R １８ R ａ and R ｂ Each is independently a hydrogen atom, a halogen atom, or a hydrocarbon group which may be substituted with a halogen atom, and R １５ ~R １８ These may be bonded to each other to form a monocycle or polycycle, and the monocycle or polycycle may have a double bond, and R １５ and R １６ And, or R １７ and R １８ They may form an alkylidene group. However, the monocyclic or polycyclic ring does not contain an aromatic ring.

[0055] The cyclic olefin-based addition copolymer in this embodiment is not limited to having the above-mentioned constituent units.

[0056] The method for producing the cyclic olefin copolymer of this embodiment is not particularly limited, and it can be produced by selecting appropriate conditions according to known methods for producing cyclic olefin copolymers. Examples of documents describing such manufacturing methods include Japanese Patent Publication No. 60-168708, Japanese Patent Publication No. 61-120816, Japanese Patent Publication No. 61-115912, Japanese Patent Publication No. 61-115916, Japanese Patent Publication No. 61-271308, Japanese Patent Publication No. 61-272216, Japanese Patent Publication No. 62-252406, Japanese Patent Publication No. 62-252407, Japanese Patent Publication No. Hei 2-173112, Japanese Patent Publication No. 2007-314806, Japanese Patent Publication No. 2010-241932, Japanese Patent Publication No. 2019-172954, Japanese Patent Publication No. 2022-154223, and Japanese Patent Publication No. 2022-155527.

[0057] The cyclic olefin copolymer of this embodiment may contain the above-described constituent units (A) and (B) in any ratio, but it is preferable that constituent unit (A) has a constituent unit (a1) derived from at least one monomer selected from the group consisting of ethylene and propylene, and a constituent unit (a2) derived from at least one α-olefin selected from the group consisting of α-olefins having 4 to 20 carbon atoms, the cyclic olefin of this embodiment contains the compound represented by the above formula (B-1), and when the total content of constituent units (A) and (B) in the cyclic olefin copolymer of this embodiment is 100 mol%, the content of constituent unit (B) in the cyclic olefin copolymer of this embodiment is 40.0 mol% or more. This makes it possible to further improve the balance between the moldability and birefringence of the copolymer.

[0058] The glass transition temperature (Tg) of the cyclic olefin copolymer in this embodiment is preferably 185.0°C or lower, more preferably 180.0°C or lower, even more preferably 175.0°C or lower, even more preferably 170.0°C or lower, even more preferably 160.0°C or lower, even more preferably 150.0°C or lower, even more preferably 140.0°C or lower, and even more preferably 135.0°C or lower, and for example, it may be 80.0°C or higher, 90.0°C or higher, and 100.0°C or lower. It may be above, it may be 110.0°C or higher, it may be 120.0°C or higher, it may be 125.0°C or higher, for example, it may be 120.0°C or higher and 185.0°C or lower, it may be 80.0°C or higher and 180.0°C or lower, it may be 90.0°C or higher and 175.0°C or lower, it may be 100.0°C or higher and 170.0°C or lower, it may be 110.0°C or higher and 160.0°C or lower, it may be 120.0°C or higher and 150.0°C or lower, it may be 120.0°C or higher and 140.0°C or lower, and it may be 125.0°C or higher and 135.0°C or lower.

[0059] Furthermore, from the viewpoint of balancing moldability and the heat resistance of the resulting molded article, it is preferable that the cyclic olefin copolymer has only one glass transition temperature (Tg) in the range of 185.0°C or lower, more preferably one in the range of 120.0°C to 180.0°C, even more preferably one in the range of 120.0°C to 175.0°C, even more preferably one in the range of 120.0°C to 170.0°C, even more preferably one in the range of 120.0°C to 160.0°C, even more preferably one in the range of 120.0°C to 150.0°C, even more preferably one in the range of 120.0°C to 140.0°C, and even more preferably one in the range of 125.0°C to 140.0°C.

[0060] The weight-average molecular weight (Mw) of the cyclic olefin copolymer in this embodiment is preferably 60,000 to 350,000, more preferably 70,000 to 330,000, even more preferably 80,000 to 310,000, even more preferably 90,000 to 300,000, even more preferably 90,000 to 220,000, even more preferably 100,000 to 220,000, even more preferably 110,000 to 220,000, even more preferably 120,000 to 220,000, and even more preferably 120,000 to 200,000, from the viewpoint of balancing moldability and the heat resistance of the resulting molded article.

[0061] Furthermore, the number-average molecular weight (Mn) of the cyclic olefin copolymer in this embodiment is preferably 20,000 to 200,000, more preferably 30,000 to 180,000, even more preferably 35,000 to 150,000, even more preferably 40,000 to 120,000, even more preferably 40,000 to 100,000, even more preferably 43,000 to 100,000, even more preferably 45,000 to 100,000, and even more preferably 45,000 to 80,000, from the viewpoint of balancing moldability and the heat resistance of the resulting molded article.

[0062] Furthermore, the molecular weight distribution (Mw / Mn) of the cyclic olefin copolymer in this embodiment is preferably 1.50 to 3.50, more preferably 1.80 to 3.20, even more preferably 2.00 to 3.00, even more preferably 2.00 to 2.50, even more preferably 2.10 to 2.40, and even more preferably 2.10 to 2.30, from the viewpoint of balancing moldability and the heat resistance of the resulting molded article.

[0063] From the viewpoint of further improving the balance between moldability and birefringence, it is preferable that at least one of the weight-average molecular weight, number-average molecular weight, and molecular weight distribution of the cyclic olefin copolymer of this embodiment is within the above range, more preferably at least two is within the above range, and even more preferably all are within the above range.

[0064] From the viewpoint of further improving the balance between moldability and birefringence, the complex viscosity (η*) of the cyclic olefin copolymer of this embodiment, as measured by the following [method], is preferably 500 Pa·s or more, more preferably 1,000 Pa·s or more, even more preferably 5,000 Pa·s or more, even more preferably 10,000 Pa·s or more, even more preferably 15,000 Pa·s or more, and preferably 1,200,000 Pa·s or less, more preferably 1,000,000 Pa·s or less, even more preferably 900,000 Pa·s or less, even more preferably 800,000 Pa·s or less, even more preferably 600,000 Pa·s or less, even more preferably 400, The pressure is preferably 000 Pa·s or less, more preferably 300,000 Pa·s or less, even more preferably 200,000 Pa·s or less, and preferably 500 Pa·s or more and 1,000,000 Pa·s or less, more preferably 1,000 Pa·s or more and 900,000 Pa·s or less, even more preferably 5,000 Pa·s or more and 800,000 Pa·s or less, even more preferably 10,000 Pa·s or more and 600,000 Pa·s or less, even more preferably 15,000 Pa·s or more and 400,000 Pa·s or less, even more preferably 15,000 Pa·s or more and 300,000 Pa·s or less, and even more preferably 15,000 Pa·s or more and 200,000 Pa·s or less. [Method] A cyclic olefin copolymer is sandwiched between ultra-heat-resistant polyimide films and vacuum-press-molded using a 1.0 mm spacer at (Tg + 110) °C, 10 MPa, and for 2 minutes to obtain a 1 mm thick test press specimen. Next, the test press specimen is placed in a jig of a viscoelasticity measuring device, heated to 250 °C to ensure close contact between the test press specimen and the jig, then cooled to the measurement temperature and measured under the following conditions: Deformation mode: shear Temperature range: 150 °C to 300 °C Heating rate: 2 °C / min Frequency: 1 rad / s Jig: Parallel plate 8 mmφ Environment: N ２ under

[0065] From the viewpoint of further improving the balance between moldability and birefringence, the average value of the phase difference measured by the following [Method] for the cyclic olefin copolymer of this embodiment is preferably less than 10.0 nm, more preferably less than 8.0 nm, even more preferably less than 7.0 nm, even more preferably less than 5.0 nm, even more preferably less than 2.0 nm, and even more preferably less than 1.0 nm. [Method] The cyclic olefin copolymer is sandwiched between ultra-heat-resistant polyimide films and vacuum-press-molded using a 0.1 mm spacer at (Tg + 110) °C, 10 MPa, and for 2 minutes to obtain a test film with a thickness of 0.1 mm. Next, the test film is stretched 1.5 times in the uniaxial direction at a stretching temperature of (Tg + 5 °C), a stretching speed of 3% / min, and a film chuck distance of 30 mm, removed from the chucks, immersed in ice water for 3 minutes to obtain a birefringence measurement film of 80 mm × 15 mm × thickness of 0.1 mm. The region between the film chucks, i.e., the stretched region, of the birefringence measurement film will be referred to as the stretched film portion. Next, for the birefringence measurement film, the phase difference of the stretched film portion is determined at measurement wavelengths of 523, 543, and 575 nm, and the average value of the phase difference at each measurement wavelength is calculated.

[0066] [Cyclic Olefin Copolymer Composition] The cyclic olefin copolymer composition of this embodiment will be described below.

[0067] The cyclic olefin copolymer composition of this embodiment includes the cyclic olefin copolymer of this embodiment described above, and optionally includes other components other than the cyclic olefin copolymer of this embodiment. In this specification, even if the cyclic olefin copolymer composition of this embodiment contains only the cyclic olefin copolymer, it is still referred to as a cyclic olefin copolymer composition.

[0068] Furthermore, from the viewpoint of further improving the balance of moldability and low birefringence performance, the content of the cyclic olefin copolymer of this embodiment in the cyclic olefin copolymer composition of this embodiment is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, and even more preferably 98% by mass or more, when the total cyclic olefin copolymer composition is considered to be 100% by mass. The content of the cyclic olefin copolymer of this embodiment in the cyclic olefin copolymer composition of this embodiment may be, for example, less than 100% by mass.

[0069] Other components include, for example, resins other than the cyclic olefin copolymer of this embodiment, hydrophilic agents, light 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, secondary antioxidants, mold release agents, and the like. Other components can be blended in amounts that do not impair the objectives of the present invention, and their blending ratio is appropriate.

[0070] The cyclic olefin copolymer composition of this embodiment can be obtained by methods such as: melt-kneading the cyclic olefin copolymer and other components of this embodiment using a known kneading apparatus such as an extruder and a Banbury mixer; dissolving the cyclic olefin copolymer and other components of this embodiment in a common solvent and then evaporating the solvent; or adding a solution of the cyclic olefin copolymer and other components of this embodiment to a poor solvent and precipitating it.

[0071] [Molded body and optical component] The molded body and optical component of this embodiment will be described below.

[0072] The molded article of this embodiment is a molded article comprising the cyclic olefin copolymer or cyclic olefin copolymer composition of this embodiment described above.

[0073] Because the molded article of this embodiment contains the cyclic olefin copolymer of this embodiment, it has a good balance of heat resistance, optical performance (transparency, haze, etc.), chemical resistance, and low moisture absorption, as well as an improved balance of moldability and low birefringence.

[0074] The optical component of this embodiment is an optical component that includes the molded body of this embodiment. Since the molded body of this embodiment contains the cyclic olefin copolymer of this embodiment, optical performance such as low birefringence is improved. Therefore, it can be suitably used as an optical component in optical systems where high-precision image identification is required.

[0075] In this embodiment, optical components refer to components used in optical systems and the like. Specifically, these include lenses for various sensors, pickup lenses, projector lenses, prisms, fθ lenses, imaging lenses, camera lenses, light guide plates, and lenses for head-mounted displays. Because of the improved optical performance, such as low birefringence, these components are particularly suitable for use in fθ lenses, imaging lenses, sensor lenses, prisms, light guide plates, or lenses for head-mounted displays.

[0076] The optical components of this embodiment may be an optical lens system formed by combining the above-mentioned various lenses with lenses different from the above-mentioned various lenses. For example, the optical lens system according to this embodiment may be a lens unit comprising a first optical lens made of a molded body containing a cyclic olefin copolymer according to this embodiment, and a second optical lens different from the first optical lens.

[0077] Furthermore, from the viewpoint of further improving the balance between moldability and low birefringence, the content of the cyclic olefin copolymer of this embodiment in the molded article of this embodiment is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, and even more preferably 98% by mass or more, when the total mass of the molded article is considered to be 100% by mass. The content of the cyclic olefin copolymer of this embodiment in the molded article of this embodiment may be, for example, less than 100% by mass.

[0078] The method for obtaining a molded article by molding the cyclic olefin copolymer or cyclic olefin copolymer composition of this embodiment is not particularly limited, and known methods can be used. Depending on the application and shape, for example, extrusion molding, injection molding, compression molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, vacuum molding, powder slush molding, calendering, foam molding, etc., can be applied. The molding conditions are appropriately selected depending on the intended use or molding method, but for example, the resin temperature in press molding may be, for example, above Tg + 50°C of the resin, or below Tg + 200°C of the resin. Specifically, it is preferably appropriately selected within the range of 180°C to 400°C, more preferably 200°C to 350°C, and even more preferably 220°C to 320°C.

[0079] Furthermore, the molded body of this embodiment may be a medical container. Examples of medical containers include syringes used in syringe barrels (hereinafter referred to as syringes) and syringes filled with drug solutions or pharmaceuticals (hereinafter also referred to as pre-filled syringes), and storage containers used in storage containers filled with drug solutions or pharmaceuticals (hereinafter also referred to as drug solution storage containers).

[0080] Here, a pre-filled syringe is a syringe-shaped preparation that is pre-filled with a drug solution or medication. There are single-chamber types filled with one type of liquid and double-chamber types filled with two types of medication. The double-chamber type may be a liquid-powder type preparation consisting of a powder and its solvent, or a liquid-liquid type preparation consisting of two types of liquid. Examples of syringes used for syringes and pre-filled syringes include prefillable syringes, pre-filled syringes for vaccines, pre-filled syringes for anticancer drugs, and needleless syringes.

[0081] Examples of drug solution storage containers include wide-mouth bottles, narrow-mouth bottles, medicine bottles, vials, infusion bottles, bulk containers, petri dishes, test tubes, and analytical cells. More specifically, examples include liquid, powder, or solid drug containers such as ampoules, press-through packages, infusion bags, drip drug containers, and eye drop containers; sample containers such as test tubes, blood collection tubes, and specimen containers for blood tests; analytical containers such as ultraviolet testing cells; sterilization containers for medical instruments such as scalpels, forceps, gauze, and contact lenses; medical devices such as disposable syringes and pre-filled syringes; laboratory equipment such as beakers, vials, ampoules, and test tube flasks; and housings for artificial organs.

[0082] Although embodiments of the present invention have been described above, these are merely examples, and various other configurations can be adopted. Furthermore, the present invention is not limited to the embodiments described above, and any modifications, improvements, etc., that can achieve the objectives of the present invention are included in the present invention.

[0083] This embodiment will be described in detail below with reference to examples and other relevant information. However, this embodiment is not limited in any way to the descriptions of these examples.

[0084] [ １３ [C-NMR Measurement] The content of constituent unit (A) and constituent unit (B) was measured using a Bruker AVANCE III cryo-500 nuclear magnetic resonance spectrometer under the following conditions: Solvent: 1,1,2,2-tetrachloroethane-d ２ Sample concentration: 40-60 mg / 0.6 mL; Pulse repetition time: 10 seconds; Number of cumulative pulses: 128-512; Measurement temperature: 120°C

[0085] Measured under the above conditions １３ The content of constituent units (A) and (B) constituting the cyclic olefin copolymer was quantified using 1C-NMR spectroscopy.

[0086] [Glass transition temperature Tg (°C)] The glass transition temperature (Tg) of a cyclic olefin copolymer was measured using a DSC-7020 manufactured by Hitachi High-Tech Science Corporation under the following temperature conditions and a nitrogen atmosphere. First, the cyclic olefin copolymer was heated from 25°C to 250°C at a heating rate of 10°C / min and held for 5 minutes. Next, it was cooled to -20°C at a cooling rate of 10°C / min and held for 5 minutes. Then, the glass transition temperature (Tg) of the cyclic olefin copolymer was determined from the endothermic curve when heating to 300°C at a heating rate of 10°C / min.

[0087] [Measurement of weight-average molecular weight (Mw) and number-average molecular weight (Mn)] The weight-average molecular weight (Mw), number-average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of cyclic olefin copolymers were determined by gel permeation chromatography (GPC). These were calculated from the molecular weight distribution curve obtained using a Waters GPC-IR6_MCT type gel permeation chromatograph, and the operating conditions were as follows. <Equipment and Conditions Used> Measurement device: Gel permeation chromatograph GPC-IR6_MCT type (Polymer Char) Analysis software: Chromatography data system Empower3 (Waters Inc.) Column: TSKgel GMH6-HT x 2 + TSKgel GMH6-HTL x 2 (inner diameter 7.5 mm x length 30 cm, manufactured by Tosoh Corporation) Mobile phase: o-dichlorobenzene [=ODCB] (containing 0.025% BHT) Detector: IR6 type infrared detector (Polymer Char) Column temperature: 140°C Flow rate: 1.0 mL / min Injection volume: 400 μL Sampling time interval: 0.5 seconds Sample concentration: 0.1% (w / v) Column calibration: Monodisperse polystyrene (manufactured by Tosoh Corporation) Molecular weight conversion: PS conversion / standard conversion method

[0088] [Preparation of films and press specimens for measuring complex viscosity (η*) and birefringence] The cyclic olefin copolymers obtained in each example and comparative example were sandwiched between ultra-heat-resistant polyimide films (product name: Upirex, manufactured by Ube Industries, Ltd.) and vacuum-press-molded using a 0.1 mm spacer at (Tg + 110) °C, 10 MPa, and for 2 minutes. This yielded test films with a thickness of 0.1 mm. Similarly, test press specimens with a thickness of 1 mm were obtained in the same manner except that the spacer was changed to a 1.0 mm spacer.

[0089] [Complex Viscosity (η*) Measurement] The complex viscosity (η*) of the 1 mm thick test press piece obtained above was determined using ARES-G2 (manufactured by T.A. Instruments). Specifically, the test press piece was clamped in a jig, heated to 250°C to ensure close contact with the jig, then cooled to the measurement temperature before measurement. <Equipment and Conditions Used> Measurement device: ARES-G2 (manufactured by T.A. Instruments) Deformation mode: Shear Temperature range: 150°C to 300°C Heating rate: 2°C / min Frequency: 1 rad / s Jig: Parallel plate 8 mmφ Environment: N ２ under

[0090] [Birefringence] The 0.1 mm thick test film obtained above was stretched 1.5 times in the uniaxial direction using an AG-1kNXplus (Shimadzu Corporation) under the conditions of a stretching temperature of (Tg + 5°C), a stretching speed of 3% / min, and a film chuck distance of 30 mm. After removing it from the chucks, it was immersed in ice water for 3 minutes to obtain a birefringence measurement film of 80 mm × 15 mm × thickness of 0.1 mm. The region between the film chucks, i.e., the stretched region, of the birefringence measurement film is called the stretched film portion. Next, using a WPA-200 (Photonic Lattice) for the birefringence measurement film, the phase difference of the stretched film portion was determined at measurement wavelengths of 523 nm, 543 nm, and 575 nm. The average value (nm) of the phase difference at each measurement wavelength was determined as the birefringence. The average value of the obtained phase difference was evaluated according to the following criteria. When the evaluation was A to C, it was determined that the desired low birefringence had been obtained. (Evaluation Criteria) A: The average value of the phase difference is less than 1.0 nm. B: The average value of the phase difference is 1.0 nm or more and less than 5.0 nm. C: The average value of the phase difference is 5.0 nm or more and less than 10.0 nm. D: The average value of the phase difference is 10.0 nm or more.

[0091] Example 1 A glass reactor with an internal volume of 500 mL (internal volume of 250 mL) that has been thoroughly purged with nitrogen is filled with 230 mL of a mixed solution of cyclohexane / hexane in a ratio of 9 / 1 and tetracyclo[4.4.0.1 ２，５ 1. ７，１０ 5.1 g of tetracyclododecene (hereinafter also simply referred to as "tetracyclododecene," Mw: 160.2 g / mol) and 1.4 g of 1-octene were charged, and the liquid and gas phases were saturated with ethylene at a rate of 99 liters / hr. 7.5 mmol of MMAO (modified methylaluminoxane) was added. Subsequently, 0.015 mmol of cyclopentadienyl(2,2,4,4-tetramethyl-3-pentaneiminato)dichlorotitanium (hereinafter referred to as titanium compound (1)) was added to initiate the polymerization reaction.

[0092] Polymerization was carried out at 50°C for 10 minutes under atmospheric pressure by continuously supplying 99 liters / hr of ethylene, after which polymerization was stopped by adding a small amount of isobutanol. After polymerization was complete, the reactants were added to 1 liter of acetone / methanol (3 / 1) mixed solvent containing a small amount of hydrochloric acid, and the polymer was precipitated. After washing with the same solvent, the mixture was dried under reduced pressure at 130°C for 10 hours to obtain 0.7 g of ethylene-octene-tetracyclododecene copolymer. The polymerization activity was 0.13 kg / mol / hr. The composition, Tg, molecular weight, complex viscosity (η*), and birefringence of the obtained copolymer are shown in Table 1.

[0093] Copolymers of Examples 2-9 and Comparative Example 2 were obtained in the same manner as in Example 1, except that the types and composition ratios of monomer compounds were changed so that the types and composition ratios of constituent units A and B were as shown in Table 1. The same evaluation as in Example 1 was performed. The evaluation results are shown in Table 1.

[0094] Comparative Example 1 A copolymer was obtained using the same method as in Example 1 described in International Publication No. 2023 / 171221, and evaluated in the same manner as in Example 1 of this application. The results are shown in Table 1.

[0095]

[0096] The copolymer of Comparative Example 1 had a low birefringence but a high complex viscosity (η*), indicating room for further improvement in moldability. On the other hand, the copolymer of Comparative Example 2 had a low complex viscosity (η*) and good moldability, but a high birefringence, indicating a need for improvement in optical performance. In contrast to these, the copolymers of Examples 1 to 9 had low birefringence and low complex viscosity (η*), resulting in improved moldability.

[0097] This application claims priority based on Japanese Patent Application No. 2025-055233, filed on 28 March 2025, and incorporates all of its disclosures herein.

Claims

1. A cyclic olefin copolymer comprising: a constituent unit (A) derived from at least two monomers selected from the group consisting of ethylene and α-olefins having 3 to 20 carbon atoms; and a constituent unit (B) derived from a cyclic olefin.

2. The structural unit (A) has a structural unit (a1) derived from at least one monomer selected from the group consisting of ethylene and propylene, and a structural unit (a2) derived from at least one α-olefin selected from the group consisting of C4-C20 α-olefins, the cyclic olefin comprises a compound represented by the following formula (B-1), and when the total content of the structural unit (A) and the structural unit (B) in the cyclic olefin-based copolymer is 100 mol%, the content of the structural unit (B) in the cyclic olefin-based copolymer is 40.0 mol% or more, the cyclic olefin-based copolymer according to claim 1. (In the formula (B-1), n is 0 or 1, m is a positive integer, q is 0 or 1, and R １ to R １８ as well as R ａ and R ｂ are each independently a hydrogen atom, a halogen atom or a hydrocarbon group optionally substituted with a halogen atom, R １５ to R １８ may be bonded to each other to form a monocyclic or polycyclic ring, the monocyclic or polycyclic ring may have a double bond, and R １５ and R １６ , or R １７ and R １８ may form an alkylidene group. Provided that the monocyclic or polycyclic ring does not contain an aromatic ring.) 3. The cyclic olefin copolymer according to claim 2, wherein when the total content of the constituent unit (a1) and the constituent unit (a2) in the constituent unit (A) is 100 mol%, the content of the constituent unit (a2) is 1.0 mol% or more and 55.0 mol% or less.

4. The cyclic olefin copolymer according to claim 2, wherein the constituent unit (a2) comprises at least one α-olefin-derived constituent unit selected from the group consisting of linear α-olefins having 4 to 20 carbon atoms.

5. The cyclic olefin copolymer according to claim 3, wherein the sum of the constituent units (a1), (a2), and (B) in the cyclic olefin copolymer exceeds 95 mol%.

6. The constituent unit (B) is tetracyclo[4.4.0.1 ２，５ 1. ７，１０ A cyclic olefin copolymer according to claim 1 or 2, comprising a constituent unit derived from ]-3-dodecene.

7. A cyclic olefin copolymer according to claim 1 or 2, which is a random addition copolymer.

8. The cyclic olefin copolymer according to claim 1 or 2, wherein when the total content of the constituent unit (A) and the constituent unit (B) in the cyclic olefin copolymer is 100 mol%, the content of the constituent unit (A) in the cyclic olefin copolymer is 30.0 mol% or more and 80.0 mol% or less.

9. The cyclic olefin copolymer according to claim 1 or 2, wherein when the total content of the constituent unit (A) and the constituent unit (B) in the cyclic olefin copolymer is 100 mol%, the content of the constituent unit (B) in the cyclic olefin copolymer is 70.0 mol% or less.

10. The cyclic olefin copolymer according to claim 1 or 2, wherein the glass transition temperature (Tg) is 185.0°C or lower.

11. The cyclic olefin copolymer according to claim 1 or 2, wherein the glass transition temperature (Tg) is in the range of 185.0°C or less.

12. The cyclic olefin copolymer according to claim 1 or 2, wherein the weight-average molecular weight (Mw) is 60,000 or more and 350,000 or less.

13. The cyclic olefin copolymer according to claim 1 or 2, wherein the number average molecular weight (Mn) is 20,000 or more and 200,000 or less.

14. The cyclic olefin copolymer according to claim 1 or 2, wherein the molecular weight distribution (Mw / Mn) is 1.50 or more and 3.50 or less.

15. The cyclic olefin copolymer according to claim 1 or 2, wherein the complex viscosity (η*) measured by the following [Method] is 1,200,000 Pa·s or less. [Method] The cyclic olefin copolymer is sandwiched between ultra-heat-resistant polyimide films and vacuum-press-molded using a 1.0 mm spacer at (Tg + 110) °C, 10 MPa, and for 2 minutes to obtain a 1 mm thick test press piece. Next, the test press piece is sandwiched in a jig of a viscoelasticity measuring device, the temperature is raised to 250 °C to make the test press piece tightly attached to the jig, and then the temperature is lowered to the measurement temperature, and the measurement is performed under the following conditions. Deformation mode: shear Temperature range: 150 °C to 300 °C Heating rate: 2 °C / min Frequency: 1 rad / s Jig: Parallel plate 8 mmφ Environment: N ２ under 16. The cyclic olefin copolymer according to claim 1 or 2, wherein the average value of the phase difference obtained by the following [Method] is less than 10.0 nm. [Method] The cyclic olefin copolymer is sandwiched between super heat-resistant polyimide films and vacuum-press-molded using a 0.1 mm spacer at (Tg + 110) °C, 10 MPa, and for 2 minutes to obtain a test film with a thickness of 0.1 mm. Next, the test film is stretched 1.5 times in the uniaxial direction at a stretching temperature of (Tg + 5 °C), a stretching speed of 3% / min, and a film chuck distance of 30 mm. It is then removed from the chucks and immersed in ice water for 3 minutes to obtain a birefringence measurement film of 80 mm × 15 mm × thickness of 0.1 mm. The region between the film chucks, i.e., the stretched region, of the birefringence measurement film is called the stretched film portion. Next, for the birefringence measurement film, the phase difference of the stretched portion of the film is determined at measurement wavelengths of 523 nm, 543 nm, and 575 nm, and the average value of the phase difference at each measurement wavelength is calculated.

17. A cyclic olefin copolymer composition comprising the cyclic olefin copolymer described in claim 1 or 2.

18. A molded article comprising the cyclic olefin copolymer described in claim 1, or the cyclic olefin copolymer composition described in claim 17.

19. An optical component comprising the molded body described in claim 18.

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