Cyclic olefin-based (CO)polymer for high intensity radiation environment, resin composition and molding

Abstract

To provide a cyclic olefin-based (co)polymer which improves impact resistance after irradiation with high intensity radiation, and a resin composition and a molding which improve impact resistance after irradiation with high intensity radiation.SOLUTION: A cyclic olefin-based (co)polymer for high intensity radiation environment contains one or more polymers selected from the group consisting of the following [I], [II], [III], [IV] and [V]. [I] Random copolymer including a constitutional unit (A) derived from α-olefin having 2 to 20 carbon atoms, and a constitutional unit (B) derived from cyclic olefin having no aromatic ring. [II] Copolymer including the constitutional unit (A), the constitutional unit (B), and a constitutional unit (C) derived from cyclic olefin having an aromatic ring. [III] One or more ring-opened polymers or ring-opened copolymers selected from the group consisting of cyclic olefin not having the aromatic ring and cyclic olefin having the aromatic ring. [IV] Hydride of the ring-opened polymer or ring-opened copolymer [III]. [V] Graft modified product of the polymer of [I], [II], [III] or [IV].SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a cyclic olefin (co)polymer, a resin composition and a molded article which are usable in a high-intensity radiation environment. [Background technology]

[0002] Cyclic olefin (co)polymers have high performance, including transparency, chemical resistance, heat resistance, and dimensional stability, and are therefore used in a wide range of applications, including medical containers, optical lenses such as fθ lenses and pickup lenses, imaging lenses used in smartphones and digital cameras, and food containers. Examples of studies on the use of cyclic olefin (co)polymers as materials for forming molded articles such as medical containers include those described in Patent Document 1. Furthermore, examples of techniques relating to cyclic olefin polymers used in food utensils and food packaging materials include those described in Patent Documents 2 and 3.

[0003] Patent Document 1 describes, for the purpose of providing a cyclic olefin resin composition having improved slip properties, excellent transparency, surface gloss, and further excellent hygiene, and a molded article thereof, the following: at least one cyclic olefin resin selected from the group consisting of an α-olefin-cyclic olefin random copolymer (a-1) derived from a cyclic olefin of a specific structure, a ring-opening (co)polymer of a cyclic olefin or a hydrogenated product thereof (a-2), and a graft modified product of (a-1) or (a-2) (a-3); or a resin composition consisting of such a cyclic olefin resin and a polyolefin, and at least one cyclic olefin resin selected from the group consisting of (a-1) to (a-3) and having a different chemical structure from the cyclic olefin resin; and a molded article thereof using the cyclic olefin resin composition that is suitable for medical containers, food containers, packaging, and the like.

[0004] Patent Document 2 describes a resin composition that contains specific amounts of a cyclic olefin polymer having a specific structure and a specific α-olefin polymer, and a packaging material and a food packaging material obtained by molding the resin composition, for the purposes of providing a resin composition that is excellent in heat resistance, moisture resistance, and light-shielding properties, i.e., excellent in light shielding properties, and is easy to tear, and is suitable as a packaging material, particularly as a packaging material for food, and to provide a packaging material and a food packaging material obtained by molding the resin composition.

[0005] Patent Document 3 describes a cyclic olefin copolymer composition containing a cyclic olefin copolymer (P) and a stabilizer (S) for the purpose of providing a molded article that is less susceptible to discoloration due to irradiation with electron beams or gamma rays and has excellent heat resistance, in which the cyclic olefin copolymer (P) has a structural unit (A) derived from an α-olefin having 2 to 20 carbon atoms, a structural unit (B) derived from a cyclic olefin having no aromatic ring, and a structural unit (C) derived from a cyclic olefin having an aromatic ring, and the stabilizer (S) has a phenolic hydroxyl group and phosphorus. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] JP 2001-26693 A [Patent Document 2] JP 2007-284504 A [Patent Document 3] Patent Publication No. 2021-054905 Summary of the Invention [Problem to be solved by the invention]

[0007] The present invention provides a cyclic olefin (co)polymer having improved impact resistance after exposure to high-intensity radiation, as well as a resin composition and a molded article having improved impact resistance after exposure to high-intensity radiation. [Means for solving the problem]

[0008] The present inventors have conducted extensive research to solve the above problems, and as a result, have found for the first time that a cyclic olefin (co)polymer having a specific structure is irradiated with high-intensity radiation exceeding 100 kGy, and has maintained excellent impact resistance even after being irradiated with high-intensity radiation, thereby completing the present invention.

[0009] According to the present invention, there are provided the following cyclic olefin (co)polymer, resin composition and molded article.

[0010] [1] A cyclic olefin (co)polymer for use in a high-intensity radiation environment, comprising one or more polymers selected from the group consisting of the following [I], [II], [III], [IV] and [V]: [I] A random copolymer comprising a structural unit (A) derived from an α-olefin having 2 to 20 carbon atoms and a structural unit (B) derived from a cyclic olefin having no aromatic ring. [II] A copolymer comprising the structural unit (A), the structural unit (B), and a structural unit (C) derived from a cyclic olefin having an aromatic ring. [III] One or more ring-opening polymers or ring-opening copolymers selected from the group consisting of the cyclic olefins having no aromatic ring and the cyclic olefins having an aromatic ring. [IV] A hydrogenated product of the ring-opened polymer or ring-opened copolymer [III] [V] A graft-modified product of the polymer [I], [II], [III] or [IV]. [2] The cyclic olefin (co)polymer for use under high intensity radiation environments according to the above [1], wherein the cyclic olefin having no aromatic ring comprises a compound represented by the following formula (B-1): [ka] (In the above formula (B-1), n ​​is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and R 1 ~R 18And R a and R b are each independently a hydrogen atom, a halogen atom, or a hydrocarbon group which may be substituted with a halogen atom; R 15 ~R 18 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 R 15 and R 16 With or R 17 and R 18 and may form an alkylidene group, provided that the aromatic ring is not included.) [3] The cyclic olefin having no aromatic ring is bicyclo[2.2.1]-2-heptene, tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene and hexacyclo[6,6,1,1 3,6 ,1 10,13 ,0 2,7 ,0 9,14 ]heptadecene-4, 2-hexene ... [4] The cyclic olefin (co)polymer for use under high intensity radiation environment according to any one of [1] to [3] above, wherein the cyclic olefin having an aromatic ring comprises one or more compounds selected from the group consisting of a compound represented by the following formula (C-1), a compound represented by the following formula (C-2), and a compound represented by the following formula (C-3): [ka] (In the above formula (C-1), n ​​and q each independently represent 0, 1, or 2; R 1 ~R 17 each independently represents 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; R 10 ~R 17 One of them is a bond, and when q=0, R 10 and R 11 , R 11and 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, the monocyclic or polycyclic ring may have a double bond, or the monocyclic or polycyclic ring may be an aromatic ring. [ka] (In the above formula (C-2), n and m are each independently 0, 1 or 2, q is 1, 2 or 3, and R 18 ~R 31 each independently represents 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 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 , R30 and R 31 , R 31 and R 31 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. [ka] (In the above formula (C-3), q is 1, 2 or 3, and R 32 ~R 39 each independently represents 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 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. [5] The cyclic olefin (co)polymer for use in a high-intensity radiation environment according to any one of the above [1] to [4], which contains at least one polymer selected from the above [I] and [II]. [6] The cyclic olefin (co)polymer for use in a high-intensity radiation environment according to any one of the above [1] to [4], which contains the polymer [I]. [7] The cyclic olefin (co)polymer for use under high intensity radiation environments according to [6], wherein the content of the structural unit (A) in the polymer [I] is more than 50 mol % and not more than 80 mol %, when the total content of the structural unit (A) and the structural unit (B) in the polymer [I] is 100 mol %. [8] The cyclic olefin (co)polymer for use in a high-intensity radiation environment according to any one of the above [1] to [4], which contains the polymer [II]. [9] The cyclic olefin (co)polymer for use in a high-intensity radiation environment according to [8], wherein the content of the structural unit (A) in the polymer [II] is more than 50 mol % and is not more than 80 mol %, when the total content of the structural unit (A), the structural unit (B) and the structural unit (C) in the polymer [II] is taken as 100 mol %.

[10] The cyclic olefin (co)polymer for use in a high-intensity radiation environment according to [8] or [9], wherein the content of the structural unit (B) in the polymer [II] is 0.1 mol % or more and less than 50 mol %, when the total content of the structural unit (A), the structural unit (B) and the structural unit (C) in the polymer [II] is 100 mol %.

[11] The cyclic olefin (co)polymer for use under high intensity radiation environments according to any one of [8] to

[10] , wherein the content of the structural unit (C) in the polymer [II] is 5 mol % or more and 95 mol % or less, when the total content of the structural unit (B) and the structural unit (C) in the polymer [II] is taken as 100 mol %.

[12] The cyclic olefin (co)polymer for use in a high-intensity radiation environment according to any one of [1] to

[11] above, which has a glass transition temperature (Tg) measured by a differential scanning calorimeter (DSC) of 120°C or higher and 180°C or lower.

[13] The cyclic olefin (co)polymer for use in a high intensity radiation environment according to any one of [1] to

[12] above, having an intrinsic viscosity [η] measured in decalin at 135° C. of 0.05 dl / g or more and 5.0 dl / g or less.

[14] The cyclic olefin (co)polymer for use in a high intensity radiation environment according to any one of [1] to

[13] above, wherein the cyclic olefin having an aromatic ring comprises one or more selected from the group consisting of benzonorbornadiene, indenenorbornene, and methylphenylnorbornene.

[15] A resin composition comprising the cyclic olefin (co)polymer for use in a high-intensity radiation environment according to any one of [1] to

[14] above.

[16] A molded article comprising the cyclic olefin (co)polymer for use in a high-intensity radiation environment according to any one of [1] to

[14] above.

[17] The molded article according to

[16] , which is a window material, a face shield for protective clothing, a see-through surface, a sight glass, an optical lens, a medical container, a circuit board, or a prepreg, which can be used in a high-intensity radiation environment. Effect of the Invention

[0011] According to the present invention, it is possible to provide a cyclic olefin (co)polymer having improved impact resistance after exposure to high-intensity radiation, as well as a resin composition and a molded article having improved impact resistance after exposure to high-intensity radiation. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] In the present disclosure, the expressions "XX or more and YY or less" and "XX to YY" representing a numerical range mean a numerical range including the endpoints, that is, the lower limit and the upper limit, unless otherwise specified. Furthermore, when numerical ranges are described in stages, the upper and lower limits of each numerical range can be combined in any manner. Furthermore, each monomer constituting the cyclic olefin (co)polymer of the present invention may be a monomer obtained from a fossil raw material, or a monomer obtained from an animal or vegetable raw material.

[0013] (High intensity radiation environment) The cyclic olefin (co)polymer according to this embodiment is used in applications under high-intensity radiation environments. In this specification, "high-intensity" means, for example, that the radiation dose exceeds 100 kGy, particularly 300 kGy or more. The radiation is not particularly limited, and examples thereof include electromagnetic radiation such as gamma rays and X-rays, particle radiation such as alpha rays, beta rays, electron beams, proton beams, neutron beams, and heavy particle beams, and cosmic rays such as solar cosmic rays and galactic cosmic rays. Examples of high-intensity radiation environments in which the radiation exposure exceeds 100 kGy (particularly 300 kGy or more) include space environments, nuclear facilities such as nuclear power plants and nuclear submarines, and high-altitude environments at altitudes of 10,000 meters or more. Applications of the cyclic olefin (co)polymer and molded article of the present invention include window materials, face shields for protective clothing, see-through surfaces, sight glasses, optical lenses, medical containers, circuit boards (particularly high-frequency circuit boards), prepregs, and the like that can be used in these high-intensity radiation environments.

[0014] For example, in applications such as medical containers, such as syringes and drug storage containers, and food containers, they may be sterilized by radiation, such as electron beams or gamma rays, before use. It is generally known that irradiating a resin with radiation, such as gamma rays or electron beams, accelerates deterioration of the resin (particularly a decrease in strength), but an irradiation dose of about 50 kGy, which is used for sterilization in applications such as medical containers and food containers, does not cause a decrease in strength that is problematic in practice, and so resins are widely used as materials that can be sterilized with gamma rays or electron beams. However, it has been found that some resins lose strength significantly when exposed to high-intensity radiation exceeding 100 kGy. However, there have been no studies or reports on irradiating resins with high-intensity radiation exceeding 100 kGy. The present inventors irradiated a cyclic olefin (co)polymer as a resin with high-intensity radiation exceeding 100 kGy and found for the first time that the resin can retain excellent strength even after exposure to high-intensity radiation.

[0015] (Cyclic olefin (co)polymers for use in high intensity radiation environments) The cyclic olefin (co)polymer (P) for use in a high-intensity radiation environment according to this embodiment will be described. The cyclic olefin (co)polymer (P) for use in a high-intensity radiation environment according to this embodiment contains one or more polymers selected from the group consisting of the following [I], [II], [III], [IV] and [V]. [I] A random copolymer comprising a structural unit (A) derived from an α-olefin having 2 to 20 carbon atoms and a structural unit (B) derived from a cyclic olefin having no aromatic ring. [II] A copolymer comprising the structural unit (A), the structural unit (B), and a structural unit (C) derived from a cyclic olefin having an aromatic ring. [III] One or more ring-opening polymers or ring-opening copolymers selected from the group consisting of the cyclic olefins having no aromatic ring and the cyclic olefins having an aromatic ring. [IV] A hydrogenated product of the ring-opened polymer or ring-opened copolymer [III] [V] A graft-modified product of the polymer [I], [II], [III] or [IV]. The cyclic olefin (co)polymer (P) for use in a high-intensity radiation environment according to this embodiment preferably contains one or more polymers selected from the group consisting of [I], [II] and [III], more preferably contains one or more polymers selected from the group consisting of [I] and [II], and further preferably contains the polymer [II], from the viewpoint of further improving the impact resistance after irradiation with high-intensity radiation while suppressing the internal haze of the resulting resin composition and molded article.

[0016] ([I] A random copolymer containing a structural unit (A) derived from an α-olefin having 2 to 20 carbon atoms and a structural unit (B) derived from a cyclic olefin having no aromatic ring) The polymer [I] according to this embodiment contains a structural unit (A) derived from an α-olefin having 2 to 20 carbon atoms, and a structural unit (B) derived from a cyclic olefin having no aromatic ring. The polymer [I] according to this embodiment contains a structural unit (A) derived from an α-olefin having 2 to 20 carbon atoms and a structural unit (B) derived from a cyclic olefin having no aromatic ring, thereby making it possible to improve the impact resistance after exposure to high-intensity radiation while suppressing internal haze in the resulting resin composition and molded article.

[0017] (Structural unit (A) derived from an α-olefin having 2 to 20 carbon atoms) The structural unit (A) according to this embodiment is a structural unit derived from an α-olefin having 2 to 20 carbon atoms. Here, the α-olefin having 2 to 20 carbon atoms may be linear or branched, and examples thereof include linear α-olefins having 2 to 20 carbon atoms, such as ethylene, 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. Among these, from the viewpoint of suppressing internal haze of the resulting resin composition and molded article while improving impact resistance after irradiation with high-intensity radiation, linear α-olefins having 2 to 4 carbon atoms are preferred, and ethylene is more preferred. Such linear or branched α-olefins may be used alone or in combination of two or more.

[0018] When the total content of the structural unit (A) and the structural unit (B) in the polymer [I] of this embodiment is taken as 100 mol%, the content of the structural unit (A) in the polymer [I] of this embodiment is preferably more than 50 mol%, more preferably 54 mol% or more, even more preferably 57 mol% or more, even more preferably 60 mol% or more, even more preferably 63 mol% or more, and preferably 80 mol% or less, more preferably 76 mol% or less, even more preferably 73 mol% or less, even more preferably 70 mol% or less, and even more preferably 68 mol% or less. By making the content of the structural unit (A) equal to or greater than the lower limit, the heat resistance and dimensional stability of the resulting resin composition and molded article can be improved, and the impact resistance after irradiation with high-intensity radiation can be improved while suppressing internal haze. In addition, by making the content of the structural unit (A) equal to or less than the upper limit, the transparency and the like of the resulting resin composition and molded article can be improved. In this embodiment, the content of the structural unit (A) is, for example, 1 H-NMR or 13 It can be measured by C-NMR.

[0019] The total content of the structural unit (A) and the structural unit (B) in the polymer [I] according to this embodiment is preferably 80 mol% or more, more preferably 90 mol% or more, even more preferably 95 mol% or more, even more preferably 98 mol% or more, even more preferably 99 mol% or more, and is, for example, 100 mol% or less.

[0020] (Structural Unit (B) Derived from Cyclic Olefin Having No Aromatic Ring) The structural unit (B) according to this embodiment is a structural unit derived from a cyclic olefin having no aromatic ring. As the structural unit (B) according to this embodiment, from the viewpoint of suppressing the internal haze of the obtained resin composition and molded article and further improving the impact resistance after irradiation with high-intensity radiation, it is preferable to include a structural unit derived from a compound represented by the following formula (B-1). [ka] (In the above formula (B-1), n ​​is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and R 1 ~R 18 And R a and R b are each independently a hydrogen atom, a halogen atom, or a hydrocarbon group which may be substituted with a halogen atom; R 15 ~R 18 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 R 15 and R 16 With or R 17 and R 18 and may form an alkylidene group, provided that the aromatic ring is not included.) Among these, as the structural unit (B) according to the present embodiment, from the viewpoint of suppressing the internal haze of the obtained resin composition and molded article while further improving the impact resistance after irradiation with high-intensity radiation, a structural unit derived from bicyclo[2.2.1]-2-heptene, a structural unit derived from tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene-derived building blocks and hexacyclo[6,6,1,1 3,6 ,1 10,13 ,0 2,7 ,0 9,14 It is preferable that the copolymer contains one or more structural units selected from structural units derived from bicyclo[2.2.1]-2-heptene and tetracyclo[4.4.0.1 2,5 .1 7,10 More preferably, the copolymer contains one or more structural units selected from structural units derived from tetracyclo[4.4.0.1 2,5 .1 7,10 It is even more preferable that the copolymer contains a structural unit derived from ]-3-dodecene. That is, as the cyclic olefin having no aromatic ring, from the viewpoint of suppressing the internal haze of the resulting resin composition and molded article while further improving the impact resistance after irradiation with high-intensity radiation, bicyclo[2.2.1]-2-heptene, tetracyclo[4.4.0.1 2,5 .1 7,10]-3-dodecene and hexacyclo[6,6,1,1 3,6 ,1 10,13 ,0 2,7 ,0 9,14 ]heptadecene-4, etc., and preferably contains one or more selected from bicyclo[2.2.1]-2-heptene and tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene, and more preferably tetracyclo[4.4.0.1 2,5 .1 7,10 It is even more preferred that the aryl group contains ]-3-dodecene.

[0021] ([II] A copolymer containing a structural unit (A) derived from an α-olefin having 2 to 20 carbon atoms, a structural unit (B) derived from a cyclic olefin having no aromatic ring, and a structural unit (C) derived from a cyclic olefin having an aromatic ring) The polymer [II] according to this embodiment contains a structural unit (A) derived from an α-olefin having 2 to 20 carbon atoms, a structural unit (B) derived from a cyclic olefin having no aromatic ring, and a structural unit (C) derived from a cyclic olefin having an aromatic ring. The polymer [II] according to this embodiment contains a structural unit (A) derived from an α-olefin having 2 to 20 carbon atoms, a structural unit (B) derived from a cyclic olefin having no aromatic ring, and a structural unit (C) derived from a cyclic olefin having an aromatic ring, thereby making it possible to improve the impact resistance after exposure to high-intensity radiation while suppressing internal haze in the resulting resin composition and molded article. The preferred aspects of the structural unit (A) and the structural unit (B) in the polymer [II] according to this embodiment are the same as those in the polymer [I] according to this embodiment, and therefore will not be described here.

[0022] (Structural Unit (C) Derived from Cyclic Olefin Having an Aromatic Ring) The structural unit (C) according to this embodiment is a structural unit derived from a cyclic olefin having an aromatic ring. The cyclic olefin having an aromatic ring according to this embodiment preferably contains one or more selected from the group consisting of a compound represented by the following formula (C-1), a compound represented by the following formula (C-2), and a compound represented by the following formula (C-3), from the viewpoint of suppressing the internal haze of the obtained resin composition and molded article and further improving the impact resistance after irradiation with high-intensity radiation. [ka] (In the above formula (C-1), n ​​and q each independently represent 0, 1, or 2; R 1 ~R 17 each independently represents 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; R 10 ~R 17 One of them 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 10may be bonded to each other to form a monocyclic or polycyclic ring, the monocyclic or polycyclic ring may have a double bond, or the monocyclic or polycyclic ring may be an aromatic ring. [ka] (In the above formula (C-2), n and m are each independently 0, 1 or 2, q is 1, 2 or 3, and R 18 ~R 31 each independently represents 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 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, the monocyclic or polycyclic ring may have a double bond, and the monocyclic or polycyclic ring may be an aromatic ring. [ka] (In the above formula (C-3), q is 1, 2 or 3, and R 32 ~R 39 each independently represents 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 may be bonded to each other to form a monocyclic or polycyclic ring, and when q=2 or 3, R36 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.

[0023] From the viewpoint of further improving the impact resistance after irradiation with high-intensity radiation while suppressing the internal haze of the resulting resin composition and molded article, in the above formula (C-1), n ​​is preferably 0 or 1, and more preferably 0. q is preferably 0 or 1, and more preferably 0. From the viewpoint of further improving the impact resistance after irradiation with high-intensity radiation while suppressing the internal haze of the resulting resin composition and molded article, in the above formula (C-2), n is preferably 0 or 1, and more preferably 0. m is preferably 0 or 1, and more preferably 1. q is preferably 1 or 2, and more preferably 1. In addition, from the viewpoint of further improving the impact resistance after irradiation with high-intensity radiation while suppressing the internal haze of the obtained resin composition and molded article, in the above formula (C-3), q is preferably 1 or 2, and more preferably 1. In addition, from the viewpoint of further improving the impact resistance after irradiation with high-intensity radiation while suppressing the internal haze of the obtained resin composition and molded article, R 1 ~R 39 are each independently preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, even more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.

[0024] Examples of the hydrocarbon group having 1 to 20 carbon atoms include, independently, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, and an aromatic hydrocarbon group. 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. Examples of the aromatic hydrocarbon group include an aryl group or an aralkyl group such as a phenyl group, a tolyl group, a naphthyl group, a benzyl group, and a phenylethyl group. These hydrocarbon groups may be substituted with a halogen atom other than a fluorine atom.

[0025] Among these, from the viewpoint of further improving the impact resistance after irradiation with high-intensity radiation while suppressing the internal haze of the resulting resin composition and molded article, the cyclic olefin having an aromatic ring according to the present embodiment preferably contains one or more selected from the group consisting of benzonorbornadiene, indenenorbornene, and methylphenylnorbornene, and more preferably contains benzonorbornadiene.

[0026] When the total content of the structural units (A), (B) and (C) in the polymer [II] of this embodiment is taken as 100 mol%, the content of the structural unit (A) in the polymer [II] of this embodiment is preferably more than 50 mol%, more preferably 54 mol% or more, even more preferably 57 mol% or more, even more preferably 60 mol% or more, even more preferably 63 mol% or more, and preferably 80 mol% or less, more preferably 76 mol% or less, even more preferably 73 mol% or less, even more preferably 70 mol% or less, and even more preferably 67 mol% or less. By making the content of the structural unit (A) equal to or greater than the lower limit, the heat resistance and dimensional stability of the resulting resin composition and molded article can be improved, and the impact resistance after irradiation with high-intensity radiation can be further improved while suppressing internal haze. In addition, by making the content of the structural unit (A) equal to or less than the upper limit, the transparency and the like of the resulting resin composition and molded article can be improved. In this embodiment, the content of the structural unit (A) is, for example, 1 H-NMR or 13 It can be measured by C-NMR.

[0027] When the total content of the structural units (A), (B) and (C) in the polymer [II] of this embodiment is taken as 100 mol%, the content of the structural unit (B) in the polymer [II] of this embodiment is preferably 0.1 mol% or more, more preferably 1 mol% or more, even more preferably 5 mol% or more, even more preferably 10 mol% or more, even more preferably 15 mol% or more, even more preferably 20 mol% or more, even more preferably 25 mol% or more, and preferably less than 50 mol%, more preferably 45 mol% or less, even more preferably 40 mol% or less, even more preferably 35 mol% or less, and even more preferably 32 mol% or less. By making the content of the structural unit (B) equal to or greater than the above lower limit, the transparency of the resulting resin composition and molded article can be improved. In addition, by making the content of the structural unit (B) equal to or less than the above upper limit, the heat resistance and dimensional stability of the resulting resin composition and molded article can be improved, and the impact resistance after irradiation with high-intensity radiation can be improved while suppressing internal haze. In this embodiment, the content of the structural unit (B) is, for example, 1 H-NMR or 13 It can be measured by C-NMR.

[0028] When the total content of the structural unit (B) and the structural unit (C) in the polymer [II] of this embodiment is taken as 100 mol%, the content of the structural unit (C) in the polymer [II] of this embodiment is preferably 5 mol% or more, more preferably 10 mol% or more, even more preferably 15 mol% or more, and preferably 95 mol% or less, more preferably 90 mol% or less, even more preferably 80 mol% or less, even more preferably 70 mol% or less, even more preferably 60 mol% or less, even more preferably 50 mol% or less, even more preferably 40 mol% or less, even more preferably 30 mol% or less, and even more preferably 25 mol% or less. By making the content of the structural unit (C) equal to or greater than the lower limit, the resulting molded article can have a high refractive index and a low Abbe number, and can further improve the impact resistance after irradiation with high-intensity radiation while suppressing internal haze. Also, by making the content of the structural unit (C) equal to or less than the upper limit, the resulting molded article can have a better balance between the refractive index and Abbe number, and can further improve the impact resistance after irradiation with high-intensity radiation while suppressing internal haze. In this embodiment, the content of the structural unit (C) is, for example, 1 H-NMR or 13 It can be measured by C-NMR.

[0029] The total content of the structural unit (A), the structural unit (B) and the structural unit (C) in the polymer [II] according to this embodiment is preferably 80 mol% or more, more preferably 90 mol% or more, even more preferably 95 mol% or more, even more preferably 98 mol% or more, even more preferably 99 mol% or more, and is, for example, 100 mol% or less.

[0030] The copolymer type of the polymer [I] and the polymer [II] according to this embodiment is not particularly limited, and examples thereof include random copolymers, block copolymers, etc. In this embodiment, from the viewpoint of obtaining a molded product having excellent optical properties such as transparency, Abbe number, refractive index, birefringence, and suppression of internal haze, and excellent impact resistance after irradiation with high-intensity radiation, it is preferable that the polymer [I] and the polymer [II] according to this embodiment are each a random copolymer.

[0031] The polymer [I] and the polymer [II] according to the present embodiment can be produced by appropriately selecting the conditions according to the methods described in, for example, JP-A-60-168708, JP-A-61-120816, JP-A-61-115912, JP-A-61-115916, JP-A-61-271308, JP-A-61-272216, JP-A-62-252406, JP-A-62-252407, JP-A-2007-314806, JP-A-2010-241932, and the like.

[0032] ([III] One or more ring-opening polymers or ring-opening copolymers selected from the group consisting of cyclic olefins having no aromatic ring and cyclic olefins having an aromatic ring) The polymer [III] according to this embodiment is one or more ring-opened polymers or ring-opened copolymers selected from the group consisting of cyclic olefins having no aromatic ring and cyclic olefins having an aromatic ring. The polymer [III] according to this embodiment has a structure obtained by ring-opening polymerization or ring-opening copolymerization of one or more olefins selected from the group consisting of cyclic olefins having no aromatic ring and cyclic olefins having an aromatic ring, and thus the polymer can have improved impact resistance after irradiation with high-intensity radiation while suppressing internal haze in the resulting resin composition and molded article. Preferred aspects of the cyclic olefin having no aromatic ring and the cyclic olefin having an aromatic ring in the polymer [III] according to this embodiment are similar to those in the polymer [I] and the polymer [II] according to this embodiment, and therefore the description thereof will be omitted here.

[0033] The ring-opening (co)polymer [III] of a cyclic olefin can be produced by a conventionally known production method, for example, by polymerizing or copolymerizing a cyclic olefin in the presence of a ring-opening polymerization catalyst.

[0034] As such a ring-opening polymerization catalyst, a catalyst consisting of a halide, nitrate or acetylacetone compound of a metal selected from tungsten, ruthenium, rhodium, palladium, osmium, indium, platinum, etc., and a reducing agent, or a catalyst consisting of a halide or acetylacetone compound of a metal selected from titanium, palladium, zirconium, molybdenum, etc., and an organoaluminum compound can be used. The ring-opened (co)polymer of cyclic olefin [III] can also be obtained by the method described in, for example, JP-A-7-324108.

[0035] ([IV] Hydrogenated ring-opened polymer or ring-opened copolymer [III]) The polymer [IV] according to this embodiment is a hydrogenated product of a ring-opening polymer or ring-opening copolymer [III] of a cyclic olefin. The hydrogenated ring-opened (co)polymer [III] of a cyclic olefin (hereinafter also referred to as the hydrogenated ring-opened (co)polymer [IV]) can be obtained by hydrogenating the ring-opened (co)polymer [III] of a cyclic olefin in the presence of a hydrogenation catalyst according to a conventional method, for example, the method described in JP-A-7-324108.

[0036] ([V] Graft-modified product of the polymer [I], [II], [III] or [IV]) [V] according to this embodiment is a graft modified product of the polymer [I], [II], [III] or [IV]. As the modifier for obtaining the graft modified product [V], for example, unsaturated carboxylic acids are used, specifically, (meth)acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, endo-cis-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid (Nadic acid TM) and other unsaturated carboxylic acids; derivatives of the above unsaturated carboxylic acids (for example, unsaturated carboxylic acid anhydrides, unsaturated carboxylic acid halides, unsaturated carboxylic acid amides, unsaturated carboxylic acid imides, ester compounds of unsaturated carboxylic acids), etc. More specifically, derivatives of unsaturated carboxylic acids include maleic anhydride, citraconic anhydride, malenyl chloride, maleimide, monomethyl maleate, dimethyl maleate, glycidyl maleate, etc.

[0037] Among these modifiers, α,β-unsaturated dicarboxylic acids and α,β-unsaturated dicarboxylic anhydrides are preferably used, and maleic acid, nadic acid and the anhydrides of these acids are more preferably used. These modifiers may be used alone or in combination of two or more kinds. The modification rate in the graft modified product [V] is desirably, for example, 10 mol % or less.

[0038] To obtain the graft modified product [V] using the polymer [I], [II], [III] or [IV] and the modifier, a conventionally known polymer modification method can be widely applied. For example, the graft modified product [V] can be obtained by a method of adding a modifier to the polymer [I], [II], [III] or [IV] in a molten state and graft polymerizing (reacting); or by a method of adding a modifier to a polymer solution of [I], [II], [III] or [IV] and graft reacting. Such a graft reaction is carried out at a temperature of, for example, 60 to 350°C. The graft reaction can also be carried out in the presence of a radical initiator such as an organic peroxide and an azo compound.

[0039] The graft modified product [V] having the above modification ratio can be obtained directly by the graft reaction between the unmodified polymer [I], [II], [III] or [IV] and the modifying agent. Alternatively, the modified product having a high modification ratio can be prepared in advance by the graft reaction between the polymer [I], [II], [III] or [IV] and the modifying agent, and then the modified product can be diluted with the unmodified polymer [I], [II], [III] or [IV] to obtain the desired modification ratio.

[0040] The glass transition temperature (Tg) of the cyclic olefin (co)polymer (P) for use in a high-intensity radiation environment according to this embodiment, measured by a differential scanning calorimeter (DSC), is preferably 120°C or higher, more preferably 130°C or higher, even more preferably 140°C or higher, and is preferably 180°C or lower, more preferably 170°C or lower, even more preferably 160°C or lower, from the viewpoints of further improving heat resistance while maintaining good transparency, haze, Abbe number, birefringence, refractive index, etc. of the obtained resin composition and molded article, suppressing internal haze, and further improving impact resistance after irradiation with high-intensity radiation.

[0041] The intrinsic viscosity [η] of the cyclic olefin (co)polymer (P) for use in a high-intensity radiation environment according to this embodiment, measured in decalin at 135°C, is preferably 0.05 dl / g or more, more preferably 0.2 dl / g or more, even more preferably 0.3 dl / g or more, even more preferably 0.4 dl / g or more, and is preferably 5.0 dl / g or less, more preferably 4.0 dl / g or less, even more preferably 2.0 dl / g or less, and even more preferably 1.0 dl / g or less, from the viewpoint of further improving the impact resistance after irradiation with high-intensity radiation while suppressing the internal haze of the resulting resin composition and molded article.

[0042] In the cyclic olefin (co)polymer (P) for use under high-intensity radiation environment according to this embodiment, from the viewpoint of further improving the impact resistance after irradiation with high-intensity radiation while suppressing the internal haze of the resulting resin composition and molded article, when a press sheet having a thickness of 2.0 mm is produced from the cyclic olefin (co)polymer (P) for use under high-intensity radiation environment, the value of the high-speed surface impact of the press sheet after irradiation with 300 kGy of electron beam measured by a high-speed surface impact test is preferably 0.30 J or more, more preferably 0.35 J or more, even more preferably 0.40 J or more, even more preferably 0.45 J or more, and even more preferably 0.50 J or more. The upper limit value of the high-speed surface impact of the press sheet after irradiation with 300 kGy of electron beam is not particularly limited, but may be, for example, 5.0 J or less, 3.0 J or less, or 1.0 J or less.

[0043] In the cyclic olefin (co)polymer (P) for use under high-intensity radiation environment according to this embodiment, from the viewpoint of suppressing the internal haze of the resin composition and molded article obtained and further improving the impact resistance after irradiation with high-intensity radiation, when a press sheet having a thickness of 2.0 mm is produced from the cyclic olefin (co)polymer (P) for use under high-intensity radiation environment, the internal haze of the press sheet after irradiation with 300 kGy of electron beam measured according to JIS K7105:2000 is preferably less than 2.00%, more preferably less than 1.80%, even more preferably less than 1.60%, even more preferably less than 1.40%, even more preferably less than 1.20%, and even more preferably less than 1.00%. The lower limit of the internal haze of the press sheet after irradiation with 300 kGy of electron beam is not particularly limited, but may be, for example, 0.01% or more, 0.05% or more, or 0.10% or more.

[0044] (Resin composition) The resin composition of the present embodiment contains the above-mentioned cyclic olefin (co)polymer (P) for use in a high-intensity radiation environment. The resin composition of the present embodiment contains the cyclic olefin (co)polymer (P) for use in high-intensity radiation environments of the present embodiment, thereby suppressing internal haze while improving impact resistance after exposure to high-intensity radiation, and therefore can be suitably used for applications in high-intensity radiation environments.

[0045] The content of the cyclic olefin (co)polymer (P) for use in a high-intensity radiation environment in the resin composition of this embodiment is, from the viewpoint of further improving the impact resistance after irradiation with high-intensity radiation while suppressing the internal haze of the resulting resin composition and molded article, preferably 80 parts by mass or more, more preferably 90 parts by mass or more, even more preferably 95 parts by mass or more, and preferably 99.9 parts by mass or less, more preferably 99.5 parts by mass or less, and even more preferably 99 parts by mass or less, when the total amount of the resin composition is 100 parts by mass.

[0046] (Other Ingredients) If necessary, the resin composition according to the present embodiment may contain weather resistance stabilizers, heat resistance stabilizers, antioxidants, metal deactivators, hydrochloric acid absorbers, antistatic agents, flame retardants, slip agents, antiblocking agents, antifogging agents, lubricants, natural oils, synthetic oils, waxes, colorants, organic or inorganic fillers, and the like to an extent that does not impair the object of the present invention, and the blending ratios of the additives are appropriate.

[0047] As the colorant, for example, various natural and synthetic dyes and various inorganic and organic pigments can be arbitrarily used.

[0048] (Molded body) The molded article according to this embodiment is a molded article containing the cyclic olefin (co)polymer (P) for use in a high-intensity radiation environment according to this embodiment. The molded article according to the present embodiment contains the cyclic olefin (co)polymer (P) for use under high-intensity radiation environments according to the present embodiment, and therefore has an excellent balance of heat resistance, transparency, haze, birefringence, chemical resistance, low moisture absorption, etc., and has a higher refractive index and a lower Abbe number than conventional resin materials. In addition, the molded article according to the present embodiment has improved impact resistance after irradiation with high-intensity radiation while suppressing internal haze, and is therefore suitable for use under high-intensity radiation environments.

[0049] The molded article according to this embodiment has excellent optical properties and impact resistance after irradiation with high-intensity radiation, and can therefore be suitably used, for example, as window materials used in high-intensity radiation environments, face shields for protective clothing, see-through surfaces, sight glasses, optical lenses, medical containers, circuit boards (particularly high-frequency circuit boards), or prepregs.

[0050] In addition, the content of the cyclic olefin (co)polymer (P) for use under high-intensity radiation environments in the molded body according to this embodiment is, from the viewpoint of further improving the performance balance of transparency, haze, birefringence, Abbe number, refractive index, and impact resistance after irradiation with high-intensity radiation, 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, and preferably 100% by mass or less, when the entire molded body is taken as 100% by mass.

[0051] The molded article according to the present embodiment can be obtained by molding a resin composition containing a cyclic olefin (co)polymer (P) for use under high-intensity radiation environments into a predetermined shape. The method of obtaining a molded article by molding a resin composition containing a cyclic olefin (co)polymer (P) for use under high-intensity radiation environments is not particularly limited, and a known method 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, calendar molding, foam molding, etc. can be applied. Among these, the injection molding method is preferred from the viewpoint of moldability and productivity. In addition, the molding conditions are appropriately selected depending on the purpose of use or the molding method, and for example, the resin temperature in injection molding is appropriately selected in the range of usually 150°C to 400°C, preferably 200°C to 350°C, more preferably 230°C to 330°C.

[0052] The molded article according to this embodiment can be used in various forms, such as a lens shape, a sphere shape, a rod shape, a plate shape, a cylinder shape, a tube shape, a fiber shape, a film shape, or a sheet shape.

[0053] The molded article according to the present embodiment may contain known additives as optional components, as long as the good physical properties of the molded article according to the present embodiment are not impaired. Examples of additives include phenolic stabilizers, higher fatty acid metal salts, antioxidants, ultraviolet absorbers, hindered amine light stabilizers, hydrochloric acid absorbers, metal deactivators, antistatic agents, antifogging agents, lubricants, slip agents, nucleating agents, plasticizers, flame retardants, phosphorus stabilizers, etc., which may be blended to the extent that the object of the present invention is not impaired, and the blending ratio is an appropriate amount.

[0054] Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various configurations other than those described above can also be adopted. Furthermore, the present invention is not limited to the above-described embodiment, and modifications and improvements within the scope of the present invention that can achieve the object of the present invention are included in the present invention. EXAMPLES

[0055] The present disclosure will be described in more detail below with reference to examples and comparative examples, but the present disclosure is not limited thereto in any way.

[0056] The components used in the examples and comparative examples are shown below. <Production of cyclic olefin (co)polymers for use in high intensity radiation environments> [Production Example 1] [Cyclic olefin copolymer for use in high intensity radiation environments (P-1)] Nitrogen was passed through a 500 ml glass reaction vessel equipped with a stirrer at a flow rate of 100 Nl / hr for 30 minutes as an inert gas, and then cyclohexane, tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene (11 mmol, hereinafter also referred to as tetracyclododecene or TD), and benzonorbornadiene (19 mmol, hereinafter also referred to as BNBD) were added. Next, the solvent temperature was raised to 50°C while stirring the polymerization solvent at a rotation speed of 600 rpm. After the solvent temperature reached a predetermined temperature, the flow gas was switched from nitrogen to ethylene, and ethylene was flowed into the reaction vessel at a feed rate of 90 Nl / hr and hydrogen at 0.2 Nl / hr. After 10 minutes had passed, methylaluminoxane (MMAO) (0.30 mmol), triphenylcarbenium tetrakis(pentafluorophenyl)borate (0.0040 mmol), and 3,5-bismethylethyl-1-pyrazolate-t-butylcyclopentadienyltitanium dichloride (0.00013 mmol) were added to the glass reaction vessel to start polymerization. After 10 minutes, 5 ml of isobutyl alcohol was added to terminate the polymerization, and a polymerization solution containing ethylene, tetracyclododecene, and BNBD copolymer was obtained. The polymerization solution was then transferred to a 2 L beaker, and 5 ml of concentrated hydrochloric acid and a stirrer were added. The mixture was left in contact with the polymer for 2 hours under strong stirring to perform deashing. The deashed polymerization solution was added to a beaker containing acetone about three times the volume of the polymerization solution under stirring to precipitate the copolymer, which was then separated from the filtrate by filtration. The resulting polymer containing the solvent was dried under reduced pressure at 130°C for 10 hours, yielding 0.18 g of ethylene-tetracyclododecene-BNBD copolymer in the form of a white powder. As a result, a cyclic olefin copolymer (P-1) for use under high-intensity radiation environments was obtained. The molar ratio of ethylene, tetracyclododecene, and BNBD in the cyclic olefin copolymer (P-1) for use under high-intensity radiation environments was ethylene / tetracyclododecene / BNBD=64 / 29 / 7 (mol%). The glass transition point (Tg) of the cyclic olefin copolymer (P-1) for use under high-intensity radiation environments was 142°C, and the intrinsic viscosity [η] was 0.58 dl / g. Here, benzonorbornadiene is represented by the following formula (1).

[0057] [ka] Here, tetracyclododecene is represented by the following formula (2).

[0058] [ka]

[0059] [Production Example 2] [Cyclic olefin copolymer for use in high intensity radiation environments (P-2)] P-2: Random copolymer of ethylene and tetracyclododecene (ethylene content: 66 mol%, tetracyclododecene (TD) content: 34 mol%, glass transition temperature: 145°C, intrinsic viscosity [η]: 0.60 dl / g) Here, the above-mentioned cyclic olefin copolymer (P-2) for use in a high-intensity radiation environment was synthesized by a method according to Polymerization Example 7 described in the Examples of WO 2008 / 068897, with the amount of each monomer changed.

[0060] [Production Example 3] [Cyclic olefin-based ring-opening polymer for use in high-intensity radiation environments (P-3)] Into a polymerization reactor whose inside had been substituted with nitrogen, 7 parts by mass of a monomer mixture (40 mol% tetracyclododecene, 40 mol% dicyclopentadiene, 20 mol% indenenorbornene), 1,600 parts by mass of dehydrated cyclohexane, 0.6 parts by mass of 1-hexene, 1.3 parts by mass of diisopropyl ether, 0.33 parts by mass of isobutyl alcohol, 0.84 parts by mass of triisobutylaluminum, and 30 parts by mass of a cyclohexane solution of tungsten hexachloride (concentration: 0.66%) were placed, and the entire amount was stirred at 55°C for 10 minutes. Next, while continuing stirring, 693 parts by mass of the monomer mixture and 72 parts by mass of a cyclohexane solution of tungsten hexachloride (concentration: 0.77%) were continuously added dropwise over 150 minutes at 55°C. After completion of the dropwise addition, stirring was continued for another 30 minutes, and then 1.0 part by mass of isopropyl alcohol was added to terminate the polymerization reaction. When the polymerization reaction solution was measured by gas chromatography, the conversion rate of the monomer to polymer was 100%. Next, 300 parts by mass of the polymerization reaction solution containing the polymer was transferred to an autoclave equipped with a stirrer, and 100 parts by mass of cyclohexane and 2.0 parts by mass of a nickel catalyst supported on diatomaceous earth (nickel loading rate: 58%) were added. After replacing the atmosphere in the autoclave with hydrogen, a hydrogenation reaction was carried out at 180°C under a hydrogen pressure of 4.5 MPa for 6 hours. After the hydrogenation reaction was completed, the mixture was filtered at a pressure of 0.25 MPa using a pressure filter with diatomaceous earth as a filter bed to obtain a colorless and transparent solution. The resulting solution was added to a beaker containing 3 times the amount of acetone with stirring to precipitate a ring-opened polymer, and a cyclic olefin ring-opened polymer for use under high-intensity radiation environments (P-3) was obtained in the same manner as in Production Example 1. The molar ratio of tetracyclododecene, dicyclopentadiene, and indenenorbornene in the cyclic olefin ring-opening polymer (P-3) for use under high-intensity radiation environments was tetracyclododecene / dicyclopentadiene / indenenorbornene=40 / 40 / 20 (mol%). The glass transition point (Tg) of the cyclic olefin ring-opening polymer (P-3) for use under high-intensity radiation environments was 136°C, and the intrinsic viscosity [η] was 0.42 dl / g. Here, dicyclopentadiene is represented by the following formula (3).

[0061] [ka] Here, indene norbornene is represented by the following formula (4). [ka]

[0062] [Comparative Example 1] Commercially available polymethyl methacrylate (manufactured by Mitsubishi Chemical Corporation) was used.

[0063] [Method for measuring the content of each structural unit constituting cyclic olefin copolymer / ring-opening polymer for use under high-intensity radiation environment] The content of structural units derived from α-olefins having 2 to 20 carbon atoms and structural units derived from cyclic olefins was measured using a JEOL "ECA500" nuclear magnetic resonance spectrometer under the following conditions. Solvent: deuterated tetrachloroethane Sample concentration: 50~100g / l-solvent Pulse repetition time: 5.5 seconds Number of times: 6000 to 16000 Measurement temperature: 120℃ Measured under the above conditions 13 The compositions of α-olefins and cyclic olefins having 2 to 20 carbon atoms were quantitatively determined by C-NMR spectroscopy.

[0064] [Glass transition temperature Tg(℃)] The glass transition temperature Tg of the cyclic olefin (co)polymer for use under high-intensity radiation environment was measured under N2 (nitrogen) atmosphere using DSC-6220 manufactured by Shimadzu Science Co., Ltd. The cyclic olefin (co)polymer for use under high-intensity radiation environment was heated from room temperature to 200°C at a heating rate of 10°C / min, held for 5 minutes, then cooled to -20°C at a heating rate of 10°C / min, held for 5 minutes. The glass transition temperature (Tg) of the cyclic olefin (co)polymer for use under high-intensity radiation environment was obtained from the endothermic curve when the temperature was raised to 200°C at a heating rate of 10°C / min.

[0065] [Intrinsic viscosity [η]] Using a moving viscometer (Rigo Co., Ltd., Type VNR053U), 0.25-0.30 g of cyclic olefin (co)polymer for use under high-intensity radiation environments was dissolved in 25 ml of decalin to prepare a sample. The specific viscosity of the cyclic olefin (co)polymer for use under high-intensity radiation environments 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 obtain the limiting viscosity [η] of the cyclic olefin (co)polymer for use under high-intensity radiation environments.

[0066] <Examples 1 to 3 and Comparative Example 1> In each of the Examples and Comparative Examples, various physical properties were measured or evaluated by the following methods, and the results are shown in Tables 1 and 2.

[0067] [Preparation of test press sheets] The cyclic olefin (co)polymers for use under high-intensity radiation environments synthesized in each example and the polymethyl methacrylate of the comparative example were sandwiched between films of Upilex (trade name, manufactured by Ube Industries, Ltd.) and vacuum press molded using a 2.0 mm spacer at 250°C, 10 MPa, and 3 minutes to obtain a test press sheet having a thickness of 2.0 mm.

[0068] [Electron beam irradiation] A test press sheet obtained by vacuum press molding was irradiated with 300 kGy of electron beam by double-sided irradiation method.

[0069] [High-speed surface impact test (high rate test)] A 1 / 2 inch diameter striker with a load cell attached was collided with the test press sheet irradiated with the electron beam at a test speed of 5 m / s under the condition of 23°C. A support table with a diameter of 1 inch was used on the back side of the test press sheet. From the obtained displacement and the test force displacement curve, the energy value up to the maximum point of the test force was calculated as the maximum impact point energy. A larger value indicates higher impact resistance, and it was determined that the effect of the present invention was achieved when the value of the high-velocity surface impact after electron beam irradiation was 0.30 J or more. The same test was also carried out using a test press sheet that had not been irradiated with electron beams.

[0070] [Transparency] The internal haze of the obtained test press sheet having a thickness of 2.0 mm and the test press sheet after irradiating the test press sheet with an electron beam and then leaving it at 23°C for 2 weeks were measured according to JIS K7105:2000, and the transparency was evaluated according to the following criteria. The internal haze was measured in pure water using a haze meter (NDH-20D manufactured by Nippon Denshoku Industries Co., Ltd.). OK: Internal haze is less than 2.00% NG: Test piece is visually cloudy or has an internal haze of 2.00% or more.

[0071] [Table 1]

[0072] [Table 2]

Claims

1. A cyclic olefin (co)polymer for use in a high-intensity radiation environment, comprising one or more polymers selected from the group consisting of the following [I], [II], [III], [IV] and [V]: [I] A random copolymer containing a structural unit (A) derived from an α-olefin having 2 to 20 carbon atoms and a structural unit (B) derived from a cyclic olefin having no aromatic ring. [II] A copolymer comprising the structural unit (A), the structural unit (B), and a structural unit (C) derived from a cyclic olefin having an aromatic ring. [III] One or more ring-opening polymers or ring-opening copolymers selected from the group consisting of the cyclic olefins having no aromatic rings and the cyclic olefins having aromatic rings. [IV] A hydrogenated product of the ring-opened polymer or ring-opened copolymer [III] [V] A graft-modified product of the polymer [I], [II], [III] or [IV].

2. 2. The cyclic olefin (co)polymer for use in a high-intensity radiation environment according to claim 1, wherein the cyclic olefin having no aromatic ring comprises a compound represented by the following formula (B-1): 【Chemical 1】 (In the above formula (B-1), n ​​is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and R １ ~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, and R １５ ~R １８ 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 R １５ and R １６ With or R １７ and R １８ and may form an alkylidene group, provided that the aromatic ring is not included.)

3. The cyclic olefin having no aromatic ring is selected from the group consisting of bicyclo[2.2.1]-2-heptene, tetracyclo[4.4.0.1]-2-heptene, and the like. ２，５ .1 ７，１０ ]-3-dodecene and hexacyclo[6,6,1,1 ３，６ , 1 １０，１３ , 0 ２，７ , 0 ９，１４ 3. The cyclic olefin (co)polymer for use in a high-intensity radiation environment according to claim 1, comprising one or more selected from the group consisting of: heptadecene-4, heptadecene-5, heptadecene-6, heptadecene-7, heptadecene-8, heptadecene-9, heptadecene-10, heptadecene-11, heptadecene-12, heptadecene-13, hepta

4. 3. The cyclic olefin (co)polymer for use in a high-intensity radiation environment according to claim 1 or 2, wherein the cyclic olefin having an aromatic ring comprises one or more compounds selected from the group consisting of a compound represented by the following formula (C-1), a compound represented by the following formula (C-2), and a compound represented by the following formula (C-3): 【Chemistry 2】 (In the above formula (C-1), n ​​and q each independently represent 0, 1, or 2; R １ ~R １７ are each independently a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom other than a fluorine atom, and R １０ ~R １７ One of them 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 monocycle or a polycycle, and the monocycle or the polycycle may have a double bond, or the monocycle or the polycycle may be an aromatic ring. 【Chemistry 3】 (In the above formula (C-2), n and m are each independently 0, 1, or 2, q is 1, 2, or 3, and R １８ ~R ３１ are each independently a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom other than a fluorine atom, and when q=1, R ２８ 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 monocycle or a polycycle, the monocycle or the polycycle may have a double bond, or the monocycle or the polycycle may be an aromatic ring. 【Chemistry 4】 (In the above formula (C-3), q is 1, 2 or 3, and R ３２ ~R ３９ are each independently a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom other than a fluorine atom, 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 ３９ may be bonded to each other to form a monocycle or a polycycle, the monocycle or the polycycle may have a double bond, or the monocycle or the polycycle may be an aromatic ring.

5. The cyclic olefin (co)polymer for use in a high-intensity radiation environment according to claim 1 or 2, comprising at least one polymer selected from the group consisting of [I] and [II].

6. The cyclic olefin (co)polymer for use in a high-intensity radiation environment according to claim 1 or 2, comprising the polymer [I].

7. 7. The cyclic olefin (co)polymer for use in a high-intensity radiation environment according to claim 6, wherein the content of the structural unit (A) in the polymer [I] is more than 50 mol% and not more than 80 mol%, when the total content of the structural unit (A) and the structural unit (B) in the polymer [I] is taken as 100 mol%.

8. The cyclic olefin (co)polymer for use in a high-intensity radiation environment according to claim 1 or 2, comprising the polymer [II].

9. 9. The cyclic olefin (co)polymer for use in a high-intensity radiation environment according to claim 8, wherein the content of the structural unit (A) in the polymer [II] is more than 50 mol% and not more than 80 mol%, when the total content of the structural unit (A), the structural unit (B), and the structural unit (C) in the polymer [II] is 100 mol%.

10. 9. The cyclic olefin (co)polymer for use in a high-intensity radiation environment according to claim 8, wherein the content of the structural unit (B) in the polymer [II] is 0.1 mol% or more and less than 50 mol%, when the total content of the structural unit (A), the structural unit (B), and the structural unit (C) in the polymer [II] is 100 mol%.

11. 9. The cyclic olefin (co)polymer for use in a high-intensity radiation environment according to claim 8, wherein the content of the structural unit (C) in the polymer [II] is 5 mol% or more and 95 mol% or less, when the total content of the structural unit (B) and the structural unit (C) in the polymer [II] is taken as 100 mol%.

12. 3. The cyclic olefin (co)polymer for use in a high-intensity radiation environment according to claim 1, which has a glass transition temperature (Tg) of 120°C or higher and 180°C or lower as measured by a differential scanning calorimeter (DSC).

13. 3. The cyclic olefin (co)polymer for use in a high-intensity radiation environment according to claim 1, which has an intrinsic viscosity [η] measured in decalin at 135°C of 0.05 dl / g or more and 5.0 dl / g or less.

14. 3. The cyclic olefin (co)polymer for use in a high-intensity radiation environment according to claim 1 or 2, wherein the cyclic olefin having an aromatic ring comprises one or more selected from the group consisting of benzonorbornadiene, indenenorbornene, and methylphenylnorbornene.

15. A resin composition comprising the cyclic olefin (co)polymer for use in a high-intensity radiation environment according to claim 1 or 2.

16. A molded article comprising the cyclic olefin (co)polymer for use in a high-intensity radiation environment according to claim 1 or 2.

17. The molded article according to claim 16, which is a window material, a face shield for protective clothing, a see-through surface, a sight glass, an optical lens, a medical container, a circuit board, or a prepreg that can be used in a high-intensity radiation environment.

Images