CYCLIC OLEFIN-BASED COPOLYMER, CYCLIC OLEFIN-BASED COPOLYMER COMPOSITION, MOLDED ARTICLE, AND MEDICAL CONTAINER

Abstract

Described is a cyclic olefin-based copolymer has a constitutional unit (A) derived from an α-olefin having 2 to 20 carbon atoms, a constitutional unit (B) derived from a cyclic olefin without an aromatic ring, and a constitutional unit (C) derived from a cyclic olefin having an aromatic ring. Also described is a medical container containing a cyclic olefin-based copolymer having a constitutional unit (A) derived from an α-olefin having 2 to 20 carbon atoms, a constitutional unit (B) derived from a cyclic olefin without an aromatic ring, and a constitutional unit (C) derived from a cyclic olefin having an aromatic ring.

Claims

1. A medical container comprising: a cyclic olefin-based copolymer having a constitutional unit (A) derived from an α-olefin having 2 to 20 carbon atoms, a constitutional unit (B) derived from a cyclic olefin without an aromatic ring, and a constitutional unit (C) derived from a cyclic olefin having an aromatic ring.

2. The medical container according to claim 1, wherein in a case where a total content of the constitutional unit (A), the constitutional unit (B), and the constitutional unit (C) in the cyclic olefin-based copolymer is 100 mol %, a content of the constitutional unit (C) in the cyclic olefin-based copolymer is equal to or greater than 0.1 mol % and equal to or smaller than 50 mol %.

3. The medical container according to claim 1, wherein in a case where a total content of the constitutional unit (B) and the constitutional unit (C) in the cyclic olefin-based copolymer is 100 mol %, a content of the constitutional unit (C) in the cyclic olefin-based copolymer is equal to or greater than 5 mol % and equal to or smaller than 95 mol %.

4. The medical container according to claim 1, wherein in a case where a total content of the constitutional unit (A), the constitutional unit (B), and the constitutional unit (C) in the cyclic olefin-based copolymer is 100 mol %, a content of the constitutional unit (A) in the cyclic olefin-based copolymer is equal to or greater than 10 mol % and equal to or smaller than 80 mol %.

5. The medical container according to claim 1, wherein the cyclic olefin without an aromatic ring contains a compound represented by the following Formula (B-1), ##STR00027## in Formula [B-1], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, R.sup.1 to R.sup.18, R.sup.a, and R.sup.b each independently represent a hydrogen atom, a halogen atom, or a hydrocarbon group which maybe substituted with a halogen atom, R.sup.15 to R.sup.18 may form a monocyclic ring or a polycyclic ring by being bonded to each other, the monocyclic ring or the polycyclic ring may have a double bond, R.sup.15 and R.sup.16 or R.sup.17 and R.sup.18 may form an alkylidene group, and the compound represented by Formula [B-1] does not have an aromatic ring.

6. The medical container according to claim 1, wherein the cyclic olefin that has an aromatic ring contains one kind of compound or two or more kinds of 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), ##STR00028## in Formula (C-1), n and q each independently represent 0, 1, or 2, R.sup.1 to R.sup.17 each independently represent a hydrogen atom, a halogen atom except for a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms that may be substituted with a halogen atom except for a fluorine atom, one of R.sup.10 to R.sup.17 is a bond, in a case where q=0, R.sup.10 and R.sup.11, R.sup.11 and R.sup.12, R.sup.12 and R.sup.13, R.sup.13 and R.sup.14, R.sup.14 and R.sup.15, or R.sup.15, and R.sup.10 may form a monocyclic ring or a polycyclic ring by being bonded to each other, in a case where q=1 or 2, R.sup.10 and R.sup.11, R.sup.11 and R.sup.17, R.sup.17 and R.sup.17, R.sup.17 and R.sup.12, R.sup.12 and R.sup.13, R.sup.13 and R.sup.14, R.sup.14 and R.sup.15, R.sup.15 and R.sup.16, R.sup.16 and R.sup.16, or R.sup.16 and R.sup.10 may form a monocyclic ring or a polycyclic ring by being bonded to each other, the monocyclic ring or the polycyclic ring may have a double bond, and the monocyclic ring or the polycyclic ring may be an aromatic ring, ##STR00029## in Formula (C-2), n and m each independently represent 0, 1, or 2, q represents 1, 2, or 3, R.sup.18 to R.sup.31 each independently represent a hydrogen atom, a halogen atom except for a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms that maybe substituted with a halogen atom except for a fluorine atom, in a case where q=1, R.sup.28 and R.sup.29, R.sup.29 and R.sup.30, or R.sup.30 and R.sup.31 may form a monocyclic ring or a polycyclic ring by being bonded to each other, in a case where q=2 or 3, R.sup.28 and R.sup.28, R.sup.28 and R.sup.29, R.sup.29 and R.sup.30, R.sup.30 and R.sup.31, or R.sup.31 and R.sup.31 may form a monocyclic ring or a polycyclic ring by being bonded to each other, the monocyclic ring or the polycyclic ring may have a double bond, and the monocyclic ring or the polycyclic ring may be an aromatic ring, ##STR00030## in Formula (C-3), q represents 1, 2, or 3, R.sup.32 to R.sup.39 each independently represent a hydrogen atom, a halogen atom except for a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms that may be substituted with a halogen atom except for a fluorine atom, in a case where q=1, R.sup.36 and R.sup.37, R.sup.37 and R.sup.38, or R.sup.38 and R.sup.39 may form a monocyclic ring or a polycyclic ring by being bonded to each other, in a case where q=2 or 3, R.sup.36 and R.sup.36, R.sup.36 and R.sup.37, R.sup.37 and R.sup.38, R.sup.38 and R.sup.39, or R.sup.39 and R.sup.39 may form a monocyclic ring or a polycyclic ring by being bonded to each other, the monocyclic ring or the polycyclic ring may have a double bond, and the monocyclic ring or the polycyclic ring may be an aromatic ring.

7. The medical container according to claim 1, wherein a glass transition temperature (Tg) of the cyclic olefin-based copolymer measured using a differential scanning calorimeter(DSC) is equal to or higher than 120° C. and equal to or lower than 180° C.

8. The medical container according to claim 1, wherein the cyclic olefin having an aromatic ring contains at least one kind of compound selected from benzonorbornadiene, indene norbornene, and methyl phenyl norbornene.

9. The medical container according to claim 1 that is a syringe or a liquid medicine storage container.

Description

EXAMPLES AND COMPARATIVE EXAMPLES ACCORDING TO FIRST INVENTION

[0264] Hereinafter, the first invention of the present application will be specifically described based on examples. However, the first invention of the present application is not limited to the examples.

[0265] <Manufacturing of Cyclic Olefin-Based Copolymer>

Manufacturing Example 1

[0266] As an inert gas, nitrogen was allowed to flow in a reaction container, which included a stirring device, had a volume of 500 ml, and was made of glass, for 30 minutes at a flow rate of 100 Nl/hr. Then, cyclohexane, tetracyclo[4.4.0.1.sup.2,5.1.sup.7,10]-3-dodecene (40 mmol, hereinafter, referred to as tetracyclododecene as well) and benzonorbornadiene (88 mmol, hereinafter, referred to as BNBD as well) were added to the container. Thereafter, the polymerization solvent was stirred at a rotation speed of 600 rpm, and in this state, the solvent temperature was increased to 50° C. After the solvent temperature reached a predetermined temperature, the gas flowing in the reaction container was changed to ethylene from nitrogen. Ethylene and hydrogen were allowed to flow in the reaction container at supply rates of 50 Nl/hr and 2.0 Nl/hr respectively. After 10 minutes, PMAO (1.8 mmol) and the catalyst (0.0030 mmol) prepared by the method described in paragraph “0112” in Japanese Unexamined Patent Publication No. 2010-241932 were added to the reaction container made of glass such that polymerization was initiated.

[0267] After 10 minutes, 5 ml of isobutyl alcohol was added thereto so as to stop the polymerization, thereby obtaining a polymerized solution containing a copolymer of ethylene, tetracyclododecene, and BNBD. Subsequently, the polymerized solution was moved to a beaker having a volume of 2 L that was additionally prepared, 5 ml of concentrated hydrochloric acid and a stirrer were added thereto, and a deliming operation was performed by bringing the copolymer into contact with the hydrochloric acid for 2 hours in a state of strongly stirring the solution. In a state of being stirred, the polymerized solution having undergone deliming was added to a beaker containing acetone that was about three times the volume of the polymerized solution, such that the copolymer was precipitated. The precipitated copolymer was separated from the filtrate by filtration. The obtained polymer containing the solvent was dried under reduced pressure for 10 hours at 130° C., thereby obtaining 4.58 g of a white powder-like ethylene.tetracyclododecene.BNBD copolymer.

[0268] In this way, a cyclic olefin-based copolymer (P-1) was obtained.

Manufacturing Examples 2 to 12

[0269] Cyclic olefin-based copolymers (P-2) to (P-11) described in Table 1 were obtained by performing the same operation as that in Manufacturing Example 1, except that the content of each of the constitutional units constituting the cyclic olefin-based copolymers was adjusted to the value described in Table 1.

[0270] Furthermore, a cyclic olefin-based copolymer (P-12) was prepared by mixing the cyclic olefin-based copolymer (P-10) with the cyclic olefin-based copolymer (P-11) at a mass ratio of 1:1 (Manufacturing Example 12).

[0271] In Table 1, BNBD means benzonorbornadiene represented by the following Formula (1), and IndNB means indene norbornene represented by the following Formula (2) . MePhNB means methyl phenyl norbornene represented by the following Formula (3).

##STR00025##

TABLE-US-00001 TABLE 1 Cyclic olefin-based copolymer P-1 P-2 P-3 P-4 P-5 P-6 P-7 P-8 P-9 P-10 P-11 Cyclic olefin having aromatic BNBD BNBD BNBD IndNB IndNB IndNB MePhNB MePhNB MePhNB N/A BNBD ring from which constitutional unit (C) is derived Composition Constitutional unit 63.0 64.1 61.0 64.4 63.3 66.4 63.4 60. 0 55.1 65.0 62.0 (A) (derived from ethylene) (mol %) Constitutional unit 21.0 28.1 8.0 25.3 21.3 11.5 26.7 20.0 10.4 35.0 0.0 (B) (derived from tetracyclododecene) (mol %) Constitutional unit 16.0 7.8 31.0 10.3 15.4 22.1 9.9 20.0 34.5 0.0 38.0 (C) (mol %)

TABLE-US-00002 TABLE 2 Compar- ative Compar- Example Example Example Example Example Example Example Example Example Exam- ative 1 2 3 4 5 6 7 8 9 ple 1 Example 2 Cyclic olefin-based copolymer P-1 P-2 P-3 P-4 P-5 P-6 P-7 P-8 P-9 P-10 P-12 Cyclic olefin having aromatic BNBD BNBD BNBD IndNB IndNB IndNB MePhNB MePhNB MePhNB N/A ring from which constitutional unit (C) is derived Composition Constitutional unit 63.0 64.1 61.0 64.4 63.3 66.4 63.4 60.0 55.1 65.0 (A) (derived from ethylene) (mol %) Constitutional unit 21.0 28.1 8.0 25.3 21.3 11.5 26.7 20.0 10.4 35.0 (B) (derived from tetracyclododecene) (mol %) Constitutional unit 16.0 7.8 31.0 10.3 15.4 22.1 9.9 20.0 34.5 0.0 (C) (mol %) Tg (° C.) 147 140 148 152 154 143 143 152 165 150 130, 150 [n] (dl/g) 0.47 0.45 0.78 0.50 0.44 0.41 0.45 0.45 0.45 0.45 0.51 Refractive index (nd) 1.56 1.55 1.57 1.55 1.56 1.56 1.55 1.55 1.56 1.54 — Abbe number 46 51 39 49 47 43 51 47 43 56 — Inner haze O O O O O O O O O O X Birefringence B A B A B B A B B A —

Examples 1 to 9 and Comparative Examples 1 and 2

[0272] In each of the examples and the comparative examples, various physical properties were measured or evaluated by the following method. The obtained results are shown in Table 2.

[0273] [Method for Measuring Content of each of Constitutional Units Constituting Cyclic Olefin-Based Copolymer]

[0274] The content of ethylene, tetracyclo[4.4.0.1.sup.2,5.1.sup.7,10]-3-dodecene, and the cyclic olefin having an aromatic ring was measured under the following conditions by using a nuclear magnetic resonance spectrometer “ECA 500” manufactured by JEOL Ltd.

[0275] Solvent: deuterated tetrachloroethane

[0276] Sample concentration: 50 to 100 g/l-solvent

[0277] Pulse repetition time: 5.5 seconds

[0278] Number of times of integration: 6,000 to 16,000

[0279] Measurement temperature: 120° C.

[0280] From a .sup.13C-NMR spectrum measured under the above conditions, the composition of each of the ethylene, the tetracyclododecene, and the cyclic olefin having an aromatic ring was quantified.

[0281] [Glass Transition Temperature Tg (° C.)]

[0282] By using DSC-6220 manufactured by Shimadzu Corporation, a glass transition temperature Tg of the cyclic olefin-based copolymer was measured in a nitrogen (N2) atmosphere. The cyclic olefin-based copolymer was heated to 200° C. from room temperature at a heating rate of 10° C./min and then kept as it was for 5 minutes. Thereafter, the copolymer was cooled to −20° C. at a cooling rate of 10° C./min and then kept as it was for 5 minutes. From a heat absorption curve formed at the time of heating the copolymer to 200° C. at a heating rate of 10° C./min, the glass transition temperature (Tg) of the cyclic olefin-based copolymer was determined.

[0283] [Intrinsic viscosity [η]]

[0284] By using a mobile viscometer (manufactured by RIGOSHA & Co., Ltd., type: VNR053U), 0.25 to 0.30 g of the cyclic olefin-based copolymer was dissolved in 25 ml of decalin, thereby obtaining a sample. Based on ASTM J1601, the specific viscosity of the cyclic olefin-based copolymer was measured at 135° C., a ratio between the specific viscosity and the concentration was extrapolated to 0, thereby determining an intrinsic viscosity [η] of the cyclic olefin-based copolymer.

[0285] [Formation of Micro-Compounder]

[0286] By using a compact kneader manufactured by Xplore Instruments BV, the cyclic olefin-based copolymers of Manufacturing Examples 1 to 10 and 12 were kneaded for 5 minutes at a kneading temperature of 280° C. and 50 rpm. Then, by using an injection molding machine manufactured by Xplore Instruments BV, the copolymers were subjected to injection molding under the conditions of a cylinder temperature of 280° C., an injection pressure of 12 to 15 bar, and a mold temperature of 135° C., thereby preparing injection molding sheets having a thickness of 1.0 mm.

[0287] [Inner Haze]

[0288] Based on JIS K7136, the inner haze of each of the 30 mm×30 mm×1.0 mm (thickness) injection molding sheets formed using the micro-compounder was measured by using benzyl alcohol. Then, the inner haze was evaluated based on the following standards.

[0289] O: less than 5%

[0290] X: equal to or higher than 5%.

[0291] [Birefringence]

[0292] For each of the 30 mm×30 mm×1.0 mm (thickness) injection molding sheets formed using the micro-compounder, by using KOBRA CCD manufactured by Oji Scientific Instruments, an average of phase differences of 20 to 35 mm from a gate direction at a measurement wavelength of 650 nm was determined.

[0293] Then, the birefringence was evaluated based on the following standards.

[0294] A: the average of phase differences was less than 30 nm.

[0295] B: the average of phase differences was equal to or greater than 30 nm and less than 40 nm.

[0296] C: the average of phase differences was equal to or greater than 40 nm.

[0297] [Refractive Index]

[0298] By using a refractometer (KPR200 manufactured by Shimadzu Corporation), for each of the 30 mm×30 mm×1.0 mm (thickness) injection molding sheets formed using the micro-compounder, a refractive index (nd) at a wavelength of 589 nm was measured based on ASTM D542.

[0299] [Abbe number (ν)]

[0300] For each of the 30 mm×30 mm×1.0 mm (thickness) injection molding sheets formed using the micro-compounder, the refractive index was measured using the Abbe refractometer at wavelengths of 486 nm, 589 nm, and 656 nm at 23° C. Furthermore, by using the following equation, an Abbe number (ν) was calculated.

v=(nD−1)/(nF−nC)

[0301] nD: refractive index at wavelength of 589 nm

[0302] nC: refractive index at wavelength of 656 nm

[0303] nF: refractive index at wavelength of 486 nm

Example 10

[0304] As a hydrophilic stabilizer, a triglycerin fatty acid ester (triglycerin oleate as an ester of triglycerin and oleaic acid (a mixture of a monoester, a diester, and a triester, proportion of ester: 41% for the monoester, 49% for the diester, and 10% for the triester)) was heated for 4 hours at 100° C. such that the stabilizer was melted. The molten stabilizer was directly put into an extruder in an amount of 0.6 parts by mass with respect to 100 parts by mass of the cyclic olefin-based copolymer (P-1), thereby obtaining a resin composition containing the cyclic olefin-based copolymer (P-1) and a distillate of an ester of triglycerin and oleaic acid.

[0305] Specifically, the cyclic olefin-based copolymer (P-1) was put into a twin screw extruder, which had screws rotating in the same direction and each having a diameter of 12 mmφ and had a vent hole at a position of L/D=34 from a resin injection portion, from the resin injection portion. Thereafter, the triglycerin fatty acid ester heated and melted at a temperature of 80° C. to 120° C. was put into the extruder from the vent hole, and melted and kneaded under the conditions of a screw rotation speed of 150 rpm and motor power of 2.2 kW, thereby obtaining a resin composition.

[0306] For the obtained resin composition, the glass transition temperature and the intrinsic viscosity [η] were measured by the same method as that in Example 1. The results are shown in Table 3.

Example 11

[0307] A resin composition was prepared in the same manner as in Example 10, except that triglycerin fatty acid ester was used in an amount of 0.8 parts by mass with respect to 100 parts by mass of the cyclic olefin-based copolymer (P-1) s described in Table 3.

[0308] For the obtained resin composition, the glass transition temperature and the intrinsic viscosity [η] were measured by the same method as that in Example 1. The results are shown in Table 3.

Example 12

[0309] A resin composition was prepared in the same manner as in Example 10, except that triglycerin fatty acid ester was used in an amount of 1.0 parts by mass with respect to 100 parts by mass of the cyclic olefin-based copolymer (P-1) as described in Table 3.

[0310] For the obtained resin composition, the glass transition temperature and the intrinsic viscosity [η] were measured by the same method as that in Example 1. The results are shown in Table 3.

Example 13

[0311] A resin composition was prepared in the same manner as in Example 10, except that as a hydrophilic stabilizer, instead of the triglycerin fatty acid ester, RIKEMAL DO-100 (manufactured by RIKEN VITAMIN Co., Ltd., containing diglycerin monooleate as a main component) was used in an amount of 0.6 parts by mass with respect to 100 parts by mass of the cyclic olefin-based copolymer (P-1) as described in Table 3.

[0312] For the obtained resin composition, the glass transition temperature and the intrinsic viscosity [η] were measured by the same method as that in Example 1. The results are shown in Table 3.

Example 14

[0313] A resin composition was prepared in the same manner as in Example 10, except that as a hydrophilic stabilizer, instead of the triglycerin fatty acid ester, RIKEMAL DO-100 was used in an amount of 1.0 part by mass with respect to 100 parts by mass of the cyclic olefin-based copolymer (P-1) as described in Table 3.

[0314] For the obtained resin composition, the glass transition temperature and the intrinsic viscosity [η] were measured by the same method as that in Example 1. The results are shown in Table 3.

Example 15

[0315] A resin composition was prepared in the same manner as in Example 10, except that as a hydrophilic stabilizer, instead of the triglycerin fatty acid ester, EXCEPARL PE-MS (manufactured by Kao Corporation, containing pentaerythritol monostearate as a main component) was used in an amount of 1.8 parts by mass with respect to 100 parts by mass of the cyclic olefin-based copolymer (P-1) as described in Table 3.

[0316] For the obtained resin composition, the glass transition temperature and the intrinsic viscosity [η] were measured by the same method as that in Example 1. The results are shown in Table 3.

Example 16

[0317] A resin composition was prepared in the same manner as in Example 10, except that as a hydrophilic stabilizer, instead of the triglycerin fatty acid ester, EXCEPARL PE-MS was used in an amount of 2.4 parts by mass with respect to 100 parts by mass of the cyclic olefin-based copolymer (P-1) as described in Table 3.

[0318] For the obtained resin composition, the glass transition temperature and the intrinsic viscosity [η] were measured by the same method as that in Example 1. The results are shown in Table 3.

Example 17

[0319] A resin composition was prepared in the same manner as in Example 10, except that instead of the cyclic olefin-based copolymer (P-1), the cyclic olefin-based copolymer (P-5) was used as described in Table 3.

[0320] For the obtained resin composition, the glass transition temperature and the intrinsic viscosity [η] were measured by the same method as that in Example 1. The results are shown in Table 3.

Example 18

[0321] A resin composition was prepared in the same manner as in Example 12, except that instead of the cyclic olefin-based copolymer (P-1), the cyclic olefin-based copolymer (P-5) was used as described in Table 3.

[0322] For the obtained resin composition, the glass transition temperature and the intrinsic viscosity [η] were measured by the same method as that in Example 1. The results are shown in Table 3.

Example 19

[0323] A resin composition was prepared in the same manner as in Example 10, except that instead of the cyclic olefin-based copolymer (P-1), the cyclic olefin-based copolymer (P-8) was used as described in Table 3.

[0324] For the obtained resin composition, the glass transition temperature and the intrinsic viscosity [η] were measured by the same method as that in Example 1. The results are shown in Table 3.

Example 20

[0325] A resin composition was prepared in the same manner as in Example 12, except that instead of the cyclic olefin-based copolymer (P-1), the cyclic olefin-based copolymer (P-8) was used as described in Table 3.

[0326] For the obtained resin composition, the glass transition temperature and the intrinsic viscosity [η] were measured by the same method as that in Example 1. The results are shown in Table 3.

[0327] <Evaluation methods for Examples 1, 5, 8, and 10 to 20 in Table 3>

[0328] (Method for Manufacturing Molded Article)

[0329] By using an injection molding machine (Micro-2 manufactured byMEIHO CO., LTD.), the resin composition was subjected to injection molding at a cylinder temperature of 320° C., thereby preparing 25 mm×25 mm×2 mmt (thickness) molded articles (test pieces). The mold temperature was set to be 135° C.

[0330] [Refractive Index and Abbe Number]

[0331] By using a refractometer (KPR3000 manufactured by Shimadzu Corporation), for each of the 25 mm×25 mm×2 mmt (thickness) molded test pieces, a refractive index (nd) at wavelengths of 486 nm, 589 nm, and 656 nm was measured based on ASTM D542. Furthermore, by using the following equation, an Abbe number (ν) was calculated. The results are shown in Table 2.

ν=(nD−1)/(nF−nC)

[0332] nD: refractive index at wavelength of 589 nm

[0333] nC: refractive index at wavelength of 656 nm

[0334] nF: refractive index at wavelength of 486 nm

[0335] [Inner Haze]

[0336] Based on JIS K-7136, the inner haze of each of the molded articles was measured by using benzyl alcohol. Then, the inner haze was evaluated based on the following standards. The results are shown in Table 2.

[0337] O: less than 5%

[0338] X: equal to or higher than 5%.

[0339] [Birefringence]

[0340] For each of the molded 25 mm×25 mm×2 mmt (thickness) test pieces, by using KOBRA CCD manufactured by Oji Scientific Instruments, an average of phase differences of 20 to 35 mm from a gate direction at a measurement wavelength of 650 nm was determined. The results are shown in Table 2.

[0341] Then, the birefringence was evaluated based on the following standards.

[0342] A: the average of phase difference was less than 10 nm.

[0343] B: the average of phase difference was equal to or greater than 10 nm and less than 20 nm.

[0344] C: the average of phase difference was equal to or greater than 20 nm.

[0345] [Appearance after Environmental Testing]

[0346] The molded 25 mm×25 mm×2 mmt (thickness) test pieces were left to stand for 48 hours in an atmosphere of a temperature of 85° C. and a relative humidity of 85%. Thereafter, the test pieces were taken out and then left to stand for 48 hours in an atmosphere with a temperature of 23° C. and a relative humidity of 50%, and then haze thereof was measured. The results are shown in Table 2.

[0347] The change (hereinafter, described as A haze), which was obtained by subtracting the haze before the environmental testing from the haze after the environmental testing, was evaluated based on the following standards.

[0348] A: less than 5%

[0349] B: equal to or higher than 5%

TABLE-US-00003 TABLE 3 Example Example Example Example Example Example Example 1 10 11 12 13 14 15 Cyclic olefin-based copolymer P-1 P-1 P-1 P-1 P-1 P-1 P-1 Cyclic olefin having aromatic ring BNBD BNBD BNBD BNBD BNBD BNBD BNBD from which constitutional unit (C) is derived Composition Constitutional unit 63.0 63.0 63.0 63.0 63.0 63.0 63.0 (A) (derived from ethylene) (mol %) Constitutional unit 21.0 21.0 21.0 21.0 21.0 21.0 21.0 (B) (derived from tetracyclododecene) (mol %) Constitutional unit 16.0 16.0 16.0 16.0 16.0 16.0 16.0 (C) (mol %) Triglycerin fatty acid ester 0.0 0.6 0.8 1.0 0.0 0.0 0.0 (part by mass) RIKEMAL DO-100 (part by mass) 0.0 0.0 0.0 0.0 0.6 1.0 0.0 EXCEPARL PE-MS (part by mass) 0.0 0.0 0.0 0.0 0.0 0.0 1.8 Tg (° C.) 147 144 142 140 144 140 134 [n] (dl/g) 0.47 0.47 0.47 0.47 0.47 0.47 0.47 Refractive index (nd) 1.56 1.56 1.56 1.56 1.56 1.56 1.56 Abbe number 46 46 46 46 46 46 46 Inner haze o o o o o o o Birefringence B B B B B B B Appearance after environmental B A A A A A A testing Example Example Example Example Example Example Example 16 5 17 18 8 19 20 Cyclic olefin-based copolymer P-1 P-5 P-5 P-5 P-8 P-8 P-8 Cyclic olefin having aromatic ring BNBD IndNB IndNB IndNB MePhNB MePhNB MePhNB from which constitutional unit (C) is derived Composition Constitutional unit 63.0 63.3 63.3 63.3 60.0 60.0 60.0 (A) (derived from ethylene) (mol %) Constitutional unit 21.0 21.3 21.3 21.3 20.0 20.0 20.0 (B) (derived from tetracyclododecene) (mol %) Constitutional unit 16.0 15.4 15.4 15.4 20.0 20.0 20.0 (C) (mol %) Triglycerin fatty acid ester 0.0 0.0 0.6 1.0 0.0 0.6 1.0 (part by mass) RIKEMAL DO-100 (part by mass) 0.0 0.0 0.0 0.0 0.0 0.0 0.0 EXCEPARL PE-MS (part by mass) 2.4 0.0 0.0 0.0 0.0 0.0 0.0 Tg (° C.) 130 154 151 147 152 149 145 [n] (dl/g) 0.47 0.44 0.44 0.44 0.45 0.45 0.45 Refractive index (nd) 1.56 1.56 1.56 1.56 1.55 1.55 1.55 Abbe number 46 47 47 47 47 47 47 Inner haze o o o o o o o Birefringence B B B B B B B Appearance after environmental A B A A B A A testing

[0350] As shown in the above tables, the optical lenses obtained in the examples had a high refractive index and an Abbe number which was lower than the Abbe number of the optical lens obtained in Comparative Example 1. That is, the optical lenses obtained in the examples satisfied various characteristics required to optical lenses and had a high refractive index and a low Abbe number. In contrast, the optical lens of Comparative Example 1, in which the cyclic olefin-based copolymer that did not contain the constitutional unit (C) derived from the cyclic olefin having an aromatic ring was used, had a high Abbe number. In Comparative Example 1, the intended optical lens was not obtained. The optical lens of Comparative Example 2 had poor inner haze and poor optical characteristics.

EXAMPLES AND COMPARATIVE EXAMPLES ACCORDING TO SECOND INVENTION

[0351] Hereinafter, the second invention of the present application will be specifically described based on examples. However, the second invention of the present application is not limited to the examples.

[0352] <Manufacturing of Cyclic Olefin-Based Copolymer>

Manufacturing Example 13

[0353] As an inert gas, nitrogen was allowed to flow in a reaction container, which included a stirring device, had a volume of 500 ml, and was made of glass, for 30 minutes at a flow rate of 100 Nl/hr. Then, cyclohexane, tetracyclo[4.4.0.1.sup.2,5.1.sup.7,10]-3-dodecene (19 mmol, hereinafter, referred to as tetracyclododecene as well) and indene norbornene (8.0 mmol, hereinafter, referred to as IndNB as well) were added to the reaction container. Thereafter, the polymerization solvent was stirred at a rotation speed of 600 rpm, and in this state, the solvent temperature was increased to 50° C. After the solvent temperature reached a predetermined temperature, the gas flowing in the reaction container was changed to ethylene from nitrogen. Ethylene and hydrogen were allowed to flow in the reaction container at supply rates of 50 Nl/hr and 0.5 Nl/hr respectively. After 10 minutes, Modified Methyl Aluminoxane (MMAO) (0.9 mmol) and the catalyst (0.0030 mmol) prepared by the method described in paragraph “0112” in Japanese Unexamined Patent Publication No. 2010-241932 were added to the reaction container made of glass such that polymerization was initiated.

[0354] After 10 minutes, 5 ml of isobutyl alcohol was added thereto so as to stop the polymerization, thereby obtaining a polymerized solution containing a copolymer of ethylene, tetracyclododecene, and IndNB. Subsequently, the polymerized solution was moved to a beaker having a volume of 2 L that was additionally prepared, 5 ml of concentrated hydrochloric acid and a stirrer were added thereto, and a deliming operation was performed by bringing the copolymer into contact with the hydrochloric acid for 2 hours in a state of strongly stirring the solution. In a state of being stirred, the polymerized solution having undergone deliming was added to a beaker containing acetone that was about three times the volume of the polymerized solution, such that the copolymer was precipitated. The precipitated copolymer was separated from the filtrate by filtration. The obtained polymer containing the solvent was dried under reduced pressure for 10 hours at 130° C., thereby obtaining 0.58 g of a white powder-like ethylene.tetracyclododecene.indene norbornene copolymer.

[0355] In this way, a cyclic olefin-based copolymer (P-13) was obtained.

Manufacturing Examples 14 to 21

[0356] Cyclic olefin-based copolymers (P-14) to (P-21) described in Table 4 were obtained by performing the same operation as that in Manufacturing Example 13, except that the content of each of the constitutional units constituting the cyclic olefin-based copolymers was adjusted to the value described in Table 4.

[0357] In Table 4, BNBD means benzonorbornadiene represented by the following Formula (1), and IndNB means indene norbornene represented by the following Formula (2) . MePhNB means methyl phenyl norbornene represented by the following Formula (3).

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Examples 21 to 28 and Comparative Example 3

[0358] In each of the examples and the comparative examples, various physical properties were measured or evaluated by the following method. The obtained results are shown in Table 4.

[0359] [Method for Measuring Content of Each of Constitutional Units Constituting Cyclic Olefin-Based Copolymer]

[0360] The content of ethylene, tetracyclo[4.4.0.1.sup.2,5.1.sup.7,10]-3-dodecene, and the cyclic olefin having an aromatic ring was measured under the following conditions by using a nuclear magnetic resonance spectrometer “ECA 500” manufactured by JEOL Ltd.

[0361] Solvent: deuterated tetrachloroethane

[0362] Sample concentration: 50 to 100 g/l-solvent

[0363] Pulse repetition time: 5.5 seconds

[0364] Number of times of integration: 6,000 to 16,000

[0365] Measurement temperature: 120° C.

[0366] From a .sup.13C-NMR spectrum measured under the above conditions, the composition of each of the ethylene, the tetracyclododecene, and the cyclic olefin having an aromatic ring was quantified.

[0367] [Glass transition temperature Tg (° C.)]

[0368] By using DSC-6220 manufactured by Shimadzu Corporation, a glass transition temperature Tg of the cyclic olefin-based copolymer was measured in a nitrogen (N2) atmosphere. The cyclic olefin-based copolymer was heated to 200° C. from room temperature at a heating rate of 10° C./min and then kept as it was for 5 minutes. Thereafter, the copolymer was cooled to −200° C. at a cooling rate of 10° C./min and then kept as it was for 5 minutes. From a heat absorption curve formed at the time of heating the copolymer to 200° C. at a heating rate of 10° C./min, the glass transition temperature (Tg) of the cyclic olefin-based copolymer was determined.

[0369] [Intrinsic Viscosity [η]]

[0370] By using a mobile viscometer (manufactured by RIGOSHA & Co., Ltd., type: VNR053U), 0.25 to 0.30 g of the cyclic olefin-based copolymer was dissolved in 25 ml of decalin, thereby obtaining a sample. Based on ASTM J1601, the specific viscosity of the cyclic olefin-based copolymer was measured at 135° C., a ratio between the specific viscosity and the concentration was extrapolated to 0, thereby determining an intrinsic viscosity [η] of the cyclic olefin-based copolymer.

[0371] (Evaluation of Cyclic Olefin-Based Copolymer Composition)

[0372] [Press Molding]

[0373] The powder obtained in Manufacturing Examples 13 to 21 was subjected to press molding under the condition of 250° C. by using a hand press machine manufactured by Toyo Seiki Seisaku-sho, Ltd., thereby preparing square plate-like test pieces having a thickness of 2 mm.

[0374] [γ-Ray Irradiation]

[0375] The square plate-like test pieces having a thickness of 2 mm obtained as above were irradiated with y-rays at 20 kGy or 50 kGy.

[0376] [Transparency]

[0377] For each of the obtained square plate-like test pieces having a thickness of 2 mm and the test pieces just finished with the y-ray irradiation, the inner haze was measured, and the transparency thereof was evaluated based on the following standards.

[0378] The inner haze was measured in benzyl alcohol by using a haze meter (NDH-20Dmanufactured by NIPPON DENSHOKU INDUSTRIES Co. , LTD).

[0379] O: the inner haze was less than 6.0%.

[0380] X: the test piece appeared turbid, or the inner haze was equal to or higher than 6.0%.

[0381] [Evaluation: Color Immediately after γ-Ray Irradiation]

[0382] The test pieces just finished with the y-ray irradiation were stacked on white paper until the thickness thereof became 20 mm. At this time, the color and brightness thereof were visually evaluated.

[0383] The color was based on the Munsell color system. The evaluation standards are as below.

[0384] A (excellent) : the brightness was 7 to 9.5, and the color was between 5.0 GY and 10 GY

[0385] B (normal): the brightness was 5 to 9.5, and the color was between 5 Y and 5 GY; here, a case corresponding to A (excellent) was ruled out.

[0386] C (bad) : the brightness was equal to or higher than 0 and less than 5 and/or the color was between 2.5 Y and 5 Y; here, a case corresponding to B (normal) was ruled out.

[0387] The evaluation standards will be more specifically described.

[0388] It has been revealed that the higher the brightness, the closer the sample to white, and the discoloration is further inhibited.

[0389] Regarding the color, assuming that the composition is used particularly as a medical container, it is apprehended that yellow may give an impression of being dirty to patients. Therefore, green was regarded as being more preferable than yellow.

[0390] [Evaluation: amount of radicals 5 days and 1 month after y-ray irradiation]

[0391] The amount of radicals in a sample 5 days and 1 month after the γ-ray irradiation was measured by Electron Spin Resonance (ESR) .

[0392] Specifically, 5 days and 1 month after the irradiation with γ-rays at a doses of 20 kGy and 50 kGy, about 6 mg of a sample was cut from each of the test pieces, put into a test tube (see the following description for more detail), and an ESR spectrum thereof was measured under the following conditions. [0393] Device: electron spin resonance spectrometer JES-TE200 manufactured by JEOL Ltd. [0394] Resonant frequency: 9.2 GHz [0395] Microwave input: 1 mW [0396] Central field: 326.5 mT [0397] Sweep range: ±15 mT [0398] Modulation frequency: 100 kHz [0399] Sweep time: 8 min [0400] Time constant: 0.1 sec [0401] Amplification degree: 25 [0402] Test tube: test tube with quartz tip for X band [0403] External standard: Mn2+standard sample supported on magnesium oxide [0404] External standard memory: 0,700 [0405] Measurement temperature: room temperature [0406] Measurement atmosphere: the atmosphere

[0407] For the relative comparison of the amount of generated radicals, a normalized value expressed as the following equation was used.

Amount of generated radicals (normalized value)=area of portion corresponding to organic radicals in spectrum/area of portion (second signal) corresponding to Mn2.sup.+ in spectrum×amount of pellets

[0408] The baseline of the ESR spectrum was corrected based on Mn2+ (second signal).

[0409] Generally, in the relative comparison of amount of radicals, for the area of the signal derived from Mn2+ as a standard, Mn2+ (third signal) is used. However, because the spectrum of the signal derived from organic radicals overlapped Mn2+ (third signal), only Mn2+ (second signal) was used in ESR performed in the present example (external standard memory=700).

[0410] Furthermore, in a case where the signal derived from organic radicals overlapped Mn2+ (third signal), the amount of generated radicals was calculated using an ESR spectrum of an external standard memory=0.

TABLE-US-00004 TABLE 4 Example Example Example Example Example Example Example Example Comparative Resin 21 22 23 24 25 26 27 28 Example 3 Cyclic olefin-based copolymer P-13 P-14 P-15 P-16 P-17 P-18 P-19 P-20 P-21 Cyclic olefin having aromatic ring IndNB IndNB IndNB BNBD BNBD IndNB MePhNB MePhNB N/A from which constitutional unit (C) is derived Constitutional unit (A) (derived 60.7 64.3 64.1 65.0 63.0 65.2 63.0 65.6 65.9 from ethylene) (mol %) Constitutional unit (B) (derived 29.6 29.2 31.8 31.0 21.0 32.6 27.0 31.2 34.1 from tetracyclododecene) (mol %) Constitutional unit (C) (mol %) 9.7 6.5 4.1 4.0 16.0 2.2 10.0 3.2 0. 0 Content of constitutional unit (C) 9.7 6.5 4.1 4.0 16.0 2.2 10.0 3.2 0. 0 with respect to total content of 100 mol % of (A), (B), and (C) (mol %) Content of constitutional unit (C) 24.7 18.2 11.4 11.4 43.2 6.3 27.0 9.3 0. 0 with respect to total content of 100 mol % of (B) and (C) (mol %) [n] (dl/g) 0.54 0.65 0.69 0.45 0.47 0.78 0.45 0.45 0.51 Tg (° C.) 161 150 150 144 147 147 143 136 145 Transparency o o o o o o o o o Color after y-ray (20 kGy) A A A A A A A A c irradiation Color after y-ray (50 kGy) A A A A A A A A c irradiation Amount of radicals 5 days after 0.4 0.4 0.3 0.4 0.3 0.4 0.4 0.3 60 γ-ray (20 kGy) irradiation Amount of radicals 5 days after 0.3 0.4 0.4 0.4 0.3 47 0.3 0.3 120 γ-ray (50 kGy) irradiation Amount of radicals 1 month after 0.2 0.3 0.2 0.3 0.2 0.1 0.2 0.2 1.2 γ-ray (50 kGy) irradiation

[0411] As shown in the above table, the molded articles (sheets) constituted with the cyclic olefin-based copolymer compositions obtained in Examples 21 to 28 were excellent in the balance between performances such as transparency and γ-ray resistance. In contrast, Comparative Example 3, in which a cyclic olefin-based copolymer that did not contain the constitutional unit (C) derived from a cyclic olefin having an aromatic ring was used, was poor in the balance between performances such as transparency and γ-ray resistance.

[0412] The present application claims priorities based on Japanese Patent Application No. 2017-228675 filed on Nov. 29, 2017 and Japanese Patent Application No. 2018-138691 filed on Jul. 24, 2018, the entire disclosure of which is incorporated into the present specification.