Cyclic olefin copolymer composition and molded body

Abstract

Provided is a cyclic olefin copolymer composition comprising a cyclic olefin copolymer (A) having a glass transition point (Tg) of more than 100.0°C and a cyclic olefin copolymer (B) having a glass transition point (Tg) of 100.0°C or less. When the total amount of the cyclic olefin copolymer (A) and the cyclic olefin copolymer (B) is taken to be 100 mass parts, the content of the cyclic olefin copolymer (A) is from more than 95.0 mass parts to 99.9 mass parts and the content of the cyclic olefin copolymer (B) is from 0.1 mass part to less than 5.0 mass parts.

Description

Cyclic olefin copolymer composition and molded article

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

[0002] Because cyclic olefin copolymers and compositions containing them have excellent optical properties, they are used, for example, as optical components such as optical lenses. Examples of technologies relating to cyclic olefin copolymer compositions used in optical components include those described in Patent Documents 1 and 2.

[0003] Patent Document 1 contains [A] (1) a cyclic olefin polymer represented by a specific general formula and (2) having a softening temperature (TMA) of 120 to 300°C, and [B] a cyclic olefin polymer having a glass transition temperature (Tg) of 50°C or less, wherein the refractive index of the olefin polymer [B] measured in accordance with ASTM D542 is n Ｄ Let [B] be the refractive index of the cyclic olefin polymer [A], and let n be the refractive index of n Ｄ When [A] is the case, |n Ｄ [B -n Ｄ A cyclic olefin polymer composition is described, characterized in that the absolute value of the difference in refractive index represented by [A]| is 0.014 or less, and the composition contains 5 to 50 parts by weight of component [B] (total amount of components [A] and [B] is 100 parts by weight) per 50 to 95 parts by weight of component [A]. Patent Document 1 states that the cyclic olefin polymer composition of Patent Document 1 has excellent transparency and heat resistance, good moldability, and excellent durability during the molding process of films or sheets.

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

[0005] International Publication No. 2008 / 068897, Japanese Patent Application Laid-Open No. 9-176397

[0006] The problem in the present invention is to provide a cyclic olefin copolymer composition with an improved balance of light transmittance and moisture and heat resistance.

[0007] According to the present invention, the following cyclic olefin copolymer composition and molded body are provided.

[0008] 1. A cyclic olefin copolymer composition comprising a cyclic olefin copolymer [A] having a glass transition temperature (Tg) exceeding 100.0 °C and a cyclic olefin copolymer [B] having a glass transition temperature (Tg) of 100.0 °C or less, wherein when the total amount of the cyclic olefin copolymer [A] and the cyclic olefin copolymer [B] is 100 parts by mass, the content of the cyclic olefin copolymer [A] is more than 95.0 parts by mass and 99.9 parts by mass or less, and the content of the cyclic olefin copolymer [B] is 0.1 parts by mass or more and less than 5.0 parts by mass. 2. The refractive index of the cyclic olefin copolymer [B] measured in accordance with ASTM D542 is n Ｄ [B], and when the refractive index of the cyclic olefin copolymer [A] is n Ｄ [A], the absolute value of the refractive index difference represented by the following formula exceeds 0.014. The cyclic olefin copolymer composition according to 1. 3. The cyclic olefin copolymer composition according to 1. or 2., wherein the glass transition temperature (Tg) of the cyclic olefin copolymer [B] is -20.0°C or higher and 90.0°C or lower. 4. The cyclic olefin copolymer composition according to any one of 1. to 3., wherein the cyclic olefin copolymer [A] comprises at least one olefin-derived structural unit (a) represented by the following general formula (Ia), and at least one structural unit selected from the group consisting of structural unit (b) and structural unit (c), wherein the structural unit (b) comprises at least one structural unit selected from the group consisting of a structural unit derived from a cyclic olefin monomer (AA) represented by the following general formula (IIa) and a structural unit derived from a cyclic olefin monomer (AC) represented by the following general formula (IVa), and the structural unit (c) comprises at least one structural unit selected from the group consisting of a structural unit derived from a cyclic olefin monomer represented by the following general formula (C-1), a structural unit derived from a cyclic olefin monomer represented by the following general formula (C-2), and a structural unit derived from a cyclic olefin monomer represented by the following general formula (C-3). In the above general formula (Ia), R ３００ This represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms. In the above general formula (IIa), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, and R ６１ ~R ７８ And R ａ１ and R ｂ１ These may be the same or different from each other, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, R ７５ ~R ７８ These elements may be bonded to each other to form a monocycle or polycycle. In the above general formula (IVa), R １００ , R １０１ These elements may be identical or different from each other, and represent a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, where f is 1 ≤ f ≤ 18. In the above general formula (C-1), n ​​and q are independently 0, 1, or 2, and 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 bonding, and 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 , R １６ 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. In the above general formula (C-2), n and m are independently 0, 1, or 2, q is 1, 2, or 3, and 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 which may be substituted with a halogen atom other than a fluorine atom, and when q = 1, R２８ and R ２９ R ２９ and R ３０ R ３０ and R ３１ may be bonded to each other to form a monocyclic or polycyclic ring, 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 may be bonded to each other to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring may be an aromatic ring. In the general formula (C-3), q is 1, 2 or 3, and 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, and 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 ３９They 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. 5. The cyclic olefin copolymer [B] includes at least one structural unit (a) derived from at least one olefin represented by the following general formula (Ia), and at least one structural unit selected from the group consisting of structural unit (b) and structural unit (c). The structural unit (b) includes at least one structural unit selected from the group consisting of a structural unit derived from a cyclic olefin monomer (AA) represented by the following general formula (IIa) and a structural unit derived from a cyclic olefin monomer (AC) represented by the following general formula (IVa). The structural unit (c) includes at least one structural unit selected from the group consisting of a structural unit derived from a cyclic olefin monomer represented by the following general formula (C-1), a structural unit derived from a cyclic olefin monomer represented by the following general formula (C-2), and a structural unit derived from a cyclic olefin monomer represented by the following general formula (C-3). The cyclic olefin copolymer composition according to any one of 1. to 4. In the general formula (Ia), R ３００ represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms. In the general formula (IIa), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, and R ６１ to R ７８ as well as R ａ１ and R ｂ１ may be the same as or different from each other, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms. R ７５ to R ７８ may be bonded to each other to form a monocyclic or polycyclic ring. ７８ In the general formula (IVa), R １００ , R １０１ may be the same as or different from each other, and represent a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and 1 ≤ f ≤ 18. In the above general formula (C-1), n ​​and q are independently 0, 1, or 2, and 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 bonding, and 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 , R １６ 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. In the above general formula (C-2), n and m are independently 0, 1, or 2, q is 1, 2, or 3, and 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 which may be substituted with a halogen atom other than a fluorine atom, and when q = 1, R２８ 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 be an aromatic ring. In the above general formula (C-3), q is 1, 2, or 3, and R ３２ ~R ３９ 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 when q = 1, R ３６ and R ３７ , R ３７ and R ３８ , R ３８ and R ３９ They may be bonded to each other to form a monocycle or polycycle, 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 ３９The rings 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. 6. The cyclic olefin copolymer composition according to 5, wherein the cyclic olefin copolymer [B] comprises one or more selected from the group consisting of [B-1] and [B-2] below. [B-1] A random copolymer comprising the constituent unit (a) and the constituent unit (c). [B-2] A random copolymer comprising the constituent unit (a) and the constituent unit (b). 7. The cyclic olefin copolymer composition according to 5 or 6, wherein the total content of the constituent unit (a), the constituent unit (b), and the constituent unit (c) in the cyclic olefin copolymer [B] is 80.0 mol% or more and 100 mol% or less, when the total content of all constituent units in the cyclic olefin copolymer [B] is 100 mol%. 8. 11. A cyclic olefin copolymer composition according to any one of 5 to 7, wherein the content of the constituent unit (a) in the cyclic olefin copolymer [B] is greater than 50.0 mol% when the total content of all constituent units in the cyclic olefin copolymer [B] is 100 mol%. 9. A cyclic olefin copolymer composition according to any one of 1 to 8, wherein the weight-average molecular weight (Mw) of the cyclic olefin copolymer [B] is 10,000 g / mol or more and 300,000 g / mol or less. 10. A cyclic olefin copolymer composition according to any one of 4 to 9, wherein the cyclic olefin copolymer [A] is a random copolymer containing the constituent unit (a) and the constituent unit (b). 11. A molded article containing the cyclic olefin copolymer composition according to any one of 1 to 10. 12. The molded article according to 11, wherein the molded article is a sensor lens, a pickup lens, a projector lens, a prism, an fθ lens, an imaging lens, a light guide plate, or a lens for a head-mounted display. 13. The molded article according to 11, wherein the molded article is a film or a sheet. 14. The molded article according to 13, wherein the molded article is an optical film or an optical sheet. 15. The molded article according to any one of 11 to 14, wherein the molded article is an injection molded product.

[0009] According to the present invention, it is possible to provide a cyclic olefin copolymer composition with an improved balance of light transmittance and heat and humidity resistance.

[0010] In this embodiment, "A to B" indicating a numerical range means A or greater and B or less unless otherwise specified. Also, in this embodiment, "having substituents" for groups such as alkyl groups means that hydrogen atoms present in the structure are substituted with substituents unless otherwise specified. The position of the substituents and the number of substituents are not particularly limited. Note that if the substituent has carbon atoms, the number of carbon atoms in the substituent is not included in the number of carbon atoms of the substituent group. For example, an ethyl group having a phenyl group as a substituent is considered an alkyl group with 2 carbon atoms. Furthermore, the various monomers in this invention may be derived from fossil raw materials, from biological sources such as biomass, or mixtures thereof.

[0011] 1. Cyclic Olefin Copolymer Composition The cyclic olefin copolymer composition of this embodiment will be described below.

[0012] The cyclic olefin copolymer composition of this embodiment comprises a cyclic olefin copolymer [A] having a glass transition temperature (Tg) greater than 100.0°C and a cyclic olefin copolymer [B] having a glass transition temperature (Tg) of 100.0°C or less, wherein when the total amount of the cyclic olefin copolymer [A] and the cyclic olefin copolymer [B] of this embodiment is 100 parts by mass, the content of the cyclic olefin copolymer [A] of this embodiment is greater than 95.0 parts by mass and less than 99.9 parts by mass, and the content of the cyclic olefin copolymer [B] of this embodiment is 0.1 parts by mass or more and less than 5.0 parts by mass.

[0013] The inventors of the present invention have found that by adjusting the glass transition temperatures and mixing ratios of the cyclic olefin copolymer [A] and the cyclic olefin copolymer [B], the balance between light transmittance and heat resistance can be improved in the cyclic olefin copolymer composition of this embodiment, thereby completing the present invention.

[0014] [Cyclic olefin copolymer [A]] The cyclic olefin copolymer composition of this embodiment (hereinafter also simply referred to as the "polymer composition") contains a cyclic olefin copolymer [A] (hereinafter also simply referred to as "polymer A").

[0015] Copolymer A is not particularly limited as long as its glass transition temperature (Tg) is greater than 100.0°C. However, from the viewpoint of further improving the light transmittance and heat resistance of the cyclic olefin copolymer composition of this embodiment, the Tg is preferably 110.0°C or higher, more preferably 115.0°C or higher, even more preferably 120.0°C or higher, even more preferably 125.0°C or higher, even more preferably 130.0°C or higher, even more preferably 135.0°C or higher, even more preferably 140.0°C or higher, even more preferably 145.0°C or higher, even more preferably 150.0°C or higher, even more preferably 155.0°C or higher, and even more preferably 160.0°C or higher. While there is no particular upper limit to Tg, from the viewpoint of further improving the light transmittance and heat resistance of the cyclic olefin copolymer composition of this embodiment, it can be, for example, 300.0°C or less, preferably 290.0°C or less, more preferably 280.0°C or less, even more preferably 270.0°C or less, even more preferably 260.0°C or less, even more preferably 250.0°C or less, even more preferably 240.0°C or less, even more preferably 230.0°C or less, even more preferably 220.0°C or less, even more preferably 210.0°C or less, and even more preferably 200.0°C or less. Furthermore, from the viewpoint of further improving the light transmittance and heat and humidity resistance of the cyclic olefin copolymer composition of this embodiment, the Tg is preferably 110.0°C to 300.0°C, more preferably 115.0°C to 300.0°C, even more preferably 120.0°C to 300.0°C, even more preferably 125.0°C to 300.0°C, even more preferably 130.0°C to 300.0°C, even more preferably 135.0°C to 290.0°C, and even more preferably 135. The temperature range is 0°C to 280.0°C, more preferably 140.0°C to 270.0°C, more preferably 145.0°C to 260.0°C, more preferably 150.0°C to 250.0°C, more preferably 150.0°C to 240.0°C, more preferably 150.0°C to 230.0°C, more preferably 155.0°C to 220.0°C, more preferably 155.0°C to 210.0°C, and more preferably 160.0°C to 200.0°C.The Tg of copolymer A can be adjusted by changing various polymerization conditions, such as the type and content ratio of the monomers used as raw materials, and the type of polymerization catalyst.

[0016] Copolymer A is a cyclic olefin copolymer obtained by copolymerizing a cyclic olefin with a monomer other than a cyclic olefin. There are no particular restrictions on the cyclic olefin or the monomer other than a cyclic olefin, but from the viewpoint of further improving the light transmittance and heat resistance of the cyclic olefin copolymer composition of this embodiment, copolymer A preferably includes at least one olefin-derived constituent unit (a) represented by the following general formula (Ia), and at least one constituent unit selected from the group consisting of the following constituent unit (b) and the following constituent unit (c). The constituent unit (b) of this embodiment includes at least one constituent unit selected from the group consisting of a constituent unit derived from a cyclic olefin monomer (AA) represented by the following general formula (IIa) and a constituent unit derived from a cyclic olefin monomer (AC) represented by the following general formula (IVa). The constituent unit (c) of this embodiment includes at least one constituent unit selected from the group consisting of a constituent unit derived from a cyclic olefin monomer represented by the following general formula (C-1), a constituent unit derived from a cyclic olefin monomer represented by the following general formula (C-2), and a constituent unit derived from a cyclic olefin monomer represented by the following general formula (C-3). Copolymer A more preferably includes a random copolymer comprising at least one olefin-derived constituent unit (a) represented by the following general formula (Ia), and at least one constituent unit selected from the group consisting of the following constituent units (b) and (c). Even more preferably, it includes a random copolymer comprising the constituent unit (a) and the constituent unit (b) of this embodiment. Copolymer A having the above composition tends to have a better balance between moisture and heat resistance and light transmittance. Each constituent unit will be described in detail below.

[0017] [Constituent Unit (a)] Constituent unit (a) is a constituent unit derived from at least one olefin represented by the following general formula (Ia).

[0018]

[0019] In the above general formula (Ia), R ３００ represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms. The constituent unit represented by the following general formula (I) corresponds to the olefin monomer represented by the above general formula (Ia). That is, the olefin monomer represented by the above general formula (Ia) undergoes addition polymerization to form the constituent unit represented by the following general formula (I).

[0020]

[0021] In the above general formula (I), R ３００ R in the above general formula (Ia) is ３００ It exhibits a similar base.

[0022] Examples of olefins represented by the above general formula (Ia) include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. Among these, from the viewpoint of further improving the balance of light transmittance and humidity and heat resistance, it is preferable to include at least one selected from the group consisting of ethylene and propylene, and more preferably ethylene. Two or more types of olefin monomers represented by the above general formula (Ia) may be used.

[0023] The content of constituent unit (a) in copolymer A is preferably more than 50 mol%, more preferably more than 50 mol% and 90 mol% or less, even more preferably more than 55 mol% and 90 mol% or less, even more preferably more than 58 mol% and 80 mol% or less, even more preferably more than 60 mol% and 70 mol% or less, and even more preferably more than 63 mol% and 65 mol% or less, when the total content of all constituent units in copolymer A is set to 100 mol%, from the viewpoint of further improving the light transmittance and moisture and heat resistance of the cyclic olefin copolymer composition of this embodiment. When the content of constituent unit (a) in copolymer A is within the above range, copolymer A has good moldability.

[0024] [Constituent Unit (b)] Constituent unit (b) includes at least one constituent unit selected from the group consisting of constituent units derived from a cyclic olefin monomer (AA) represented by general formula (IIa) and constituent units derived from a cyclic olefin monomer (AC) represented by general formula (IVa), and preferably includes a constituent unit derived from a cyclic olefin monomer (AA) represented by general formula (IIa). Each cyclic olefin monomer will be described in detail below.

[0025] (Cyclic olefin monomer (AA)) A cyclic olefin monomer (AA) is represented by the following general formula (IIa).

[0026]

[0027] In the above general formula (IIa), u is 0 or 1, v is 0 or a positive integer, preferably an integer between 0 and 4, more preferably an integer between 0 and 3, even more preferably an integer between 0 and 2, even more preferably 0 or 1, w is 0 or 1, R ６１ ~R ７８ And R ａ１ and R ｂ１ These may be the same or different from each other, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, R ７５ ~R ７８These elements may be bonded to each other to form a monocycle or polycycle.

[0028] Specifically, examples of alkyl groups having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, amyl, hexyl, octyl, decyl, dodecyl, and octadecyl groups; examples of halogenated alkyl groups having 1 to 20 carbon atoms include halogenated versions of the groups listed as alkyl groups having 1 to 20 carbon atoms; examples of cycloalkyl groups having 3 to 15 carbon atoms include cyclohexyl groups; and examples of aromatic hydrocarbon groups having 6 to 20 carbon atoms include aryl groups such as phenyl, tolyl, naphthyl, benzyl, and phenylethyl groups, as well as aralkyl groups.

[0029] Specific examples of cyclic olefin monomers represented by general formula (IIa) include the compounds described in paragraphs 0037-0063 of International Publication No. 2006 / 118261. Furthermore, cyclic olefin monomers can be obtained, for example, from dicyclopentadiene and ethylene. The ethylene may include constituent units derived from biomass-derived monomers (ethylene).

[0030] The cyclic olefin monomer represented by the above general formula (IIa) is preferably bicyclo[2.2.1]-2-heptene (also called norbornene) and tetracyclo[4.4.0.1 ２，５ 1. ７，１０ The copolymer contains at least one selected from the group consisting of ]-3-dodecene (also called tetracyclododecene), and more preferably contains tetracyclododecene. Because these cyclic olefin monomers have a rigid ring structure, the elastic modulus of copolymer A and the molded article is easily maintained. Two or more types of cyclic olefin monomers represented by the above general formula (IIa) may be used.

[0031] The constituent unit represented by the following general formula (II) corresponds to the cyclic olefin monomer represented by the above general formula (IIa). That is, the cyclic olefin monomer represented by the above general formula (IIa) undergoes addition polymerization to form the constituent unit represented by the following general formula (II).

[0032]

[0033] In the above general formula (II), u, v, w, R ６１ ~R ７８ And R ａ１ and R ｂ１ These are u, v, w, R in the above general formula (IIa). ６１ ~R ７８ And R ａ１ and R ｂ１ It may represent a similar base or value.

[0034] (Cyclic olefin monomers (ACs)) Cyclic olefin monomers (ACs) are represented by the following general formula (IVa).

[0035]

[0036] In the above general formula (IVa), R １００ and R １０１ These may be the same or different from each other, and represent a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, where f is 1 ≤ f ≤ 18, preferably 1 ≤ f ≤ 12, more preferably 1 ≤ f ≤ 8, even more preferably 1 ≤ f ≤ 6, and even more preferably 1 ≤ f ≤ 4.

[0037] Specifically, examples of hydrocarbon groups having 1 to 5 carbon atoms include methyl groups, ethyl groups, propyl groups, and isopropyl groups.

[0038] Specific examples of cyclic olefin monomers represented by general formula (IVa) include the compounds described in paragraphs 0037 to 0063 of International Publication No. 2006 / 118261. Two or more types of olefin monomers represented by the above general formula (IVa) may be used.

[0039] The constituent unit represented by the following general formula (IV) corresponds to the cyclic olefin monomer represented by the above general formula (IVa). That is, the cyclic olefin monomer represented by the above general formula (IVa) undergoes addition polymerization to form the constituent unit represented by the following general formula (IV).

[0040]

[0041] In the above general formula (IV), R１００ and R １０１ Furthermore, f is R in the above general formula (IVa). １００ and R １０１ It may also show a base or value similar to f.

[0042] [Constituent Unit (c)] Constituent unit (c) includes at least one constituent unit selected from the group consisting of constituent units derived from cyclic olefin monomers represented by general formula (C-1), constituent units derived from cyclic olefin monomers represented by general formula (C-2), and constituent units derived from cyclic olefin monomers represented by general formula (C-3). Preferably, it includes at least one constituent unit selected from the group consisting of constituent units derived from cyclic olefin monomers represented by the following general formula (C-1) and constituent units derived from cyclic olefin monomers represented by the following general formula (C-3), and more preferably, it includes a constituent unit derived from a cyclic olefin monomer represented by the following general formula (C-3). Each cyclic olefin monomer will be described in detail below.

[0043] (Cyclic olefin monomer represented by general formula (C-1))

[0044]

[0045] In the above general formula (C-1), n ​​and q are each independently 0, 1, or 2, where n is preferably 0 or 1, more preferably 0, and q is preferably 0 or 1, 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 is preferably independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrogen atom, and when q = 0, R １０ and R １１ , R １１ and R １２ , R１２ 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 , R １６ 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.

[0046] Examples of hydrocarbon groups having 1 to 20 carbon atoms include alkyl groups such as methyl, ethyl, propyl, isopropyl, amyl, hexyl, octyl, decyl, dodecyl, and octadecyl groups; cycloalkyl groups such as cyclohexyl groups; aryl groups such as phenyl, tolyl, naphthyl, benzyl, and phenylethyl groups; and aromatic hydrocarbon groups such as aralkyl groups. These groups may be substituted with halogen atoms other than fluorine atoms.

[0047] Two or more types of cyclic olefin monomers represented by the above general formula (C-1) may be used.

[0048] Among the general formulas (C-1) above, the cyclic olefin monomer represented by the general formula (C-1A) below is preferred. Each substituent in general formula (C-1A) is defined as in general formula (C-1) above.

[0049]

[0050] (Cyclic olefin monomer represented by general formula (C-2))

[0051]

[0052] In the above general formula (C-2), n and m are each independently 0, 1, or 2, q is 1, 2, or 3, m is preferably 0 or 1, more preferably 1, n is preferably 0 or 1, more preferably 0, q is preferably 1 or 2, more preferably 1, R １８ ~R ３１ 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 １８ ~R ３１ Each of these is preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrogen atom, and 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 be an aromatic ring.

[0053] Examples of hydrocarbon groups having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, amyl, hexyl, octyl, decyl, dodecyl, and octadecyl groups; examples of cycloalkyl groups having 3 to 15 carbon atoms among hydrocarbon groups having 1 to 20 carbon atoms include cyclohexyl groups; examples of aromatic hydrocarbon groups having 6 to 20 carbon atoms among hydrocarbon groups having 1 to 20 carbon atoms include aryl groups such as phenyl, tolyl, naphthyl, benzyl, and phenylethyl groups, as well as aralkyl groups. These groups may be substituted with halogen atoms other than fluorine atoms.

[0054] Two or more types of cyclic olefin monomers represented by the above general formula (C-2) may be used.

[0055] (Cyclic olefin monomer represented by general formula (C-3))

[0056] In general formula (C-3), q is 1, 2, or 3, and R ３２ ~R ３９ 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 when q = 1, R ３６ and R ３７ , R ３７ and R ３８ , R ３８ and R ３９ They may be bonded to each other to form a monocycle or polycycle, 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 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.

[0057] In the above general formula (C-3), q is 1, 2, or 3, preferably 1 or 2, more preferably 1, and R ３２ ~R ３９ 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 ３２ ~R ３９ Each is preferably independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrogen atom, and when q = 1, R ３６ and R ３７ , R ３７ and R ３８ , R ３８ and R ３９ They may be bonded to each other to form a monocycle or polycycle, 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 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.

[0058] Examples of hydrocarbon groups having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, amyl, hexyl, octyl, decyl, dodecyl, and octadecyl groups; examples of cycloalkyl groups having 3 to 15 carbon atoms among hydrocarbon groups having 1 to 20 carbon atoms include cyclohexyl groups; examples of aromatic hydrocarbon groups having 6 to 20 carbon atoms among hydrocarbon groups having 1 to 20 carbon atoms include aryl groups such as phenyl, tolyl, naphthyl, benzyl, and phenylethyl groups, as well as aralkyl groups. These groups may be substituted with halogen atoms other than fluorine atoms.

[0059] Two or more types of cyclic olefin monomers represented by the above general formula (C-3) may be used.

[0060] The constituent unit (c) preferably comprises a constituent unit derived from at least one compound selected from the group consisting of methylphenylnorbornene, indenenorbornene, and benzonorbornadiene, and more preferably comprises a constituent unit derived from benzonorbornadiene.

[0061] The total content of constituent units (a), (b), and (c) in copolymer A is preferably 80 mol% to 100 mol%, more preferably 90 mol% to 100 mol%, even more preferably 95 mol% to 100 mol%, and even more preferably 97 mol% to 100 mol%, when the total content of all constituent units in copolymer A is taken as 100 mol%, but it may also contain constituent units derived from other monomer components that do not fall under any of constituent units (a), (b), and (c), as long as it does not hinder the effects of the present invention.

[0062] Copolymer A of this embodiment can be manufactured by selecting appropriate conditions according to methods described in, for example, Japanese Patent Publication No. 2018-145349, International Publication No. 2015 / 122415, Japanese Patent Publication No. 2007-063409, Japanese Patent Publication No. Hei 2-173112, Japanese Patent Publication No. 2010-241932, Japanese Patent Publication No. Sho 60-168708, Japanese Patent Publication No. Sho 61-120816, Japanese Patent Publication No. Sho 61-115912, Japanese Patent Publication No. Sho 61-115916, Japanese Patent Publication No. Sho 61-271308, Japanese Patent Publication No. Sho 61-272216, Japanese Patent Publication No. Sho 62-252406, Japanese Patent Publication No. Sho 62-252407, etc.

[0063] (Refractive Index) The refractive index n of copolymer A of this embodiment, measured in accordance with ASTM D542. Ｄ [A] is preferably 1.450 to 1.600, more preferably 1.475 to 1.590, even more preferably 1.500 to 1.580, even more preferably 1.525 to 1.550, even more preferably 1.535 to 1.550, and even more preferably 1.538 to 1.548, from the viewpoint of further improving the light transmittance and moisture and heat resistance of the cyclic olefin copolymer composition of this embodiment.

[0064] (Weight-average molecular weight (Mw)) The weight-average molecular weight (Mw) of copolymer A in this embodiment, measured as a polystyrene equivalent by gel permeation chromatography (GPC), is preferably 10,000 g / mol or more, more preferably 50,000 g / mol or more, even more preferably 70,000 g / mol or more, even more preferably 90,000 g / mol or more, and even more preferably 100,000 g / mol or more, and there is no particular upper limit, but for example it is 5,000,000 g / mol or less, preferably 3,000,000 g / mol or less, more preferably 1,000,000 g / mol or less, and even more preferably 500,000 g / mol or more. It is less than or equal to ol, more preferably 200,000 g / mol or less, even more preferably 150,000 g / mol or less, and from the viewpoint of further improving heat resistance, it is preferably 10,000 g / mol or more and 5,000,000 g / mol or less, more preferably 10,000 g / mol or more and 3,000,000 g / mol or less, even more preferably 50,000 g / mol or more and 1,000,000 g / mol or less, even more preferably 70,000 g / mol or more and 500,000 g / mol or less, even more preferably 90,000 g / mol or more and 200,000 g / mol or less, and even more preferably 100,000 g / mol or more and 150,000 g / mol or less. The Mw of copolymer A can be adjusted by changing various polymerization conditions, such as the types and content ratios of monomers constituting the copolymer, and the type of polymerization catalyst.

[0065] (Intrinsic viscosity (η)) From the viewpoint of further improving heat resistance, the intrinsic viscosity (η) of copolymer A in this embodiment, as measured in decalin at 135°C, is preferably 0.01 dl / g or more and 3.0 dl / g or less, more preferably 0.1 dl / g or more and 2.0 dl / g or less, even more preferably 0.2 dl / g or more and 1.5 dl / g or less, even more preferably 0.3 dl / g or more and 1.0 dl / g or less, and even more preferably 0.4 dl / g or more and 0.7 dl / g or less. The intrinsic viscosity of copolymer A can be adjusted by changing the type and content ratio of monomers constituting the copolymer, as well as various conditions related to polymerization, such as the type of polymerization catalyst.

[0066] (Initial Internal Haze) Using a press-molded 3 mm thick square plate of copolymer A of this embodiment, the initial internal haze measured in benzyl alcohol in accordance with JIS K7136:2000 is preferably less than 5.0%, more preferably less than 3.0%, even more preferably less than 2.0%, even more preferably less than 1.5%, even more preferably less than 1.0%, even more preferably less than 0.8%, even more preferably less than 0.5%, and even more preferably less than 0.2%. The initial internal haze can be adjusted by changing the type and content ratio of monomers constituting copolymer A, as well as various polymerization conditions such as the type of polymerization catalyst.

[0067] [Cyclic olefin copolymer [B]] The cyclic olefin copolymer composition of the present invention (hereinafter also simply referred to as "copolymer composition") contains a cyclic olefin copolymer [B] (hereinafter also simply referred to as "copolymer B").

[0068] Copolymer B is not particularly limited as long as its glass transition temperature (Tg) is 100.0°C or lower. However, from the viewpoint of further improving the light transmittance and heat resistance of the cyclic olefin copolymer composition of this embodiment, the Tg is preferably -20.0°C or higher, more preferably -15.0°C or higher, even more preferably -10.0°C or higher, even more preferably -5.0°C or higher, even more preferably -2.5°C or higher, even more preferably 0.0°C or higher, even more preferably 2.5°C or higher, even more preferably 5.0°C or higher, and even more preferably 6.0°C or higher. From the viewpoint of further improving the light transmittance and heat and humidity resistance of the cyclic olefin copolymer composition in the application form, the temperature is preferably 95.0°C or lower, more preferably 90.0°C or lower, even more preferably 85.0°C or lower, even more preferably 80.0°C or lower, and even more preferably 75.0°C or lower. Furthermore, from the viewpoint of further improving the light transmittance and heat and humidity resistance of the cyclic olefin copolymer composition of this embodiment, the temperature is preferably -20.0°C to 95.0°C, more preferably -15.0°C to 95.0°C, even more preferably -10.0°C to 95.0°C, and further Preferably -5.0°C to 95.0°C, more preferably -2.5°C to 95.0°C, more preferably 0.0°C to 90.0°C, more preferably 2.5°C to 85.0°C, more preferably 5.0°C to 80.0°C, more preferably 6.0°C to 75.0°C, and from the viewpoint of making it easier to mix with copolymer A of this embodiment, more preferably 70.0°C or lower, more preferably 60.0°C or lower, more preferably 50.0°C or lower, more preferably 40.0°C or lower, more preferably 30.0°C or lower, and more preferably More preferably, the temperature is 20.0°C or lower, and from the viewpoint of improving the balance between light transmittance, heat and humidity resistance, and ease of mixing with copolymer A of this embodiment, it is preferably -20.0°C to 70.0°C, more preferably -15.0°C to 60.0°C, even more preferably -10.0°C to 50.0°C, even more preferably -5.0°C to 40.0°C, even more preferably -2.5°C to 30.0°C, even more preferably 0.0°C to 20.0°C, even more preferably 2.5°C to 20.0°C, and even more preferably 5.0°C to 20.0°C.By containing copolymer B, the cyclic olefin copolymer composition of this embodiment (hereinafter also simply referred to as the composition) can exhibit excellent light transmittance even when the environment changes from a high-temperature, high-humidity atmosphere to a normal-temperature, normal-humidity atmosphere. The Tg of copolymer B can be adjusted by changing various conditions related to polymerization, such as the type and content ratio of the monomers used as raw materials, and the type of polymerization catalyst.

[0069] From the viewpoint of making copolymer A and copolymer B of this embodiment easier to mix, when the glass transition temperature of copolymer A of this embodiment is Tg(A) and the glass transition temperature of copolymer B of this embodiment is Tg(B), it is preferable that |Tg(A)-Tg(B)| is 80.0°C or higher, and more preferably 100.0°C or higher. The upper limit of |Tg(A)-Tg(B)| is not particularly limited, but for example it can be 200.0°C or lower, 180.0°C or lower, or 160.0°C or lower. |Tg(A)-Tg(B)| can be 80.0°C or higher and 200.0°C or lower, 100.0°C or higher and 200.0°C or lower, or 100.0°C or higher and 160.0°C or lower.

[0070] Copolymer B is a cyclic olefin copolymer obtained by copolymerizing a cyclic olefin with a monomer other than a cyclic olefin. There are no particular restrictions on the cyclic olefin or the monomer other than a cyclic olefin, but from the viewpoint of further improving the light transmittance and heat resistance of the cyclic olefin copolymer composition of this embodiment, copolymer B preferably includes at least one constituent unit (a) derived from an olefin represented by the general formula (Ia) and at least one constituent unit selected from the group consisting of the constituent unit (b) and the constituent unit (c). The constituent unit (b) of this embodiment includes at least one constituent unit selected from the group consisting of a constituent unit derived from a cyclic olefin monomer (AA) represented by the general formula (IIa) and a constituent unit derived from a cyclic olefin monomer (AC) represented by the general formula (IVa). The constituent unit (c) of this embodiment includes at least one constituent unit selected from the group consisting of a constituent unit derived from a cyclic olefin monomer represented by the general formula (C-1), a constituent unit derived from a cyclic olefin monomer represented by the general formula (C-2), and a constituent unit derived from a cyclic olefin monomer represented by the general formula (C-3). Copolymer B more preferably includes a random copolymer comprising at least one olefin-derived constituent unit (a) represented by the general formula (Ia) above, and at least one constituent unit selected from the group consisting of the constituent unit (b) and the constituent unit (c), and more preferably includes one or more selected from the group consisting of [B-1] and [B-2] below, and more preferably includes [B-1] below. [B-1] A random copolymer comprising the constituent unit (a) and the constituent unit (c) of this embodiment. [B-2] A random copolymer comprising the constituent unit (a) and the constituent unit (b) of this embodiment. Copolymer B having the above composition tends to have a better balance between moisture and heat resistance and light transmittance. The constituent units (a), (b), and (c) above can be the same as the constituent units (a), (b), and (c) that can be used in copolymer A, respectively.

[0071] The content of constituent unit (a) in copolymer B is preferably more than 50.0 mol%, more preferably more than 60.0 mol%, even more preferably more than 65.0 mol%, even more preferably more than 70.0 mol%, and even more preferably more than 80.0 mol%, when the total content of all constituent units in copolymer B is set to 100 mol%, from the viewpoint of improving the light transmittance and heat resistance of the cyclic olefin copolymer composition of this embodiment, and preferably less than 100 mol%, more preferably 9 The content is less than 5.0 mol%, more preferably less than 93.0 mol%, even more preferably less than 91.0 mol%, and even more preferably less than 89.0 mol%, and from the viewpoint of improving the light transmittance and moisture and heat resistance of the cyclic olefin copolymer composition of this embodiment, it is preferably more than 50.0 mol% and less than 100 mol%, more preferably more than 60.0 mol% and less than 95.0 mol%, even more preferably more than 65.0 mol% and less than 93.0 mol%, even more preferably more than 70.0 mol% and less than 91.0 mol%, and even more preferably more than 80.0 mol% and less than 89.0 mol. The content of constituent unit (a) in copolymer B is within the above range, resulting in good moldability of copolymer B.

[0072] The content of constituent unit (c) in copolymer B is preferably 0.1 mol% or more, more preferably 1.0 mol% or more, even more preferably 5.0 mol% or more, and even more preferably 10.0 mol% or more, when the total content of all constituent units in copolymer B is 100 mol%, from the viewpoint of improving the light transmittance and heat resistance of the cyclic olefin copolymer composition of this embodiment, and preferably 50.0 The content is mol% or less, more preferably 40.0 mol% or less, even more preferably 35.0 mol% or less, and even more preferably 30.0 mol% or less. Furthermore, from the viewpoint of improving the light transmittance and moisture and heat resistance of the cyclic olefin copolymer composition of this embodiment, it is preferably 0.1 mol% to 50.0 mol%, more preferably 1.0 mol% to 40.0 mol%, even more preferably 5.0 mol% to 35.0 mol%, and even more preferably 10.0 mol% to 30.0 mol. By having the content of constituent unit (c) in copolymer B within the above range, the moldability of copolymer B can be improved and the mechanical strength of the molded article can be increased.

[0073] The total content of constituent units (a), (b), and (c) in copolymer B is preferably 80.0 mol% to 100 mol%, more preferably 90.0 mol% to 100 mol%, even more preferably 95.0 mol% to 100 mol%, and even more preferably 97.0 mol% to 100 mol%, when the total content of all constituent units in copolymer B is taken as 100 mol%, but it may also contain constituent units derived from other monomer components that do not fall under any of constituent units (a), (b), and (c), as long as it does not hinder the effects of the present invention.

[0074] Copolymer B of this embodiment can be manufactured by selecting appropriate conditions according to methods described in, for example, Japanese Patent Publication No. 2018-145349, International Publication No. 2015 / 122415, Japanese Patent Publication No. 2007-063409, Japanese Patent Publication No. Hei 2-173112, Japanese Patent Publication No. 2010-241932, etc.

[0075] (Refractive Index) The refractive index n of copolymer B of this embodiment, measured in accordance with ASTM D542. Ｄ [B] is preferably 1.450 to 1.600, more preferably 1.475 to 1.590, even more preferably 1.500 to 1.580, even more preferably 1.525 to 1.550, even more preferably 1.535 to 1.550, and even more preferably 1.538 to 1.548, from the viewpoint of further improving the light transmittance and moisture and heat resistance of the cyclic olefin copolymer composition of this embodiment.

[0076] (Weight-average molecular weight (Mw)) The weight-average molecular weight (Mw) of copolymer B in this embodiment, as measured as a polystyrene equivalent by gel permeation chromatography (GPC), is preferably 1,000 g / mol or more, more preferably 10,000 g / mol or more, more preferably 15,000 g / mol or more, even more preferably 20,000 g / mol or more, even more preferably 25,000 g / mol or more, even more preferably 28,000 g / mol or more, and from the viewpoint of improving light transmittance, it is preferably 1,000,000 g / mol or less, more preferably 500,000 g / mol or less, even more preferably 300,000 g / mol or less, even more preferably 250,000 g / mol or less, even more preferably 200,000 g / mol or less, and even more preferably The saturation is 150,000 g / mol or less, more preferably 100,000 g / mol or less, and from the viewpoint of improving the balance of performance between moisture resistance, heat resistance and light transmittance, it is preferably 1,000 g / mol or more and 1,000,000 g / mol or less, more preferably 1,000 g / mol or more and 500,000 g / mol or less, and even more preferably 10,000 g / mol or more and 300,000 g / mol or less, and further Preferably, the molecular weight is 10,000 g / mol or more and 250,000 g / mol or less; more preferably 15,000 g / mol or more and 200,000 g / mol or less; even more preferably 20,000 g / mol or more and 200,000 g / mol or less; even more preferably 25,000 g / mol or more and 150,000 g / mol or less; and even more preferably 28,000 g / mol or more and 100,000 g / mol or less. The molecular weight of copolymer B can be adjusted by changing the type and content ratio of monomers constituting the copolymer, as well as various polymerization conditions such as the type of polymerization catalyst.

[0077] (Intrinsic viscosity (η)) The intrinsic viscosity (η) of copolymer B in this embodiment, as measured in decalin at 135°C, is preferably 0.05 dl / g or more and 2.0 dl / g or less, more preferably 0.07 dl / g or more and 1.8 dl / g or less, even more preferably 0.1 dl / g or more and 1.5 dl / g or less, and even more preferably 0.2 dl / g or more and 1.3 dl / g or less, from the viewpoint of further improving heat resistance. The intrinsic viscosity of copolymer B can be adjusted by changing the type and content ratio of monomers constituting the copolymer, as well as various conditions related to polymerization, such as the type of polymerization catalyst.

[0078] [Other Components] The cyclic olefin copolymer composition of this embodiment may further contain other resins, elastomers, etc., such as styrene-based thermoplastic elastomers, to the extent that it does not impair the objectives of the present invention. Examples of styrene-based thermoplastic elastomers include block copolymers of styrenes and conjugated diene compounds. Specifically, examples include styrene-butadiene diblock copolymers, styrene-butadiene-styrene triblock copolymers, styrene-isoprene diblock copolymers, styrene-isoprene-styrene triblock copolymers, hydrogenated styrene-butadiene diblock copolymers, hydrogenated styrene-butadiene-styrene triblock copolymers, hydrogenated styrene-isoprene diblock copolymers, and hydrogenated styrene-isoprene-styrene triblock copolymers.

[0079] Furthermore, the cyclic olefin copolymer composition of this embodiment may contain various additives, such as dyes, pigments, stabilizers, plasticizers, antistatic agents, ultraviolet absorbers, antioxidants, lubricants, fillers, hydrophilic agents, etc., as needed, to the extent that the objectives of the present invention are not impaired.

[0080] [Cyclic Olefin Copolymer Composition] The cyclic olefin copolymer composition of this embodiment (hereinafter also simply referred to as "the composition") has a refractive index of copolymer B measured in accordance with ASTM D542, which is n Ｄ Let [B] be the refractive index of copolymer A, and n ＤWhen [A] is used, the absolute value of the refractive index difference expressed by the following formula is preferably greater than 0.014, and more preferably greater than 0.015, from the viewpoint of further improving the light transmittance and moisture and heat resistance of the cyclic olefin copolymer composition of this embodiment.

[0081]

[0082] In the polymer compositions described in Patent Documents 1 and 2, it is necessary to control the absolute values ​​of the refractive index difference between the resin (corresponding to the cyclic olefin copolymer [A] in this embodiment) and the rubber (corresponding to the cyclic olefin copolymer [B] in this embodiment) to 0.014 or less and 0.015 or less, respectively. In the field of resin compositions, it is generally not easy to control the absolute value of the refractive index difference between two types of resins to be blended, so there was room for improvement in terms of ease of manufacture for the polymer compositions described in Patent Documents 1 and 2. In this regard, by setting the absolute value of the refractive index difference to the above numerical range, it becomes possible to sufficiently secure the absolute value of the refractive index difference, thereby improving the ease of manufacture.

[0083] In the cyclic olefin polymer composition of this embodiment, when the total amount of the cyclic olefin copolymer [A] and the cyclic olefin copolymer [B] of this embodiment is 100 parts by mass, the content of the cyclic olefin copolymer [A] of this embodiment is preferably more than 85.0 parts by mass, more preferably more than 90.0 parts by mass, even more preferably more than 95.0 parts by mass, and even more preferably more than 98.0 parts by mass, from the viewpoint of further improving the light transmittance and heat resistance of the cyclic olefin copolymer composition of this embodiment. Furthermore, from the viewpoint of further improving the light transmittance and heat resistance of the cyclic olefin copolymer composition of this embodiment, it is preferably more than 85.0 parts by mass and 99.9 parts by mass or less, more preferably more than 90.0 parts by mass and 99.9 parts by mass or less, even more preferably more than 95.0 parts by mass and 99.9 parts by mass or less, and even more preferably more than 98.0 parts by mass and 99.9 parts by mass or less.

[0084] In the cyclic olefin polymer composition of this embodiment, when the total amount of the cyclic olefin copolymer [A] and the cyclic olefin copolymer [B] of this embodiment is 100 parts by mass, the content of the cyclic olefin copolymer [B] of this embodiment is preferably 0.2 parts by mass or more, more preferably 0.4 parts by mass or more, and even more preferably 0.5 parts by mass or more, from the viewpoint of further improving the light transmittance and heat resistance of the cyclic olefin copolymer composition of this embodiment, and preferably less than 3.0 parts by mass, more preferably less than 2.0 parts by mass, and even more preferably less than 1.5 parts by mass, and from the viewpoint of further improving the light transmittance and heat resistance of the cyclic olefin copolymer composition of this embodiment, it is preferably 0.2 parts by mass or more and less than 3.0 parts by mass, more preferably 0.4 parts by mass or more and less than 2.0 parts by mass, and even more preferably 0.5 parts by mass or more and less than 1.5 parts by mass.

[0085] In the cyclic olefin polymer composition of this embodiment, when the total amount of the cyclic olefin copolymer composition of this embodiment is 100 parts by mass, the total content of the cyclic olefin copolymer [A] and the cyclic olefin copolymer [B] of this embodiment is preferably 80 parts by mass or more and 100 parts by mass or less, more preferably 90 parts by mass or more and 100 parts by mass or less, and even more preferably 95 parts by mass or more and 100 parts by mass or less.

[0086] Using a press-formed 3 mm thick square plate of the composition of this embodiment, the initial internal haze measured in benzyl alcohol in accordance with JIS K7136 is preferably less than 10%, more preferably less than 5%. Furthermore, the change in internal haze before and after the moist heat test described later (Δinternal haze) is preferably less than 10%, more preferably less than 5%.

[0087] The composition of this embodiment can be obtained by melt-kneading the cyclic olefin copolymer [A] and the cyclic olefin copolymer [B] of this embodiment in a known kneading device such as an extruder or a Banbury mixer; by dissolving the cyclic olefin copolymer [A] and the cyclic olefin copolymer [B] of this embodiment in a common solvent and then evaporating the solution; or by adding the solutions of the cyclic olefin copolymer [A] and the cyclic olefin copolymer [B] of this embodiment to a poor solvent and precipitating them.

[0088] The composition of this embodiment can be used as a molded article by known molding methods. For example, extrusion molding, injection molding, compression molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, vacuum molding, foam molding, etc., are applicable. Among these, injection molding and extrusion molding are preferred from the viewpoint of moldability and productivity, and injection molding is more preferred.

[0089] Specific applications of the composition of this embodiment include lenses for various sensors, pickup lenses, projector lenses, prisms, fθ lenses, imaging lenses, light guide plates, and lenses for head-mounted displays.

[0090] The composition of this embodiment exhibits excellent transparency, low birefringence, heat resistance, heat aging resistance, chemical resistance, and low water absorption, and in particular can stably maintain excellent transparency even under environmental changes. Such a cyclic olefin resin composition according to the present invention can be suitably used in optical molded articles.

[0091] 2. Molded body, polarizing plate protective film, polarizing plate, and liquid crystal display device The molded body, polarizing plate protective film, polarizing plate, and liquid crystal display device of this embodiment will be described below.

[0092] The molded article of this embodiment contains the cyclic olefin copolymer composition of this embodiment.

[0093] The molded body of this embodiment is preferably a sensor lens, pickup lens, projector lens, prism, fθ lens, imaging lens, light guide plate, or lens for a head-mounted display.

[0094] The molded article of this embodiment is preferably a film or a sheet, and more preferably an optical film or an optical sheet.

[0095] Furthermore, the composition of this embodiment exhibits excellent transparency, low birefringence, heat resistance, heat aging resistance, chemical resistance, and low water absorption. In particular, it can stably maintain excellent transparency even under environmental changes. Therefore, the molded article of this embodiment containing the composition of this embodiment can be suitably used for the optical applications described above.

[0096] When the total mass of the molded article of this embodiment is considered to be 100% by mass, the total content of the cyclic olefin copolymer [A] and the cyclic olefin copolymer [B] 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. This improves transparency, low birefringence, heat resistance, heat aging resistance, chemical resistance, and low water absorption, and in particular, it is possible to stably maintain excellent transparency even under environmental changes.

[0097] The method for obtaining the molded article of this embodiment is not particularly limited and can be obtained by known methods. For example, it can be obtained by extrusion molding, injection molding, compression molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, vacuum molding, powder slush molding, calendering, or foam molding, but from the viewpoint of improving productivity, the molded article of this embodiment is preferably an injection molded article.

[0098] The polarizing plate protective film of this embodiment includes the cyclic olefin polymer composition of this embodiment.

[0099] The polarizing plate of this embodiment is provided with the polarizing plate protective film of this embodiment on at least one side of the polarizer.

[0100] The liquid crystal display device of this embodiment includes the polarizing plate of this embodiment.

[0101] 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.

[0102] The present invention will now be described in detail with reference to examples, but the present invention is not limited to these examples. In these examples, various physical properties were measured or evaluated by the following methods.

[0103] (1) Glass transition temperature (Tg) 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. First, the cyclic olefin copolymer was heated from room temperature to 200°C at a heating rate of 10°C / min and held for 5 minutes. Then, it was cooled to -40°C at a cooling rate of 10°C / min and held for 5 minutes. The glass transition temperature (Tg) of the cyclic olefin copolymer was then determined from the endothermic curve when heating to 200°C at a heating rate of 10°C / min.

[0104] (2) Weight-average molecular weight (Mw) The weight-average molecular weight (Mw) of the cyclic olefin copolymer was determined by gel permeation chromatography (GPC). Specifically, the weight-average molecular weight (Mw) of the cyclic olefin copolymer was calculated from the molecular weight distribution curve obtained using the following measuring apparatus under the following conditions. <Equipment and Conditions Used> Measurement device: Gel permeation chromatograph alliance GPC2000 (Waters Corporation) Analysis software: Chromatography data system Empower (trademark, Waters Corporation) 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: 1.0 mL / min Injection volume: 400 μL Sampling time interval: 1 second Sample concentration: 0.15% (w / v) Molecular weight calibrated monodisperse polystyrene (Tosoh Corporation) / molecular weight 495 to molecular weight 20.6 million

[0105] (3) Initial internal haze and Δ internal haze Initial internal haze was measured using press-formed 3 mm thick square plates of the cyclic olefin copolymer composition, evaluated in benzyl alcohol in accordance with JIS K7136. For the press-formed 3 mm thick square plates of the cyclic olefin copolymer composition, measurements were taken before and after the moist heat test described later. The internal haze value before the moist heat test (initial internal haze as described above) was subtracted from the internal haze value after the moist heat test to measure the Δ internal haze, which is the change in internal haze before and after the moist heat test. The measured initial internal haze and Δ internal haze were evaluated according to the following criteria. (Evaluation criteria) A: 0% or more, less than 5% B: 5% or more, less than 10% C: 10% or more

[0106] (4) Conditions for the moist heat test A 3 mm thick square plate press-formed from a cyclic olefin copolymer composition was left standing for 168 hours in an atmosphere of 65°C and 90% relative humidity, and then removed and left standing for 48 hours in an atmosphere of 23°C and 50% relative humidity.

[0107] (5) Method for measuring the content of each constituent unit constituting the cyclic olefin copolymer The content of each constituent unit in copolymers [A] and [B] was measured using a JEOL Ltd. "ECA500" nuclear magnetic resonance spectrometer under the following conditions: Solvent: Deuterated tetrachloroethane Sample concentration: 50-100 g / l-solvent Pulse repetition time: 5.5 seconds Number of integrations: 6000-16000 Measurement temperature: 120°C Measurement was performed under the above conditions. １３ The compositions of copolymers [A] and [B] were quantified by C-NMR spectroscopy.

[0108] (6) Intrinsic viscosity [η] Using a mobile viscometer (Rigousha, type VNR053U), 0.25 to 0.30 g of the cyclic olefin copolymer was dissolved in 25 ml of decalin to prepare the 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.

[0109] (7) refractive index n Ｄ [A] and n Ｄ [B] Measurement Method Using a multi-wavelength Abbe refractometer (ATAGO DR-M4 / 1550), the refractive index (nD) at a wavelength of 589 nm was measured for press-formed 3 mm thick square plates of the cyclic olefin copolymer [A] obtained in the polymerization example, in accordance with ASTM D542. Ｄ [A]) was used. The refractive index (nD) was measured in the same manner as above, except that a 3 mm thick press-formed rectangular plate of cyclic olefin copolymer [A] was replaced with a 3 mm thick press-formed rectangular plate of cyclic olefin copolymer [B]. This was then expressed as refractive index (n Ｄ [B])

[0110] [Polymerization Example 1] Cyclic Olefin Copolymer [B-1] The copolymerization reaction of ethylene with benzonorbornadiene (BNBD), represented by the following formula, was carried out as follows.

[0111]

[0112] <Preparation of Catalyst> The following complex compound (A1) was synthesized according to paragraph 0140 of Japanese Patent Publication No. 2010-241932.

[0113]

[0114] A catalyst solution was prepared by diluting methylaluminoxane and the above complex compound (A1) with toluene.

[0115] <Polymerization> In a stirred polymerizer, copolymerization of ethylene and BNBD was carried out using the catalyst solution prepared by the above method to obtain a copolymer solution. Here, ethylene was supplied into the polymerizer together with hydrogen gas.

[0116] <Decalcification and Crystallization> The copolymer solution was added to an acetone / methanol mixed solvent containing hydrochloric acid, and catalyst residue present in the copolymer solution was removed (demalcification) and crystallized.

[0117] <Solvent Removal> The crystallized copolymer solution was filtered and heated to 130°C to remove the solvent and unreacted monomers, thereby obtaining ethylene / BNBD copolymer (B-1). The obtained ethylene / BNBD copolymer (B-1) was unhydrogenated. The basic properties of the obtained ethylene / BNBD copolymer (B-1) are shown in Table 1.

[0118] [Polymerization Examples 2-4] Copolymers (B-2), (B-3), and (B-4) were obtained in the same manner except that the amount of cyclic monomer and the amount of hydrogen were changed. The obtained ethylene / BNBD copolymers (B-2), (B-3), and (B-4) were not hydrogenated. The basic properties are shown in Table 1. In Table 1, TD is tetracyclo[4.4.0.1 ２，５ 1. ７，１０ ]-3- means Dodecen.

[0119]

[0120] [Polymerization Example 5] Cyclic Olefin Copolymer [A] Ethylene and tetracyclo[4.4.0.1] represented by the following formula ２，５ 1. ７，１０ The copolymerization reaction with ]-3-dodecene (TD) was carried out as follows.

[0121]

[0122] <Preparation of Catalyst> Methylaluminoxane and the above complex compound (A1) were diluted with toluene to prepare a catalyst solution.

[0123] <Polymerization> In a stirred polymerizer, the catalyst solution prepared by the above method was used as a catalyst to carry out a copolymerization reaction between ethylene and tetracyclo[4.4.0.12,5.17,10]-3-dodecene to obtain a copolymer solution. Here, ethylene was supplied into the polymerizer together with hydrogen gas.

[0124] <Decalcification> Water and an aqueous sodium hydroxide solution were added to the obtained copolymer solution to stop the polymerization reaction and remove the catalyst residue present in the copolymer solution (decalcification). Pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] was added to the decalcified solution as a stabilizer and mixed in a stirring tank for 1 hour.

[0125] <Solvent Removal> The solution, mixed with a stabilizer, was heated to 180°C to remove the solvent and unreacted monomers, thereby obtaining a molten cyclic olefin copolymer (A-1) (a random copolymer of ethylene and tetracyclo[4.4.0.12,5.17,10]-3-dodecene). The obtained cyclic olefin polymer (A-1) was not hydrogenated. The basic properties of the obtained cyclic olefin polymer (A-1) are shown in Table 2.

[0126] [Polymerization Example 6] Copolymer (A-2) was obtained in the same manner except that the amount of cyclic monomer and the amount of hydrogen were changed. The obtained cyclic olefin polymer (A-2) was not hydrogenated. The basic properties are shown in Table 2. In Table 2, BNBD means benzonorbornadiene.

[0127]

[0128] [Example 1] 99.0 parts by mass of cyclic olefin copolymer (A-1) and 1.0 part by mass of cyclic olefin copolymer (B-1) were melt-kneaded at 260°C using a laboplast mill, and the resulting mixture was molded using a hot press. For a 3 mm thick square plate molded at a molding temperature of 260°C, the initial internal haze, Δ internal haze, and absolute value of the refractive index difference (|n) were measured.Ｄ [B -n Ｄ [A]|) was evaluated. The results are shown in Table 3.

[0129] [Examples 2-6, Comparative Examples 2-6] Molded articles were prepared in the same manner as in Example 1, except that the types of copolymers [A] and [B] used and the amounts of copolymers [A] and [B] were changed as shown in Table 3, and the same evaluation as in Example 1 was performed. The results are shown in Table 3.

[0130] [Comparative Example 1] A molded article was prepared in the same manner as in Example 1, except that a cyclic olefin polymer (A-1) was used alone, and the same evaluation as in Example 1 was performed. The results are shown in Table 3.

[0131]

[0132] As described above, the molded articles obtained in each example exhibited excellent transparency and excellent resistance to humid and heat. Comparative Example 1 showed transparency but insufficient resistance to humid and heat. Comparative Examples 2 to 6 did not undergo humid and heat testing because they had high initial internal haze and poor transparency.

[0133] This application claims priority based on Japanese Patent Application No. 2024-208120, filed on 29 November 2024, and incorporates all of its disclosures herein.

Claims

1. A cyclic olefin copolymer composition comprising a cyclic olefin copolymer [A] having a glass transition temperature (Tg) greater than 100.0°C and a cyclic olefin copolymer [B] having a glass transition temperature (Tg) of 100.0°C or less, wherein when the total amount of the cyclic olefin copolymer [A] and the cyclic olefin copolymer [B] is 100 parts by mass, the content of the cyclic olefin copolymer [A] is greater than 95.0 parts by mass and less than 99.9 parts by mass, and the content of the cyclic olefin copolymer [B] is 0.1 parts by mass or more and less than 5.0 parts by mass.

2. The refractive index of the cyclic olefin copolymer [B] measured in accordance with ASTM D542 is n Ｄ Let [B] be the refractive index of the cyclic olefin copolymer [A] be n Ｄ The cyclic olefin copolymer composition according to claim 1, wherein, when [A] is set, the absolute value of the refractive index difference expressed by the following formula exceeds 0.

014.

3. The cyclic olefin copolymer composition according to claim 1 or 2, wherein the glass transition temperature (Tg) of the cyclic olefin copolymer [B] is -20.0°C or higher and 90.0°C or lower.

4. The cyclic olefin copolymer [A] includes at least one constitutional unit (a) derived from an olefin represented by the following general formula (Ia), and at least one constitutional unit selected from the group consisting of constitutional unit (b) and constitutional unit (c). The constitutional unit (b) includes at least one constitutional unit selected from the group consisting of a constitutional unit derived from a cyclic olefin monomer (AA) represented by the following general formula (IIa) and a constitutional unit derived from a cyclic olefin monomer (AC) represented by the following general formula (IVa). The constitutional unit (c) includes at least one constitutional unit selected from the group consisting of a constitutional unit derived from a cyclic olefin monomer represented by the following general formula (C-1), a constitutional unit derived from a cyclic olefin monomer represented by the following general formula (C-2), and a constitutional unit derived from a cyclic olefin monomer represented by the following general formula (C-3). The cyclic olefin copolymer composition according to claim 1 or 2. In the general formula (Ia), R ３００ represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms. In the general formula (IIa), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, and R ６１ to R ７８ and R ａ１ and R ｂ１ may be the same as or different from each other, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms. R ７５ to R ７８ may be bonded to each other to form a monocyclic or polycyclic ring. In the general formula (IVa), R １００ , R １０１ may be the same as or different from each other and represent a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and f satisfies 1 ≤ f ≤ 18. In the general formula (C-1), n and q are each independently 0, 1, or 2, and R １ to 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 bonding, and 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 , R １６ 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. In the above general formula (C-2), n and m are independently 0, 1, or 2, q is 1, 2, or 3, and 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 which may be substituted with a halogen atom other than a fluorine atom, and 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 be an aromatic ring. In the above general formula (C-3), q is 1, 2, or 3, and R ３２ ~R ３９ 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 when q = 1, R ３６ and R ３７ , R ３７ and R ３８ , R ３８ and R ３９ They may be bonded to each other to form a monocycle or polycycle, 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 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.

5. The cyclic olefin copolymer [B] includes at least one structural unit (a) derived from an olefin represented by the following general formula (Ia), and at least one structural unit selected from the group consisting of structural unit (b) and structural unit (c). The structural unit (b) includes at least one structural unit selected from the group consisting of a structural unit derived from a cyclic olefin monomer (AA) represented by the following general formula (IIa) and a structural unit derived from a cyclic olefin monomer (AC) represented by the following general formula (IVa). The structural unit (c) includes at least one structural unit selected from the group consisting of a structural unit derived from a cyclic olefin monomer represented by the following general formula (C-1), a structural unit derived from a cyclic olefin monomer represented by the following general formula (C-2), and a structural unit derived from a cyclic olefin monomer represented by the following general formula (C-3). The cyclic olefin copolymer composition according to claim 1 or 2. In the general formula (Ia), R ３００ represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms. In the general formula (IIa), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, R ６１ ~R ７８ as well as R ａ１ and R ｂ１ may be the same as or different from each other, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms. R ７５ ~R ７８ may be bonded to each other to form a monocyclic or polycyclic ring. In the general formula (IVa), R １００ , R １０１ may be the same as or different from each other and represent a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and f satisfies 1≤f≤18. In the general formula (C-1), n and q are each independently 0, 1 or 2, and R １ ~R １７ is each independently a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom excluding a hydrogen atom and a fluorine atom, or a halogen atom excluding a fluorine atom, and R １０ to R １７ one of which is a bond, and when q = 0, R １０ and R １１ , R １１ and R １２ , R １２ and R １３ , R １３ and R １４ , R １４ and R １５ , R １５ and R １０ may be bonded to each other to form a monocyclic or polycyclic ring, 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 , R １６ and R １６ , R １６ and R １０ may be bonded to each other to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring may have a double bond, and the monocyclic or polycyclic ring may be an aromatic ring. In the general formula (C-2), n and m are each independently 0, 1 or 2, q is 1, 2 or 3, and R １８ to R ３１ are each independently a hydrogen atom, a halogen atom excluding a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom excluding a fluorine atom, and 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 be an aromatic ring. In the above general formula (C-3), q is 1, 2, or 3, and R ３２ ~R ３９ 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 when q = 1, R ３６ and R ３７ , R ３７ and R ３８ , R ３８ and R ３９ They may be bonded to each other to form a monocycle or polycycle, 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 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.

6. The cyclic olefin copolymer composition according to claim 5, wherein the cyclic olefin copolymer [B] comprises one or more selected from the group consisting of [B-1] and [B-2] below: [B-1] A random copolymer comprising the constituent unit (a) and the constituent unit (c). [B-2] A random copolymer comprising the constituent unit (a) and the constituent unit (b).

7. The cyclic olefin copolymer composition according to claim 5, wherein the total content of constituent unit (a), constituent unit (b), and constituent unit (c) in the cyclic olefin copolymer [B] is 80.0 mol% or more and 100 mol% or less, when the total content of all constituent units in the cyclic olefin copolymer [B] is set to 100 mol%.

8. The cyclic olefin copolymer composition according to claim 5, wherein the content of the constituent unit (a) in the cyclic olefin copolymer [B] is greater than 50.0 mol% when the total content of all constituent units in the cyclic olefin copolymer [B] is 100 mol%.

9. The cyclic olefin copolymer composition according to claim 1 or 2, wherein the weight-average molecular weight (Mw) of the cyclic olefin copolymer [B] is 10,000 g / mol or more and 300,000 g / mol or less.

10. The cyclic olefin copolymer composition according to claim 4, wherein the cyclic olefin copolymer [A] is a random copolymer comprising the constituent unit (a) and the constituent unit (b).

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

12. The molded body according to claim 11, wherein the molded body is a sensor lens, a pickup lens, a projector lens, a prism, an fθ lens, an imaging lens, a light guide plate, or a lens for a head-mounted display.

13. The molded article according to claim 11, wherein the molded article is a film or a sheet.

14. The molded body according to claim 13, wherein the molded body is an optical film or an optical sheet.

15. The molded article according to claim 11, which is an injection-molded product.

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