Cyclic olefin copolymer composition and molded article

Abstract

To provide a compact that is less in the discoloration due to electron beam or gamma ray irradiation, and, is excellent in the heat resistance.SOLUTION: A cyclic olefinic copolymer composition comprising a cyclic olefin copolymer (P) and a stabilizer (S), in which the cyclic olefinic copolymer (P) has a constituent unit (A) derived from alpha-olefin having 2 to 20 carbon atoms, a constituent unit (B) derived from a cyclic olefin not having an aromatic ring, and a constituent unit (C) derived from a cyclic olefin having an aromatic ring, and the stabilizer (S) has a phenolic hydroxide group and phosphorous.SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] Cyclic olefin resins offer an excellent balance of properties such as transparency and chemical resistance. Therefore, their use as a material for forming molded articles, such as medical devices and food utensils, is being considered. Examples of technologies related to resin compositions containing such cyclic olefin resins include those described in Patent Documents 1 and 2.

[0003] Patent Document 1 describes a cyclic olefin resin composition containing two specific cyclic olefin resins. It also describes that this composition can be used to obtain molded articles with improved slip properties, excellent transparency and surface gloss, and superior hygiene.

[0004] Patent Document 2 describes a cyclic olefin resin composition comprising 60 to 90 parts by weight of a cyclic olefin resin and 10 to 40 parts by weight of an aromatic vinyl-conjugated diene block copolymer and / or its hydrogenated product having a number average molecular weight of 75,000 to 500,000. It also describes that a molded article with excellent impact strength and moisture resistance can be obtained using this composition.

[0005] Furthermore, Patent Document 3 describes that by using a cyclic olefin copolymer containing α-olefin-derived structural units, structural units derived from cyclic olefins without aromatic rings, and structural units derived from cyclic olefins having aromatic rings as the resin constituting the medical container, it is possible to provide a medical container that exhibits less discoloration due to electron beam or gamma ray irradiation and has excellent transparency. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2001-26693 [Patent Document 2] Japanese Patent Application Publication No. 8-277353 [Patent Document 3] International Publication No. 2019 / 107363 [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] For example, molded parts such as medical instruments and food utensils may be used after sterilization. During this sterilization process, the molded parts may be irradiated with electron beams or gamma rays. Our investigations have revealed that conventional molded articles using cyclic olefin resins may discolor and have reduced heat resistance when irradiated with electron beams or gamma rays.

[0008] This invention was made in view of these circumstances. In other words, this invention provides a molded article that exhibits minimal discoloration due to electron beam or gamma ray irradiation and has excellent heat resistance. [Means for solving the problem]

[0009] The inventors diligently studied to solve the above problems. As a result, they discovered that by using a combination of a cyclic olefin copolymer having a specific structure and a stabilizer having a phenolic hydroxyl group and phosphorus, a molded article with less discoloration due to electron beam or gamma ray irradiation and excellent heat resistance can be obtained, thus completing the present invention.

[0010] In other words, the present invention provides the following cyclic olefin copolymer composition and molded article.

[0011] [1] A cyclic olefin copolymer composition comprising a cyclic olefin copolymer (P) and a stabilizer (S), The above 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. The above stabilizer (S) has a phenolic hydroxyl group and phosphorus. Cyclic olefin copolymer composition. [2] In the cyclic olefin copolymer composition described in the above [1], The cyclic olefin copolymer composition in which the above stabilizer (S) contains at least one selected from a mixture of a phenolic compound and a phosphorus compound and a compound having a phenolic hydroxyl group and phosphorus as a constituent element. [3] In the cyclic olefin copolymer composition described in the above [1] or [2], The cyclic olefin copolymer composition in which the cyclic olefin having no aromatic ring contains a compound represented by the following formula (B-1). [Chemical formula] (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 as well as 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, 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 also R 15 and R 16 or R 17 and R 18 may form an alkylidene group. However, it does not contain an aromatic ring.) [4] In the cyclic olefin copolymer composition according to any one of the above [1] to [3], A cyclic olefin copolymer composition comprising one or more cyclic olefins having the above-mentioned aromatic rings, selected from the group consisting of compounds represented by the following formula (C-1), compounds represented by the following formula (C-2), and compounds represented by the following formula (C-3). [ka] (In the above equation (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 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 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. [ka] (In the above equation (C-2), n and m are independently 0, 1, or 2, q is 1, 2, or 3, R 18 ~R 31 Each of these is independently a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms that may be substituted with a halogen atom other than a fluorine atom, 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 have a double bond, and the monocycle or polycycle may be an aromatic ring. [ka] (In the above equation (C-3), q is 1, 2, or 3, 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 that 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 R39 , 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] In the cyclic olefin copolymer composition described in any one of the above [1] to [4], A cyclic olefin copolymer composition comprising at least one cyclic olefin having the above-mentioned aromatic ring, selected from benzonorbornane, indenenorbornene, and methylphenylnorbornene. [6] A molded article comprising the cyclic olefin copolymer composition described in any one of the above [1] to [5]. [7] In the molded article described in [6] above, A molded body that is a medical device or a food utensil. [Effects of the Invention]

[0012] According to the present invention, it is possible to provide a molded article that exhibits minimal discoloration due to electron beam or gamma ray irradiation and has excellent heat resistance. [Modes for carrying out the invention]

[0013] The present invention will be described below based on embodiments. In these embodiments, unless otherwise specified, "A~B" indicating a numerical range represents A or greater and B or less.

[0014] 1. Cyclic olefin copolymer composition The cyclic olefin copolymer composition according to this embodiment comprises a cyclic olefin copolymer (P) and a stabilizer (S), and may optionally contain other components besides the cyclic olefin copolymer (P) and stabilizer (S). The cyclic olefin copolymer (P) comprises a structural unit (A) derived from an α-olefin having 2 to 20 carbon atoms, a structural unit (B) derived from a cyclic olefin without an aromatic ring, and a structural unit (C) derived from a cyclic olefin having an aromatic ring, and the stabilizer (S) comprises a phenolic hydroxyl group and phosphorus.

[0015] Furthermore, the content of the cyclic olefin copolymer (P) in the cyclic olefin copolymer composition according to this embodiment is preferably 50% to 100% by mass, more preferably 70% to 100% by mass, even more preferably 80% to 100% by mass, and particularly preferably 90% to 100% by mass, when the total cyclic olefin copolymer composition is considered to be 100% by mass, from the viewpoint of further improving the balance of performance of the heat resistance, transparency, and gamma-ray or electron beam resistance of the resulting molded article. The cyclic olefin copolymer composition according to this embodiment, by containing the cyclic olefin copolymer (P) in the above-mentioned ratio, can further improve the gamma-ray or electron-ray resistance performance of the resulting molded article while satisfying the good transparency required for medical containers.

[0016] <Cyclic olefin copolymer (P)> The cyclic olefin copolymer (P) according to this embodiment comprises a structural unit (A) derived from an α-olefin having 2 to 20 carbon atoms, a structural unit (B) derived from a cyclic olefin without an aromatic ring, and a structural unit (C) derived from a cyclic olefin having an aromatic ring.

[0017] The cyclic olefin copolymer (P) according to this embodiment includes a structural unit (A) derived from an α-olefin having 2 to 20 carbon atoms, a structural unit (B) derived from a cyclic olefin without an aromatic ring, and a structural unit (C) derived from a cyclic olefin having an aromatic ring, thereby improving the radiation resistance of the molded article while maintaining good transparency. From the above, it is possible to obtain a molded article that exhibits less discoloration due to electron beam or gamma ray irradiation and has excellent transparency using the cyclic olefin copolymer (P) according to this embodiment.

[0018] (Ethylene-derived constituent unit (A)) The constituent unit (A) according to this embodiment is a constituent unit derived from an α-olefin having 2 to 20 carbon atoms. Here, the α-olefins having 2 to 20 carbon atoms may be linear or branched, and examples 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, linear α-olefins having 2 to 4 carbon atoms are preferred, and ethylene is particularly preferred. Such linear or branched α-olefins can be used individually or in combination of two or more.

[0019] When the total content of the above-mentioned constituent units (A), (B), and (C) in the cyclic olefin copolymer (P) according to this embodiment is set to 100 mol%, the content of the above-mentioned constituent unit (A) in the cyclic olefin copolymer (P) according to this embodiment is preferably 10 mol% or more and 80 mol% or less, more preferably 30 mol% or more and 75 mol% or less, and even more preferably 40 mol% or more and 70 mol% or less. By having the content of the above constitutional unit (A) be at least the above lower limit value, the heat resistance and dimensional stability of the resulting molded body can be improved. Further, by having the content of the above constitutional unit (A) be at most the above upper limit value, the moldability and the like of the resulting molded body can be improved. In the present embodiment, the content of the constitutional unit (A) is, for example, 1 measurable by 1H-NMR or 13 13C-NMR.

[0020] (Constitutional unit (B) derived from cyclic olefin) The constitutional unit (B) according to the present embodiment is a constitutional unit derived from a cyclic olefin having no aromatic ring. From the viewpoint of further improving the refractive index of the resulting molded body, the constitutional unit (B) according to the present embodiment preferably includes a constitutional unit derived from a compound represented by the following formula (B-1). [Chemical formula] (In the above formula [B-1], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, R 1 ~R 18 as well as R a and R b are each independently a hydrogen atom, a halogen atom or a hydrocarbon group which may be substituted by 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 or R 17 and R 18 may form an alkylidene group. However, it does not contain an aromatic ring.) Among these, as the constitutional unit (B) according to the present embodiment, a constitutional unit derived from 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 ,02,7 ,0 9,14 Preferably, it contains at least one constituent unit selected from constituent units derived from heptadecene-4, etc., including a constituent unit derived from bicyclo[2.2.1]-2-heptene and tetracyclo[4.4.0.1 2,5 .1 7,10 It is more preferable to include at least one constituent unit selected from constituent units derived from ]-3-dodecene, and tetracyclo[4.4.0.1 2,5 .1 7,10 It is particularly preferable that the constituent units include those derived from ]-3-dodecene.

[0021] When the total content of the above-mentioned constituent units (A), (B), and (C) in the cyclic olefin copolymer (P) according to this embodiment is set to 100 mol%, the content of constituent unit (B) in the cyclic olefin copolymer (P) is preferably 5 mol% or more and 60 mol% or less, more preferably 10 mol% or more and 55 mol% or less, and even more preferably 15 mol% or more and 45 mol% or less. In this embodiment, the content of constituent unit (B) is, for example, 1 H-NMR or 13 It can be measured by 13C-NMR.

[0022] (Constituent unit (C) derived from cyclic olefins having aromatic rings) The constituent unit (C) in this embodiment is a constituent unit derived from a cyclic olefin having an aromatic ring. Examples of cyclic olefins having an aromatic ring according to this embodiment include the compound represented by the following formula (C-1), the compound represented by the following formula (C-2), and the compound represented by the following formula (C-3). These cyclic olefins having an aromatic ring may be used individually or in combination of two or more. Among these, the compound represented by the following formula (C-3) is preferred.

[0023] [ka]

[0024] In the above formula (C-1), n ​​and q are each independently 0, 1, or 2. n is preferably 0 or 1, and more preferably 0. q is preferably 0 or 1, and more preferably 0. R 1 ~R 17 Each of these is independently a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom other than a fluorine atom, and R 10 ~R 17 One of them is a bonding hand, R 15 It is preferable that the coupling is a joint. R 1 ~R 17 Each of these is preferably independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrogen atom. Also, when q=0, R 10 and R 11 , R 11 and R 12 , R 12 and R 13 , R 13 and R 14 , R 14 and R 15 , R 15 and R 10 They may be bonded to each other to form a monocycle or polycycle, and when q=1 or 2, R 10 and R 11 , R 11 and R 17 , R 17 and R 17 , R 17 and R 12 , R 12 and R 13 , R 13 and R 14 , R 14 and R 15 , R 15 and R 16 , R 16 and R 16 , R 16 and R 10These 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. Among the compounds represented by the above formula (C-1), the compound represented by the following formula (C-1A) is preferred.

[0025] [ka]

[0026] [ka] In the above formula (C-2), n and m are each independently 0, 1, or 2, and q is 1, 2, or 3. m is preferably 0 or 1, and more preferably 1. n is preferably 0 or 1, and more preferably 0. q is preferably 1 or 2, and more preferably 1. R 18 ~R 31 Each of these is independently a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms that may be substituted with a halogen atom other than a fluorine atom. R 18 ~R 31 Each of these is preferably independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrogen atom. Also, when q=1, R 28 and R 29 , R 29 and R 30 , R 30 and R 31 They may be bonded to each other to form a monocycle or polycycle, and when q=2 or 3, R 28 and R 28 , R 28 and R 29 , R 29 and R 30 , R 30 and R 31 , R 31 and R 31These 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.

[0027] [ka] In the above formula (C-3), q is 1, 2, or 3, preferably 1 or 2, and more preferably 1. 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 that may be substituted with a halogen atom other than a fluorine atom. R 32 ~R 39 Each of these is preferably independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrogen atom. Also, 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.

[0028] Furthermore, examples of hydrocarbon groups having 1 to 20 carbon atoms include, independently, alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 15 carbon atoms, and aromatic hydrocarbon groups. More specifically, alkyl groups include methyl, ethyl, propyl, isopropyl, amyl, hexyl, octyl, decyl, dodecyl, and octadecyl groups; cycloalkyl groups include cyclohexyl groups; and aromatic hydrocarbon groups include aryl or aralkyl groups such as phenyl, tolyl, naphthyl, benzyl, and phenylethyl groups. These hydrocarbon groups may be substituted with halogen atoms other than fluorine atoms.

[0029] Among these, the cyclic olefin having an aromatic ring according to this embodiment is preferably one having one aromatic ring, for example, at least one selected from benzonorbornane, indenenorbornane, and methylphenylnorbornane is preferred, and benzonorbornane is more preferred.

[0030] When the total content of the above-mentioned constituent units (A), (B), and (C) in the cyclic olefin copolymer (P) according to this embodiment is set to 100 mol%, the content of constituent unit (C) in the cyclic olefin copolymer (P) is preferably 0.1 mol% or more and 50 mol% or less, more preferably 1 mol% or more, even more preferably 3 mol% or more, and more preferably 40 mol% or less, even more preferably 30 mol% or less, even more preferably 25 mol% or less, and particularly preferably 20 mol% or less. In this embodiment, the content of constituent unit (C) is, for example, 1 H-NMR or 13 It can be measured by 13C-NMR.

[0031] When the total content of the above-mentioned constituent units (B) and (C) in the cyclic olefin copolymer (P) according to this embodiment is set to 100 mol%, the content of the above-mentioned constituent units (C) in the cyclic olefin copolymer (P) according to this embodiment is preferably 5 mol% to 95 mol%, more preferably 5 mol% to 70 mol%, and even more preferably 5 mol% to 50 mol%. In this embodiment, the content of constituent unit (B) and constituent unit (C) is, for example, 1 H-NMR or 13 It can be measured by 13C-NMR.

[0032] The copolymerization type of the cyclic olefin copolymer (P) according to this embodiment is not particularly limited, but examples include random copolymers and block copolymers. In this embodiment, from the viewpoint of obtaining a molded article with excellent transparency and heat resistance, the cyclic olefin copolymer (P) according to this embodiment is preferably a random copolymer.

[0033] The cyclic olefin copolymer (P) according to this embodiment can be manufactured by selecting appropriate conditions according to the methods described in, for example, Japanese Patent Publication No. 60-168708, Japanese Patent Publication No. 61-120816, Japanese Patent Publication No. 61-115912, Japanese Patent Publication No. 61-115916, Japanese Patent Publication No. 61-271308, Japanese Patent Publication No. 61-272216, Japanese Patent Publication No. 62-252406, Japanese Patent Publication No. 62-252407, Japanese Patent Publication No. 2007-314806, Japanese Patent Publication No. 2010-241932, etc.

[0034] The glass transition temperature (Tg) of the cyclic olefin copolymer (P) according to this embodiment, as measured by differential scanning calorimeter (DSC), is preferably 120°C to 180°C, more preferably 125°C to 170°C, and even more preferably 130°C to 165°C, from the viewpoint of further improving heat resistance while maintaining good transparency of the resulting molded article.

[0035] The intrinsic viscosity [η] (in decalin at 135°C) of the cyclic olefin copolymer (P) according to this embodiment is, for example, 0.05 to 5.0 dl / g, preferably 0.2 to 4.0 dl / g, more preferably 0.3 to 2.0 dl / g, and particularly preferably 0.4 to 1.0 dl / g. If the intrinsic viscosity [η] is above the lower limit, the mechanical strength of the resulting molded article can be improved. Furthermore, if the intrinsic viscosity [η] is below the upper limit, the moldability can be improved.

[0036] <Stabilizer (S)> The stabilizer (S) according to this embodiment has a phenolic hydroxyl group and phosphorus. Examples of stabilizers (S) having a phenolic hydroxyl group and phosphorus include mixtures of phenolic compounds and phosphorus compounds, and compounds having a phenolic hydroxyl group and phosphorus as a constituent element (also called phenol-phosphorus compounds). These stabilizers may be used individually or in combination of two or more. Among these, phenol-phosphorus compounds are preferred. The cyclic olefin copolymer composition according to this embodiment, by containing a stabilizer (S), can effectively reduce discoloration and radical generation caused by electron beam or gamma ray irradiation while maintaining good performance in terms of moldability, mechanical strength, heat resistance, and transparency of the molded article.

[0037] The content of the stabilizer (S) in the cyclic olefin copolymer composition according to this embodiment is preferably 1.5 parts by mass or less, more preferably 0.5 parts by mass or less, even more preferably 0.2 parts by mass or less, and preferably 0.005 parts by mass or more, when the content of the cyclic olefin copolymer (P) is 100 parts by mass. If the content of stabilizer (S) is below the above upper limit, the amount of radicals generated by electron beam or gamma ray irradiation in the resulting molded article can be effectively suppressed. If the content of stabilizer (S) is above the above lower limit, discoloration due to resin degradation during molding can be suppressed, and the transparency of the resulting molded article can be improved.

[0038] Phenol-phosphorus compounds are compounds that contain both a phenolic hydroxyl group and phosphorus in a single molecule. Phenol-phosphorus compounds, for example, contain a phenol structure and a trivalent phosphorus atom in a single molecule. The phenol structure may have an alkyl group with 1 to 4 carbon atoms bonded to a phenyl group. More specifically, examples include 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane and 6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-t-butyldibenzo[d,f][1,3,2]dioxaphosfepine. A commercially available phenol-phosphorus compound is Sumilizer-GP, manufactured by Sumitomo Chemical Co., Ltd. Sumilizer-GP is 6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-t-butyldibenzo[d,f][1,3,2]dioxaphosfepine.

[0039] If the stabilizer (S) is a mixture of a phenolic compound and a phosphorus compound, the ratio of the phenolic compound to the phosphorus compound contained in the stabilizer (S) is, for example, phenolic compound:phosphorus compound = 1:9 to 9:1 (molar ratio).

[0040] There are no particular restrictions on phosphorus compounds. For example, known phosphorus antioxidants can be used.

[0041] There are no particular restrictions on the phosphorus-based antioxidant; conventionally known phosphorus-based antioxidants (e.g., phosphite-based antioxidants) can be used. Specifically, triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris(nonylphenyl) phosphite, tris(dinonylphenyl) phosphite, tris(2,4-di-t-butylphenyl) phosphite, tris(2-t-butyl-4-methylphenyl) phosphite, tris(cyclohexylphenyl) phosphite, 2,2-methylenebis(4,6-di-t-butylphenyl)octyl phosphite, 9,10-dihydro-9-oxa- Monophosphenanthrene-10-oxide, 10-(3,5-di-t-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphenanthrene, 6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetrakis-t-butyldibenzo[d,f][1.3.2]dioxaphosfepine, etc. Phyto compounds; 4,4'-Butylidene-bis(3-methyl-6-t-butylphenyl-di-tridecyl phosphite), 4,4'-Isopropylidene-bis(phenyl-di-alkyl(C12~C15) phosphite), 4,4'-Isopropylidene-bis(diphenyl monoalkyl(C12~C15) phosphite), 1,1,3-Tris(2-methyl-4-di-tridecyl phosphite-5-t-butylphenyl)butane, Tetrakis(2,4-di-t-butylphenyl)-4,4'-bife Examples include diphosphite compounds such as nitrene diphosphite, cyclic neopentanetetraylbis(isodecyl phosphite), cyclic neopentanetetraylbis(nonylphenyl phosphite), cyclic neopentanetetraylbis(2,4-di-t-butylphenyl phosphite), cyclic neopentanetetraylbis(2,4-dimethylphenyl phosphite), and cyclic neopentanetetraylbis(2,6-di-t-butylphenyl phosphite).

[0042] Preferably used phosphorus compounds are trivalent organophosphorus compounds. More specifically, phosphorus compounds are compounds having a structure in which the three hydrogen atoms of phosphorous acid (P(OH)3) are each substituted by the same or different organic groups. More specifically, the phosphorus-based compound is preferably a compound represented by the following general formulas (c1), (c2), or (c3).

[0043] [ka]

[0044] In general formulas (c1), (c2), and (c3), R 1 If there are multiple instances, each independently represents an alkyl group. R 2 If there are multiple instances, each represents an aromatic group independently. R 3 This represents an alkyl group, cycloalkyl group, aryl group, or aralkyl group. X represents a single bond or a divalent linking group.

[0045] R 1 The alkyl group preferably has 1 to 10 carbon atoms, and more preferably a t-butyl group. R 2 Examples of aromatic groups include phenyl groups, naphthyl groups, and groups in which these are substituted with alkyl groups, etc. R 3 The number of carbon atoms is preferably 1 to 30, more preferably 3 to 20, and even more preferably 6 to 18. R 3 Preferably, the substituent is an aryl group or an aralkyl group, and more preferably an aralkyl group. These aryl groups or aralkyl groups may be further substituted with substituents (for example, alkyl groups or hydroxyl groups having 1 to 6 carbon atoms). When X is a divalent linking group, specific examples include alkylene groups (such as methylene groups) and ether groups (-O-). X is preferably a single bond. Other commercially available options include the Irgafos 168 (manufactured by BASF).

[0046] For phosphorus compounds, one type may be used, or two or more types may be used.

[0047] Regarding phenolic compounds, for example, acrylate-based phenolic compounds described in Japanese Patent Publication No. 63-179953 and Japanese Patent Publication No. 1-168643, such as 2-t-6-(3-t-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 2,4-di-tertiary amyl-6-(1-(3,5-di-tertiary amyl-2-hydroxyphenyl)ethyl)phenyl acrylate; 2,6-di-t-4-methylphenol, 2,6-di-t-4-ethylphenol, octadecyl-3-(3,5-di-t-4- Hydroxyphenyl)propionate, 2,2'-methylene-bis(4-methyl-6-t-phenol), 4,4'-butylidene-bis(6-tm-cresol), 4,4'-thiobis(3-methyl-6-t-phenol), bis(3-cyclohexyl-2-hydroxy-5-methylphenyl)methane, 3,9-bis(2-(3-(3-t-4-hydroxy-5-methylphenyl)propionyloxy)-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane, 1,1,3-tris( 2-methyl-4-hydroxy-5-t-phenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-4-hydroxybenzyl)benzene, tetrakis(methylene-3-(3',5'-di-t-4'-hydroxyphenylpropionate)methane [i.e., pentaerythrimethyl-tetrakis(3-(3,5-di-t-4-hydroxyphenylpropionate)], triethylene glycol bis(3-(3-t-4-hydroxy-5-methylphenyl)propionate), tocopherol, etc. Lukyl-substituted phenolic compounds; triazine group-containing phenolic compounds such as 6-(4-hydroxy-3,5-di-t-anilino)-2,4-bisoctylthio-1,3,5-triazine, 6-(4-hydroxy-3,5-dimethylanilino)-2,4-bisoctylthio-1,3,5-triazine, 6-(4-hydroxy-3-methyl-5-t-anilino)-2,4-bisoctylthio-1,3,5-triazine, and 2-octylthio-4,6-bis-(3,5-di-t-4-oxyanilino)-1,3,5-triazine;6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetrakis-t-butyldibenzo[d,f][1.3.2]dioxaphosfepine, etc., can be used. Other commercially available products include Irganox 1010, Irganox 1035, Irganox 1076, Irganox 1098, Irganox 1135, Irganox 1330, Irganox 1520L, Irganox 245, Irganox 259, Irganox 3144, Irganox 565 (all manufactured by BASF), and Sumilizer GS(F) (all manufactured by Sumitomo Chemical Co., Ltd.).

[0048] Regarding phenolic compounds, one type may be used, or two or more types may be used.

[0049] <Other ingredients> The molded article or cyclic olefin copolymer composition according to this embodiment may optionally contain known additives as optional components, provided that they do not impair the good physical properties of the molded article according to this embodiment. Examples of additives that can be included are higher fatty acid metal salts, antioxidants, ultraviolet absorbers, hindered amine compounds, hydrochloric acid absorbers, metal deactivators, antistatic agents, antifogging agents, lubricants, slip agents, nucleating agents, plasticizers, flame retardants, hydrophilic stabilizers, etc., in amounts that do not impair the objectives of the present invention, and the proportion of these additives is appropriate.

[0050] The cyclic olefin copolymer composition according to this embodiment may optionally contain a hydrophilic stabilizer. Including a hydrophilic stabilizer is preferable because it can suppress the deterioration of optical performance under high temperature and high humidity conditions. The hydrophilic stabilizer is preferably a fatty acid ester of a fatty acid and a polyhydric alcohol. More preferably, it is a fatty acid ester of a fatty acid and a polyhydric alcohol having one or more ether groups.

[0051] Examples of fatty acid esters include monoglycerin fatty acid esters, diglycerin fatty acid esters, triglycerin fatty acid esters, pentaerythritol monostearate, pentaerythritol distearate, and pentaerythritol tristearate. A fatty acid ester of a fatty acid and a polyhydric alcohol having one or more ether groups is an ester of a fatty acid and a polyhydric alcohol having one or more ether groups. Note that the ether groups of the polyhydric alcohol do not include the ether groups in the ester group. Examples of polyhydric alcohols having one or more ether groups include monoglycerin, diglycerin, triglycerin, tetraglycerin, and sorbitan. In this embodiment, the fatty acid ester preferably includes monoglycerin fatty acid ester, diglycerin fatty acid ester, and triglycerin fatty acid ester. Diglycerin fatty acid ester is obtained in which at least one of the four hydroxyl groups contained in diglycerin is esterified with a fatty acid.

[0052] Examples of fatty acids include saturated fatty acids such as butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, capric acid, lauric acid, myristic acid, palmitic acid, and stearic acid; monounsaturated fatty acids such as crotonic acid, myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, gadolic acid, and eicosenoic acid; diunsaturated fatty acids such as linoleic acid, eicosadienoic acid, and docosadenoic acid; triunsaturated fatty acids such as linolenic acid, pinolenic acid, eleostearic acid, and eicosatrienoic acid; and tetraunsaturated fatty acids such as stearidonic acid, arachidonic acid, and eicosatetraenoic acid.

[0053] Examples of diglycerin fatty acid esters include diglycerin monocaprylate, diglycerin dicaprylate, diglycerin monocaprate, diglycerin dicaprate, diglycerin monolaurate, diglycerin dilaurate, diglycerin monomyristate, diglycerin dimyristate, diglycerin monopalmitate, diglycerin dipalmitate, diglycerin monostearate, diglycerin distearate, diglycerin monobehenate, and diglycerin dibehenate; and diglycerin unsaturated fatty acid esters such as diglycerin monooleate and diglycerin diolate; and one or more selected from these can be used in combination. In this embodiment, the diglycerin fatty acid ester is preferably an ester of diglycerin with a saturated or unsaturated fatty acid having 12 to 18 carbon atoms selected from the above.

[0054] Furthermore, from the viewpoint of the effects of this embodiment, it is preferable to contain diglycerin unsaturated fatty acid esters as the main component, and more preferably diglycerin monooleate as the main component. The diglycerin skeleton is hydrophilic, and the fatty acids improve compatibility with the resin, so transparency is maintained and heat and humidity resistance is excellent.

[0055] The cyclic olefin copolymer composition according to this embodiment may contain at least one diglycerin fatty acid ester. Preferred embodiments of the at least one diglycerin fatty acid ester include a monoester alone or a combination of a monoester and a diester.

[0056] Triglycerol fatty acid esters are esters of fatty acids and triglycerol. The triglycerol fatty acid ester according to this embodiment is obtained in which at least one of the five hydroxyl groups contained in triglycerol is esterified with a fatty acid.

[0057] Triglycerin fatty acid esters include triglycerin monocaprylate, triglycerin dicaprylate, triglycerin tricaprylate, triglycerin monocaprate, triglycerin dicaprate, triglycerin tricaprate, triglycerin monolaurate, triglycerin dilaurate, triglycerin trilaurate, triglycerin monomyristate, triglycerin dimyristate, triglycerin trimyristate, triglycerin monopalmitate, triglycerin dipalmitate Examples include triglycerin saturated fatty acid esters such as triglycerin tripalmylate, triglycerin monostearate, triglycerin distearate, triglycerin tristearate, triglycerin monobehenate, triglycerin dibehenate, and triglycerin tripehenate; and triglycerin unsaturated fatty acid esters such as triglycerin monooleate, triglycerin dioleate, and triglycerin trioleate; and one or more selected from these can be used in combination. The triglycerin fatty acid ester according to this embodiment preferably comprises an ester of triglycerin with a saturated or unsaturated fatty acid having 8 to 24 carbon atoms, and more preferably comprises an ester of triglycerin with a saturated or unsaturated fatty acid having 12 to 18 carbon atoms.

[0058] Examples of triglycerin fatty acid esters according to this embodiment include monoesters alone, mixtures of monoesters and diesters, or mixtures of monoesters, diesters, and triesters. Examples of such triglycerol fatty acid esters include compounds described in Japanese Patent Publication No. 2006-232714, Japanese Patent Publication No. 2002-275308, Japanese Patent Publication No. 10-165152, and the like. Examples of commercially available hydrophilic stabilizers according to this embodiment include Rikemar DO-100 (manufactured by Riken Vitamin Co., Ltd.) and Excepal PE-MS (manufactured by Kao Corporation). In the cyclic olefin copolymer composition according to this embodiment, the lower limit of the hydrophilic stabilizer content is preferably 0.05 parts by mass or more, and more preferably 0.4 parts by mass or more, per 100 parts by mass of the cyclic olefin copolymer (P). The upper limit of the hydrophilic stabilizer content is preferably 3.0 parts by mass or less, more preferably 2.5 parts by mass or less, and even more preferably 1.2 parts by mass or less, per 100 parts by mass of the cyclic olefin copolymer (P).

[0059] <Method for producing cyclic olefin copolymer compositions> The cyclic olefin copolymer composition according to this embodiment can be obtained by methods such as: melt-kneading a cyclic olefin copolymer (P), a stabilizer (S), and optionally other components other than the cyclic olefin copolymer (P) and stabilizer (S) using a known kneading apparatus such as an extruder and a Banbury mixer; dissolving the cyclic olefin copolymer (P), a stabilizer (S), and optionally other components other than the cyclic olefin copolymer (P) and stabilizer (S) in a common solvent and then evaporating the solvent; or adding a solution of the cyclic olefin copolymer (P), a stabilizer (S), and optionally other components other than the cyclic olefin copolymer (P) and stabilizer (S) to a poor solvent and precipitating them.

[0060] 2. Molded body The molded article according to this embodiment contains the cyclic olefin copolymer composition according to this embodiment. The molded article according to this embodiment contains the cyclic olefin copolymer composition according to this embodiment, and therefore exhibits an excellent balance of transparency, heat resistance, and gamma-ray or electron-ray resistance. This molded article shows minimal discoloration due to electron-ray or gamma-ray irradiation. The molded article according to this embodiment can reduce the amount of radicals generated by electron beam or gamma ray irradiation. Therefore, the molded article according to this embodiment can reduce the risk of deterioration of the contents.

[0061] Furthermore, from the viewpoint of further improving the balance of radiation resistance, heat resistance, and transparency performance, the content of the cyclic olefin copolymer (P) in the molded article according to this embodiment is preferably 50% to 100% by mass, more preferably 70% to 100% by mass, even more preferably 80% to 100% by mass, and particularly preferably 90% to 100% by mass, when the total mass of the molded article is considered to be 100% by mass.

[0062] The method for molding the cyclic olefin copolymer composition according to this embodiment to obtain a molded article is not particularly limited, and known methods can be used. Depending on the application and shape, for example, extrusion molding, injection molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, vacuum molding, powder slush molding, calendering, foam molding, etc., can be applied. Among these, injection molding is preferred from the viewpoint of moldability and productivity. Furthermore, the molding conditions are appropriately selected depending on the intended use or molding method, but for example, the resin temperature in injection molding is usually appropriately selected within the range of 150°C to 400°C, preferably 200°C to 350°C, and more preferably 230°C to 330°C.

[0063] Furthermore, by irradiating the molded body manufactured as described above with gamma rays or electron beams, for example, a gamma-ray or electron-beam-irradiated molded body (a molded body irradiated with gamma rays or electron beams) can be obtained. This molded body is clean because it has been sterilized or disinfected by irradiation, and discoloration and radical generation are suppressed. The irradiation dose is not particularly limited, but is usually 5 to 100 kilogray (kGy), preferably 10 to 80 kilogray.

[0064] Examples of molded articles according to this embodiment include medical devices and food utensils. Examples of medical devices include syringes used in syringe barrels (hereinafter referred to as syringes) and syringes filled with drug solutions or medications (hereinafter also referred to as pre-filled syringes), storage containers used in storage containers filled with drug solutions or medications (hereinafter also referred to as drug solution storage containers), and biochips.

[0065] Here, a pre-filled syringe is a syringe-shaped preparation that is pre-filled with a drug solution or medication. There are single-chamber types that are filled with one type of liquid and double-chamber types that are filled with two types of medication. Most pre-filled syringes are single-chamber types, but double-chamber types include liquid-powder preparations consisting of powder and its solvent, and liquid-liquid preparations consisting of two types of liquid. An example of a solution in a single-chamber type is heparin solution. Examples of syringes used for pre-filled syringes and pre-filled syringes include prefillable syringes, pre-filled syringes for vaccines, pre-filled syringes for anticancer drugs, and needleless syringes.

[0066] Examples of drug solution storage containers include wide-mouth bottles, narrow-mouth bottles, medicine bottles, vials, infusion bottles, bulk containers, petri dishes, test tubes, and analytical cells. More specifically, examples include liquid, powder, or solid drug containers such as ampoules, press-through packages, infusion bags, drip drug containers, and eye drop containers; sample containers such as test tubes, blood collection tubes, and specimen containers for blood tests; analytical containers such as ultraviolet testing cells; sterilization containers for medical instruments such as scalpels, forceps, gauze, and contact lenses; medical devices such as disposable syringes and pre-filled syringes; laboratory equipment such as beakers, vials, ampoules, and test tube flasks; and housings for artificial organs.

[0067] Examples of food-related utensils include food containers, food trays, and food packaging materials.

[0068] The molded article according to this embodiment has good transparency. Transparency is evaluated by internal haze. Furthermore, it is preferable that the light transmittance is also good. Light transmittance is defined by spectral light transmittance or total light transmittance depending on the application.

[0069] When use is expected across the entire spectrum of light or multiple wavelengths, good total light transmittance is necessary. The total light transmittance without an anti-reflective coating on the surface should be 85% or higher, preferably 88-93%. A total light transmittance of 85% or higher ensures the required amount of light. Known methods can be used to measure total light transmittance, and the measuring equipment is not limited. For example, in accordance with ASTM D1003, the cyclic olefin copolymer composition according to this embodiment is formed into a 3 mm thick sheet, and the total light transmittance of the sheet obtained by forming the cyclic olefin copolymer composition according to this embodiment is measured using a haze meter.

[0070] Furthermore, the molded article according to this embodiment exhibits excellent light transmittance for light with wavelengths of 450 nm to 800 nm. Furthermore, by applying a known anti-reflective coating to the surface, the light transmittance can be further improved.

[0071] The embodiments of the present invention have been described above, but these are merely examples, and various other configurations can also 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. [Examples]

[0072] The present invention will be described in detail below based on examples, but the present invention is not limited to these examples.

[0073] <Manufacturing of cyclic olefin copolymers> [Manufacturing Example 1] In a 500 ml glass reaction vessel equipped with a stirring device, nitrogen was passed through as an inert gas at a flow rate of 100 Nl / hr for 30 minutes, followed by 245 mL of cyclohexane and tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene (14.4 mmol, hereinafter also referred to as tetracyclododecene) and benzonorbornadiene (5.0 mmol, hereinafter also referred to as BNBD) were added. The polymerization solvent was then stirred at 600 rpm while the solvent temperature was raised to 50°C. After the solvent temperature reached the predetermined temperature, the flow gas was switched from nitrogen to ethylene, and ethylene was supplied to the reaction vessel at a rate of 50 Nl / hr and hydrogen at 2 Nl / hr. After 10 minutes, MMAO (0.45 mmol) and a catalyst (0.0015 mmol) prepared by the method described in paragraph 0112 of Japanese Patent Application Publication No. 2010-241932 were added to the glass reaction vessel to start polymerization. After 10 minutes, 5 ml of isobutyl alcohol was added to stop the polymerization, yielding a polymerization solution containing a copolymer of ethylene, tetracyclododecene, and BNBD. The polymerization solution was then transferred to a separately prepared 2 L beaker, and 5 ml of concentrated hydrochloric acid and a stirring bar were added. The mixture was then contacted under strong stirring for 2 hours to perform decalcification. The decalcified polymerization solution was added to a beaker containing approximately three times the volume of acetone under stirring to precipitate the copolymer. The precipitated copolymer 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 0.7 g of white powdery ethylene-tetracyclododecene-BNBD copolymer. Based on the above, a cyclic olefin copolymer (P-1) was obtained. The molar ratio of ethylene, tetracyclododecene, and BNBD in the cyclic olefin copolymer (P-1) is ethylene / tetracyclododecene / BNBD = 66 / 30 / 4 (mol%). The glass transition temperature (Tg) of the cyclic olefin copolymer (P-1) is 145°C, and the intrinsic viscosity [η] is 0.55 dl / g. Here, benzonorbornadiene is represented by the following formula (1).

[0074] [ka]

[0075] <Examples 1-3 and Comparative Examples 1-6> To 100 parts by mass of the obtained cyclic olefin copolymer (P-1), the following stabilizers were added in the proportions shown in Table 1. Here, each stabilizer was dissolved in acetone before use. Next, the mixture was heated at 120°C using a vacuum dryer to remove the acetone component and obtain the respective cyclic olefin copolymer compositions. (Stabilizer) Phenolic compound 1: Irganox 1010 (manufactured by BASF) Phenolic compound 2: Irganox 1076 (manufactured by BASF) Phosphorus compound 1: Irgafos168 (manufactured by BASF) Phenol-phosphorus compound 1: Sumilizer-GP (manufactured by Sumitomo Chemical Co., Ltd.) Hindered amine compound 1: Tinubin 622LD (manufactured by BASF)

[0076] In each example and comparative example, various physical properties were measured or evaluated by the following methods, and the results are shown in Table 1.

[0077] [Method for measuring the content of each constituent unit of a cyclic olefin copolymer] Ethylene, tetracyclo[4.4.0.1 2,5 .1 7,10 The content of ]-3-dodecene and cyclic olefins having aromatic rings was measured using a JEOL Corporation "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 Cumulative number of times: 6,000 to 16,000 Measurement temperature: 120℃ Measurements were taken under the conditions described above. 13The compositions of ethylene, tetracyclododecene, and cyclic olefins containing aromatic rings were quantified using 1C-NMR spectroscopy.

[0078] [Glass transition temperature Tg (°C)] The glass transition temperature (Tg) of a cyclic olefin copolymer was measured under an N2 (nitrogen) atmosphere using a Shimadzu Science DSC-6220. The cyclic olefin copolymer was heated from room temperature to 200°C at a heating rate of 10°C / min, held for 5 minutes, and then cooled to -20°C at a cooling rate of 10°C / min, held for 5 minutes. The glass transition temperature (Tg) of the cyclic olefin copolymer was then determined from the endothermic curve obtained when heating to 200°C at a heating rate of 10°C / min.

[0079] [Intrinsic viscosity [η]] Using a mobile viscometer (Rigousha, type VNR053U), 0.25-0.30 g of 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 according to ASTM J1601, and the intrinsic viscosity [η] of the cyclic olefin copolymer was determined by extrapolating the ratio of this specific viscosity to the concentration to a concentration of 0.

[0080] [Oxidation Induction Time (OIT) Test (Heat Resistance Evaluation)] The obtained cyclic olefin copolymer composition was dried at 120°C for 12 hours using a vacuum dryer. After drying, 5 mg of the evaluation sample was weighed out, heated to 220°C under a nitrogen atmosphere, and then oxidized by flowing oxygen at 20°C / min. The oxidation onset time (minutes) on the DSC was measured. The values ​​in Table 1 indicate the time (minutes) from when the oxygen flow started until the exothermic peak began to rise.

[0081] <Method for manufacturing evaluation test specimens> [Press forming] Using a vacuum heat press, the process was performed at 270°C, with 20 de-bubbling cycles and a pressure of 10 kg / cm². 2 Under conditions of 30 minutes in total, the obtained cyclic olefin copolymer composition was pressed onto a 30 × 30 × 1 mm thick plate to obtain a test specimen.

[0082] [Gamma ray irradiation] The test specimens obtained as described above were irradiated with 50 kGy of gamma rays.

[0083] [Evaluation: Radical levels 5 days after gamma ray irradiation] The amount of radicals in the sample 5 days after gamma ray irradiation was measured by electron spin resonance (ESR). Specifically, a specimen was cut out 5 days after irradiation with a gamma ray dose of 50 kGy, placed in a test tube (details below), and its ESR spectrum was measured under the following conditions. • Equipment: JEOL Electronic Spin Resonance Spectrometer JES-TE200 ·Resonance frequency: 9.2GHz • Microwave input: 0.1~2.0mW • Sweep range: 30mT Modulation amplitude: 1mT • Standard sample: TEMPOL-Free Rasical (manufactured by Tokyo Chemical Industry Co., Ltd.) ·Measurement temperature: room temperature • Measurement atmosphere: Air Under the above conditions, the amount of radicals was measured, and the amount of organic radicals per 1 mg of test specimen (spins / mg) was determined using a calibration curve created from the ESR spectra of a standard sample of known concentration (TEMPOL-free radicals).

[0084] [Evaluation: Hue immediately after gamma ray irradiation] The color of the sample was visually evaluated 5 days after gamma ray irradiation. Regarding color, especially when considering its use as a medical container, yellow is avoided because it gives patients an impression of uncleanliness. Therefore, green and blue are preferable to yellow, but colorless and transparent is the most preferable.

[0085] [Table 1]

Claims

1. A cyclic olefin copolymer composition comprising a cyclic olefin copolymer (P) and a stabilizer (S), The cyclic olefin copolymer (P) comprises a constituent unit (A) derived from an α-olefin having 2 to 20 carbon atoms, a constituent unit (B) derived from a cyclic olefin without an aromatic ring, and a constituent unit (C) derived from a cyclic olefin having an aromatic ring. The stabilizer (S) has a phenolic hydroxyl group and phosphorus, For use in medical devices or food processing equipment, The content of the stabilizer (S) in the cyclic olefin copolymer composition is 0.005 parts by mass or more and 0.2 parts by mass or less, when the content of the cyclic olefin copolymer (P) is 100 parts by mass. The cyclic olefin having the aromatic ring comprises one or more compounds selected from the group consisting of the compound represented by the following formula (C-1), the compound represented by the following formula (C-2), and the compound represented by the following formula (C-3). A cyclic olefin copolymer composition in which, when the total content of constituent units (A), (B), and (C) in the cyclic olefin copolymer (P) is 100 mol%, the content of constituent unit (A) in the cyclic olefin copolymer (P) is 10 mol% or more and 80 mol% or less. 【Chemistry 2】 (In the above formula (C-1), n and q are each independently 0, 1, or 2, and R １１ , １０ , １４ , １０ , １３ , １６ , １２ , １６ , １７ , １５ , １７ , １４ , １１ , １３ , １０ , １２ , １７ , １６ , １７ , １６ , １５ ~R １７ are each independently a halogen atom excluding a hydrogen atom and 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 one of R １０ ~R １７ 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<00​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​ 【Transformation 3】 (In the above formula (C-2), n and m are independently 0, 1, or 2, and q is 1, 2, or 3, 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 have a double bond, and the monocycle or polycycle may be an aromatic ring. 【Chemistry 4】 (In the above formula (C-3), q is 1, 2 or 3, 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.

2. The cyclic olefin copolymer composition according to claim 1, wherein the α-olefin having 2 to 20 carbon atoms is a linear α-olefin having 2 to 4 carbon atoms.

3. The cyclic olefin copolymer composition according to claim 2, wherein the α-olefin having 2 to 20 carbon atoms is ethylene.

4. The cyclic olefin copolymer composition according to any one of claims 1 to 3, wherein the cyclic olefin having an aromatic ring comprises one or more compounds selected from the group consisting of compounds represented by the following formula (C-1) and compounds represented by the following formula (C-3).

5. The α-olefin having 2 to 20 carbon atoms is a linear α-olefin having 2 to 4 carbon atoms, The cyclic olefin copolymer composition according to claim 1, wherein the cyclic olefin having the aromatic ring comprises one or more compounds selected from the group consisting of compounds represented by the following formula (C-1) and compounds represented by the following formula (C-3).

6. The α-olefin having 2 to 20 carbon atoms is ethylene, The cyclic olefin copolymer composition according to claim 1 or 2, wherein the cyclic olefin having the aromatic ring comprises one or more compounds selected from the group consisting of compounds represented by the following formula (C-1) and compounds represented by the following formula (C-3).

7. In the cyclic olefin copolymer composition according to any one of claims 1 to 6, A cyclic olefin copolymer composition wherein the stabilizer (S) comprises at least one selected from a mixture of a phenolic compound and a phosphorus compound and a compound having a phenolic hydroxyl group and phosphorus as a constituent element.

8. In the cyclic olefin copolymer composition according to claim 7, The stabilizer (S) comprises a mixture of a phenolic compound and a phosphorus compound. A cyclic olefin copolymer composition in which the ratio of the phenol compound to the phosphorus compound contained in the stabilizer (S) is phenol compound:phosphorus compound = 1:9 to 9:1 (molar ratio).

9. In the cyclic olefin copolymer composition according to any one of claims 1 to 8, A cyclic olefin copolymer composition comprising a cyclic olefin that lacks the aromatic ring, the compound represented by the following formula (B-1). 【Chemistry 1】 (In the above formula [B-1], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, R １ ~R １８ And R ａ and R ｂ Each is independently a hydrogen atom, a halogen atom, or a hydrocarbon group which may be substituted with a halogen atom, and R １５ ~R １８ These may be bonded to each other to form a monocycle or polycycle, and the monocycle or polycycle may have a double bond, and R １５ and R １６ And, or R １７ and R １８ They may form alkylidene groups. (However, they do not contain aromatic rings.)

10. In the cyclic olefin copolymer composition according to any one of claims 1 to 9, A cyclic olefin copolymer composition comprising the cyclic olefin having the aromatic ring, wherein the cyclic olefin comprises at least one selected from benzonorbornane, indenenorbornene, and methylphenylnorbornene.

11. A molded article comprising the cyclic olefin copolymer composition according to any one of claims 1 to 10.

12. In the molded article according to claim 11, A molded body that is a medical device or a food utensil.

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