Specification
Title of invention: Cyclic olefin copolymer, cyclic olefin copolymer composition, molded article and medical container
Technical field
[0001]
　The present invention relates to a cyclic olefin copolymer, a cyclic olefin copolymer composition, a molded article and a medical container.
Background technology
[0002]
　A cyclic olefin polymer is used for optical lenses such as an imaging lens, an fθ lens, and a pickup lens. Cyclic olefin-based polymers used in molded articles such as optical lenses are required to have characteristics such as high transparency, excellent dimensional stability, and excellent heat resistance.
　Further, for example, image pickup lenses used in smartphones, digital cameras, and the like are required to further improve the refractive index while keeping the value of birefringence low in order to reduce the size and thickness.
[0003]
　Examples of the technology relating to the cyclic olefin polymer used for such an optical lens include those described in Patent Document 1 (JP-A-10-287713) and Patent Document 2 (JP-A-2010-235719). Can be mentioned.
[0004]
　Patent Document 1 discloses (A) a linear or branched α-olefin having 2 to 20 carbon atoms, (B) a cyclic olefin represented by a predetermined chemical formula, and (C) an aromatic vinyl compound. The ultimate viscosity [η] is in the range of 0.1 to 10 dl / g, and is derived from the content ratio of the structural unit derived from the above (B) cyclic olefin and the above (C) aromatic vinyl compound. It describes a cyclic olefin-based copolymer that satisfies a specific relationship with the content ratio of constituent units.
[0005]
　In Patent Document 2, 30 to 70 mol% of a structural unit (A) derived from ethylene or an α-olefin having 3 to 20 carbon atoms, a structural unit (B) derived from a cyclic olefin represented by a predetermined chemical formula (B) 20% to 50 mol %, and 0.1 to 20 mol% of the structural unit (C) derived from an aromatic vinyl compound, and the intrinsic viscosity [η], 1 H-NMR and glass transition temperature satisfy predetermined requirements. A cyclic olefin polymer characterized by the above is described.
[0006]
　Further, the cyclic olefin resin has an excellent performance balance such as transparency and chemical resistance. Therefore, for example, it is being studied to be used as a material for forming a molded product such as a medical container. Examples of the technique relating to the resin composition containing such a cyclic olefin resin include those described in Patent Document 3 and Patent Document 4.
[0007]
　Patent Document 3 describes a cyclic olefin resin composition containing two specific cyclic olefin resins. It is described that the composition provides a molded article having improved slip properties, excellent transparency, surface gloss, and hygiene.
[0008]
　Patent Document 4 discloses that 60 to 90 parts by weight of a cyclic olefin resin, an aromatic vinyl/conjugated diene block copolymer having a number average molecular weight of 75,000 to 500,000 and/or a hydrogenated product of 10 to 40 thereof. A cyclic olefin resin composition consisting of parts by weight is described. Then, it is described that the composition provides a molded article having excellent impact strength and moisture resistance.
Prior art documents
Patent literature
[0009]
Patent Document 1: Japanese Patent Application Laid-Open No. 10-287713
Patent Document 2: Japanese Patent Application Laid-Open No. 2010-235719
Patent Document 3: Japanese Patent Application Laid-Open No. 2001-26693
Patent Document 4: Japanese Patent Application Laid-Open No. 8-277353
Summary of the invention
Problems to be Solved by the Invention
[0010]
　According to a study by the present inventors, in applications such as optical lenses, a resin material whose Abbe number can be adjusted to be lower than that of a conventional resin material is used for the purpose of improving image quality and improving the degree of freedom in designing an optical lens. It became clear that there was a demand.
　The first invention of the present invention has been made in view of the above circumstances, and provides a cyclic olefin copolymer having a high refractive index and capable of adjusting the Abbe number to be lower than that of a conventional resin material. ..
[0011]
　A medical container such as a syringe or a drug solution storage container is usually filled with the contents after sterilization. During this sterilization, the container may be irradiated with electron beams or gamma rays.
　According to the study by the present inventors, it has become clear that discoloration may occur in a conventional medical container using a cyclic olefin resin due to electron beam or gamma ray irradiation.
[0012]
　The second invention of the present case has been made in view of such circumstances. That is, the second invention of the present application is to provide a medical container which has little discoloration due to electron beam or gamma ray irradiation and is excellent in transparency.
Means for solving the problem
[0013]
　The present inventors have diligently studied to solve the above-mentioned problems of the first invention of the present invention. As a result, a constitutional unit derived from ethylene, bicyclo[2.2.1]-2-heptene and tetracyclo[4.4.0.1 2,5 . Higher by using a cyclic olefin-based copolymer having a structural unit derived from at least one compound selected from 1 7,10 ]-3-dodecene and a structural unit derived from a cyclic olefin having an aromatic ring. The inventors have found that the Abbe number can be adjusted to be lower than that of a conventional resin material while having a refractive index, and have completed the first invention of the present case.
[0014]
　That is, according to the first invention of the present case, the following cyclic olefin copolymer, cyclic olefin copolymer composition and molded article are provided.
[0015]
[1]
　Derived from 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 cyclic olefin having an aromatic ring.
A cyclic olefin-based copolymer having a structural unit (C) .
[2] In
　the cyclic olefin-based copolymer according to the above [1],
　a total content of the structural unit (A), the structural unit (B) and the structural unit (C) in the cyclic olefin-based copolymer. A cyclic olefin-based copolymer in which the content of the structural unit (A) in the cyclic olefin-based copolymer is 10 mol% or more and 80 mol% or less when the amount is 100 mol %.
[3] In
　the cyclic olefin-based copolymer according to the above [1] or [2],
　the total content of the structural unit (B) and the structural unit (C) in the cyclic olefin-based copolymer is 100. A cyclic olefin copolymer in which the content of the structural unit (C) in the cyclic olefin copolymer is 5 mol% or more and 95 mol% or less, when defined as mol %.
[4] In
　the cyclic olefin-based copolymer according to any one of the above [1] to [3], the cyclic olefin
　having no aromatic ring is a compound represented by the following formula (B-1). A cyclic olefin-based copolymer containing.
[Chemical 1]

(In the above formula [B-1], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and R 1 to R 18 and R a and R b are respectively Independently, it is a hydrogen atom, a halogen atom or a hydrocarbon group which may be substituted with a halogen atom, and R 15 to R 18 may be bonded to each other to form a monocycle or a polycycle, and The monocycle or polycycle may have a double bond, and R 15 and R 16 or R 17 and R 18 may form an alkylidene group, provided that an aromatic ring is included. no.)
[5]
　in the cycloolefin-based copolymer according to any one of the above [1] to [4],
　cyclic olefins having the aromatic ring is a compound represented by the following formula (C-1) A cyclic olefin-based copolymer containing one or more selected from the group consisting of a compound represented by the following formula (C-2) and a compound represented by the following formula (C-3).
[Chemical 2]

(In the formula (C-1), n ​​and q are each independently 0, 1 or 2, and R 1 to R 17 are independently hydrogen atom, a halogen atom excluding a fluorine atom, or a fluorine atom is excluded. It is a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom, one of R 10 to 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 , and R 15 and R 10 may be bonded to each other to form a monocyclic or polycyclic ring, and q=1 Or when it is 2, R 10 and R 11 , R 11And R 17 , R 17 and R 17 , R 17 and R 12 , R 12 and R 13 , R 13 and R 14 , R 14 and R 15 , R 15 and R 16 , R 16 and R 16 , R 16 and R. 10 may be bonded to each other to form a monocycle or a polycycle, and the monocycle or the polycycle may have a double bond, and the monocycle or the polycycle is an aromatic ring. It may be. )
[Formula 3]

in (above formula (C-2), n and m are each independently 0, 1 or 2, q is 1, 2 or 3, R 18 ~ R 31Each independently represents a hydrogen atom, a halogen atom excluding a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom excluding a fluorine atom, and when q=1, R 28 And R 29 , R 29 and R 30 , R 30 and R 31 may be coupled to each other to form a monocyclic or polycyclic, 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 , and R 31 and R 31 may be bonded to each other to form a monocycle or a polycycle, and the monocycle or the polycycle forms a double bond. It may have, and the monocycle or polycycle may be an aromatic ring. )
[Chemical 4]

(In the above formula (C-3), q is 1, 2 or 3, and R 32 to R 39 are independently substituted with hydrogen atom, halogen atom excluding fluorine atom, or halogen atom excluding fluorine atom, respectively. Which is a hydrocarbon group having 1 to 20 carbon atoms, and when q=1, R 36 and R 37 , R 37 and R 38 , and R 38 and R 39 are bonded to each other to form a monocyclic or polycyclic ring. And when q = 2 or 3, R 36 and R 36 , R 36 and R 37 , R 37 and R 38 , R 38 and R 39 , R 39 and R 39.May be bonded to each other to form a monocyclic or polycyclic ring, the monocyclic or polycyclic ring may have a double bond, and the monocyclic or polycyclic ring is an aromatic ring. It may be. )
[6]
　above [1] to the cyclic olefin copolymer according to any one of [5],
　when fabricated injection molded sheet having a thickness of 1.0mm made of the cyclic olefin copolymer , A cyclic olefin-based copolymer in which the Abbe number (ν) of the injection-molded sheet is 35 or more and 55 or less.
[7]
　The
　glass transition temperature of the cyclic olefin-based copolymer according to any one of [1] to [6], which is measured by a differential scanning calorimeter (DSC). A cyclic olefin-based copolymer having a (Tg) of 120° C. or higher and 180° C. or lower.
[8] In
　the cyclic olefin copolymer according to any one of the above [1] to [7], the
　ultimate viscosity [η] measured in decalin at 135 ° C. is 0.05 dl / g or more and 5.0 dl or more. /G or less cyclic olefin-based copolymer.
[9] In
　the cyclic olefin-based copolymer according to any one of [1] to [8]
　above, when a 1.0 mm-thick injection-molded sheet made of the cyclic olefin-based copolymer is prepared, A cyclic olefin copolymer having a birefringence of 1 nm or more and 200 nm or less of the injection-molded sheet.
[10]
　In the cyclic olefin-based copolymer according to any one of [1] to [9], the cyclic olefin
　having an aromatic ring includes at least one selected from benzonorbornadiene, indenenorbornene, and methylphenylnorbornene. Cyclic olefin copolymer.
[11]
　A cyclic olefin-based copolymer composition containing the cyclic olefin-based copolymer according to any one of the above [1] to [10].
[12]
　The cyclic olefin-based copolymer composition according to the above [11], which further contains a hydrophilic stabilizer.
[13]
　
[Birefringence]
　A 30 mm×30 mm×1.0 mm thick injection-molded sheet molded with a micro compounder was measured with a KOBRA CCD manufactured by Oji Scientific Instruments at a measurement wavelength of 650 nm and a phase difference of 20 to 35 mm from the gate direction. The average value of was calculated.
　Next, the birefringence was evaluated according to the following criteria.
A: Average value of retardation is less than 30 nm.
O: Average value of retardation is 30 nm or more and less than 40 nm.
X: Average value of retardation is 40 nm or more.
[0138]
[Refractive index]
　Refractive index (nd) of an injection-molded sheet of 30 mm × 30 mm × thickness 1.0 mm molded with a microcompound using a refractive index meter (KPR200 manufactured by Shimadzu Science Co., Ltd.) at a wavelength of 589 nm according to ASTM D542. ) Was measured respectively.
[0139]
[Abbe number (ν)] With
　respect to an injection-molded sheet of 30 mm×30 mm×thickness of 1.0 mm formed by a micro compounder, the Abbe refractometer was used to measure the refractive index at wavelengths of 486 nm, 589 nm and 656 nm at 23° C. The Abbe number (ν) was calculated using the following formula.
ν=(nD-1)/(nF-nC)
nD: Refractive index at wavelength 589 nm
nC: Refractive index at
wavelength 656 nm nF: Refractive index at wavelength 486 nm
[0140]
As a
　hydrophilic stabilizer, triglycerin fatty acid ester (triglycerin oleate which is an ester of triglycerin and oleic acid (mixture of monoester, diester and triester, ester ratio 41% monoester, diester 49 %, triester 10%)) in a molten state heated at 100° C. for 4 hours, and directly loaded into the extruder in an amount of 0.6 part by mass relative to 100 parts by mass of the cyclic olefin copolymer (P-1). Then, a resin composition containing a cyclic olefin copolymer (P-1), a distilled product of an ester of triglycerin and oleic acid was obtained.
　Specifically, using a twin-screw extruder with co-rotation, a screw diameter of 12 mmφ, and an L/D=48 having a vent hole at a position L/D=34 from the resin charging part, a cyclic olefin-based copolymer ( P-1) was charged from the resin charging part, then the above triglycerin fatty acid ester which was heated and melted at 80 to 120° C. was charged from the vent hole, and the screw rotation speed was 150 rpm and the motor power was 2.2 kW. The resin composition was obtained by melt-kneading under the conditions.
　The glass transition temperature and the intrinsic viscosity [η] of the obtained resin composition were measured in the same manner as in Example 1. The results are shown in Table 3.
[0141]
As shown in
　Table 3, the same as in Example 10 except that the 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 copolymer (P-1). A resin composition was prepared in the same manner.
　With respect to the obtained resin composition, the glass transition temperature and the ultimate viscosity [η] were measured by the same method as in Example 1. The results are shown in Table 3.
[0142]
As shown in
　Table 3, the same as in Example 10 except that the triglycerin fatty acid ester was used in an amount of 1.0 part by mass with respect to 100 parts by mass of the cyclic olefin copolymer (P-1). A resin composition was prepared in the same manner.
　With respect to the obtained resin composition, the glass transition temperature and the ultimate viscosity [η] were measured by the same method as in Example 1. The results are shown in Table 3.
[0143]
As shown in
　Table 3, a cyclic olefin copolymer using Riquemar DO-100 (manufactured by RIKEN Vitamin, the main component is diglycerin monooleate) instead of triglycerin fatty acid ester as a hydrophilic stabilizer. A resin composition was prepared in the same manner as in Example 10 except that the amount of (P-1) was 0.6 parts by mass relative to 100 parts by mass.
　With respect to the obtained resin composition, the glass transition temperature and the ultimate viscosity [η] were measured by the same method as in Example 1. The results are shown in Table 3.
[0144]
As shown in
　Table 3, 1.0 mass by mass of Riquemar DO-100 was changed to triglycerin fatty acid ester as a hydrophilic stabilizer with respect to 100 parts by mass of the cyclic olefin copolymer (P-1). A resin composition was prepared in the same manner as in Example 10 except that the resin composition was used in the amount of parts.
　With respect to the obtained resin composition, the glass transition temperature and the ultimate viscosity [η] were measured by the same method as in Example 1. The results are shown in Table 3.
[0145]
As shown in
　Table 3, a cyclic olefin copolymer using Exepearl PE-MS (manufactured by Kao Corporation, the main component is pentaerythritol monostearate) instead of triglycerin fatty acid ester as a hydrophilic stabilizer. (P-1) A resin composition was prepared in the same manner as in Example 10 except that it was used in an amount of 1.8 parts by mass with respect to 100 parts by mass.
　With respect to the obtained resin composition, the glass transition temperature and the ultimate viscosity [η] were measured by the same method as in Example 1. The results are shown in Table 3.
[0146]
As shown in
　Table 3, 2.4 parts by mass of Exepearl PE-MS was used as a hydrophilic stabilizer in place of triglycerin fatty acid ester based on 100 parts by mass of the cyclic olefin copolymer (P-1). A resin composition was prepared in the same manner as in Example 10 except that the resin composition was used in the amount of parts.
　With respect to the obtained resin composition, the glass transition temperature and the ultimate viscosity [η] were measured by the same method as in Example 1. The results are shown in Table 3.
[0147]
As shown in
　Table 3, the same procedure as in Example 10 except that the cyclic olefin copolymer (P-5) was used instead of the cyclic olefin copolymer (P-1). A resin composition was prepared.
　With respect to the obtained resin composition, the glass transition temperature and the ultimate viscosity [η] were measured by the same method as in Example 1. The results are shown in Table 3.
[0148]
As
　described in Table 3, the procedure of Example 12 was repeated except that the cyclic olefin copolymer (P-1) was replaced with the cyclic olefin copolymer (P-5). A resin composition was prepared.
　With respect to the obtained resin composition, the glass transition temperature and the ultimate viscosity [η] were measured by the same method as in Example 1. The results are shown in Table 3.
[0149]
As shown in
　Table 3, the same procedure as in Example 10 except that the cyclic olefin copolymer (P-8) was used instead of the cyclic olefin copolymer (P-1). A resin composition was prepared.
　With respect to the obtained resin composition, the glass transition temperature and the ultimate viscosity [η] were measured by the same method as in Example 1. The results are shown in Table 3.
[0150]
As
　described in Table 3, the procedure of Example 12 was repeated except that the cyclic olefin copolymer (P-1) was replaced with the cyclic olefin copolymer (P-8). A resin composition was prepared.
With respect to the obtained resin composition, the glass transition temperature and the ultimate viscosity [η] were measured by the same method as in Example 1. The results are shown in Table 3.
[0151]

( Method for producing molded body
　) A resin composition was prepared using an injection molding machine (Micro-2 manufactured by Mayho Co., Ltd.) at a cylinder temperature of 320°C. Was injection-molded to prepare a molded body (test piece) of 25 mm×25 mm×thickness 2 mmt. The mold temperature was set to 135°C.
[0152]
[Refractive index/Abbe number] Using a
　refractometer (KPR3000 manufactured by Shimadzu Science Co., Ltd.), the refractive index at a wavelength of 486 nm, 589 nm and 656 nm of a molded test piece of 25 mm×25 mm×thickness 2 mmt according to ASTM D542 (nd ) Was measured. Furthermore, the Abbe number (ν) was calculated using the following formula. The results are shown in Table 2.
ν=(nD-1)/(nF-nC)
nD: Refractive index at wavelength 589 nm
nC: Refractive index at
wavelength 656 nm nF: Refractive index at wavelength 486 nm
[0153]
[Internal Haze] The internal haze of the
　molded product was measured according to JIS K-7136 using benzyl alcohol. Then, the internal haze was evaluated according to the following criteria. The results are shown in Table 2.
○: Less than 5%
×: 5% or more
[0154]
[Birefringence] With
　respect to the molded test piece of 25 mm×25 mm×thickness of 2 mmt, an average value of the phase difference of 20 to 35 mm from the gate direction was determined at a measurement wavelength of 650 nm using a KOBRA CCD manufactured by Oji Scientific Instruments. The results are shown in Table 2.
　Next, the birefringence was evaluated according to the following criteria.
⊚: Average value of retardation is less than 10 nm
◯: Average value of retardation is 10 nm or more and less than 20 nm
×: Average value of retardation is 20 nm or more
[0155]
[Appearance after Environmental Test] A
　molded test piece of 25 mm×25 mm×thickness of 2 mmt was left for 48 hours in an atmosphere of a temperature of 85° C. and a relative humidity of 85%. After that, the film was taken out and left for 48 hours in an atmosphere having a temperature of 23° C. and a relative humidity of 50%, and then the haze was measured. The results are shown in Table 2.
The amount of change obtained by subtracting the haze before the environmental test from the haze after the environmental test (hereinafter, Δhaze) was evaluated according to the following criteria.
◎: Less than 5%
○: 5% or more
[0156]
[Table 3]

[0157]
　As described above, the optical lenses obtained in the examples had a high refractive index and a lower Abbe number than the optical lens obtained in Comparative Example 1. That is, the optical lenses obtained in the examples showed a high refractive index and a low Abbe number while satisfying various characteristics required for the optical lens. On the other hand, the optical lens of Comparative Example 1 using the cyclic olefin-based copolymer that does not contain the structural unit (C) derived from the cyclic olefin having an aromatic ring has a high Abbe number, and the intended optical lens cannot be obtained. .. The optical lens of Comparative Example 2 had a bad internal haze and was inferior in optical characteristics.
[0158]
Hereinafter, the second invention of the present invention will be specifically described based on examples, but the second invention of the present invention is not limited to these examples.
[0159]

[Production Example 13]
　Nitrogen as an inert gas was passed for 30 minutes at a flow rate of 100 Nl/hr in a glass reaction vessel having a volume of 500 ml equipped with a stirrer, and then cyclohexane and tetracyclo were used. [4.4.0.1 2,5 . 1 7,10 ]-3-dodecene (19 mmol, hereinafter also referred to as tetracyclododecene) and indene norbornene (8.0 mmol, hereinafter also referred to as IndNB) were added. Next, the solvent temperature was raised to 50° C. while stirring the polymerization solvent at a rotation speed of 600 rpm. After the solvent temperature reached a predetermined temperature, the flow gas was switched from nitrogen to ethylene, and ethylene was passed through the reaction vessel at a feed rate of 50 Nl/hr and hydrogen at 0.5 Nl/hr, and after 10 minutes, MMAO was passed. (Modified Methylaluminoxane) (0.9 mmol) and the catalyst (0.0030 mmol) prepared by the method described in paragraph 0112 of JP 2010-241932 A were added to a glass reaction vessel to initiate polymerization.
　After 10 minutes, 5 ml of isobutyl alcohol was added to terminate the polymerization to obtain a polymerization solution containing a copolymer of ethylene, tetracyclododecene and IndNB. Thereafter, the polymerization solution was transferred to a separately prepared beaker having a volume of 2 L, 5 ml of concentrated hydrochloric acid and a stirrer were added, and the mixture was contacted for 2 hours under strong stirring for deashing operation. The decalcified polymerization solution was added with stirring to a beaker containing about 3 times the volume of this polymerization solution with acetone to precipitate a copolymer, and the precipitated copolymer was separated from the filtrate by filtration. The polymer containing the obtained solvent was dried under reduced pressure at 130° C. for 10 hours to obtain 0.58 g of a white powdery ethylene/tetracyclododecene/indene norbornene copolymer.
　As described above, a cyclic olefin-based copolymer (P-13) was obtained.
[0160]
[Production Examples 14 to 21] The same
　operation as in Production Example 13 was carried out except that the content value of each structural unit constituting the cyclic olefin copolymer was adjusted to be the value shown in Table 4. The cyclic olefin copolymers (P-14) to (P-21) shown in Table 4 were obtained.
　Here, BNBD in Table 4 means benzonorbornadiene represented by the following formula (1), and IndNB means indene norbornene represented by the following formula (2). MePhNB means methylphenyl norbornene represented by the following formula (3).
[0161]
[Chemical 32]

[0162]
[Chemical 33]

[0163]
[Chemical 34]

[0164]
In
　each of the Examples and Comparative Examples, various physical properties were measured or evaluated by the following methods, and the obtained results are shown in Table 4.
[0165]
[Measurement Method of Content of Each Structural Unit Constituting Cyclic Olefin Copolymer]
　Ethylene, tetracyclo[4.4.0.1 2,5 . The content of 1 7,10 ]-3-dodecene and the cyclic olefin having an aromatic ring was measured by using an “ECA500 type” nuclear magnetic resonance apparatus manufactured by JEOL Ltd. under the following conditions.
　Solvent: heavy tetrachloroethane
　Sample concentration: 50 to 100 g/l-solvent
　pulse repetition time: 5.5 seconds
　Number of integrations: 6000 to 16000 times
　Measurement temperature: 120° C. 13 C-NMR spectrum
　measured under the above conditions The compositions of ethylene, tetracyclododecene and cyclic olefin having an aromatic ring were quantified respectively.
[0166]
[Glass Transition Temperature Tg (° C.)] The glass transition temperature Tg of the cyclic olefin-based copolymer was measured under
　N 2 (nitrogen) atmosphere using DSC-6220 manufactured by Shimadzu Science . The cyclic olefin copolymer was heated from room temperature to 200 ° C. at a heating rate of 10 ° C./min and then held for 5 minutes, and then cooled to −20 ° C. at a temperature lowering rate of 10 ° C./min and then held for 5 minutes. .. Then, the glass transition point (Tg) of the cyclic olefin copolymer was determined from the endothermic curve when the temperature was raised to 200 ° C. at a heating rate of 10 ° C./min.
[0167]
[Intrinsic Viscosity [η]] A
　moving viscometer (type VNR053U, manufactured by Rikyu Co., Ltd.) was used to dissolve 0.25 to 0.30 g of the cyclic olefin copolymer in 25 ml of decalin as a sample. According to ASTM J1601, the specific viscosity of the cyclic olefin-based copolymer was measured at 135° C., and the ratio of the specific viscosity to the concentration was extrapolated to 0 to determine the intrinsic viscosity [η] of the cyclic olefin-based copolymer.
[0168]
(Evaluation of Cyclic Olefin Copolymer Composition)
[Press Molding]
　The powders obtained in the above Production Examples 13 to 21 were press molded at 250° C. using a hand press manufactured by Toyo Seiki Co., Ltd. A square plate test piece having a thickness of 2 mm was produced.
[0169]
[Gamma Ray Irradiation]
　The 2 mm thick square plate test piece obtained above was irradiated with gamma rays of 20 kGy or 50 kGy.
[0170]
[Transparency]
　The internal haze of the obtained square plate test piece having a thickness of 2 mm and the test piece immediately after gamma ray irradiation was measured, and the transparency was evaluated according to the following criteria.
　The internal haze was measured in benzyl alcohol using a haze meter (NDH-20D manufactured by Nippon Denshoku Kogyo Co., Ltd.).
　◯: Internal haze is less than 6.0%
　×: The test piece is visually opaque, or the internal haze is 6.0% or more.
[0171]
[Evaluation: Hue immediately after gamma ray irradiation]
　Test pieces immediately after gamma ray irradiation were stacked on white paper with a thickness of 20 mm. The hue and lightness at this time were visually evaluated.
　The hue was based on the Munsell color system. The evaluation criteria are as follows.
　Good (good): The lightness is 7 to 9.5 and the hue is between 5.0 GY and 10 GY.
　Δ (normal): The lightness is 5 to 9.5 and the hue is between 5Y and 5GY. However, the case where the above ○ (good) is applicable is excluded.
　X (bad): The brightness is 0 or more and less than 5, and / or the hue is between 2.5Y and 5Y. However, the case corresponding to the above △ (normal) is excluded.
[0172]
　A supplementary note about the above evaluation criteria.
　As for the brightness, the larger the value, the closer to white, and it is clear that discoloration is suppressed.
　Regarding the hue, in consideration of use as a medical container in particular, yellow is avoided because it gives a patient an unclean impression, and thus green is preferable to yellow.
[0173]
[Evaluation: Radical amount
　after 5 days and 1 month after gamma ray irradiation ] The radical amount of the sample after 5 days and 1 month after gamma ray irradiation was measured by an electron spin resonance method (Electron Spin Rssonance (ESR)).
　Specifically, about 6 mg of a test piece after 5 days and 1 month after irradiation with gamma rays having doses of 20 kGy and 50 kGy was cut out, put into a test tube (details below), and ESR spectrum was measured under the following conditions. ..
[0174]
-Device: electron spin resonance device JES-TE200 manufactured by JEOL
-Resonance frequency: 9.2 GHz
-Microwave input: 1 mW
-Central magnetic field: 326.5 mT
-Sweep width: ±15 mT
-Modulation frequency: 100 kHz
-Sweep time: 8 min.
・Time constant: 0.1 sec
・Amplification degree: 25
・Sample tube: Sample tube of quartz at the tip corresponding to X band
・External aim: Mn 2+ standard sample supported on magnesium oxide
・External standard memory: 0, 700
・Measurement Temperature: Room temperature
/Measurement atmosphere: Atmosphere
[0175]
　The normalized value shown in the following formula was used for the relative comparison of the amount of radicals generated.
[0176]
[Number 1]

[0177]
　The baseline of the ESR spectrum was corrected based on Mn 2+ (second signal).
　Usually, in the relative comparison of the amount of radicals, Mn 2+ (third signal) is used as the area of the reference Mn 2+ -derived signal . However, since the spectrum of radicals derived from organic radicals and Mn 2+ (third signal) overlap, Mn 2+ (second signal) was used in all measurements this time (external standard memory=700). 　When the organic radical-derived signal overlapped with Mn 2+ (third signal), it was calculated using the ESR spectrum of external standard memory = 0.
[0178]
[Table 4]

[0179]
　As described above, the molded products (sheets) composed of the cyclic olefin-based copolymer compositions obtained in Examples 21 to 28 were excellent in transparency and gamma ray resistance performance balance. On the other hand, Comparative Example 3 using a cyclic olefin-based copolymer that does not contain a structural unit (C) derived from a cyclic olefin having an aromatic ring was inferior in the performance balance of transparency and gamma ray resistance.
[0180]
　This application claims priority based on Japanese Patent Application No. 2017-228675 filed on November 29, 2017 and Japanese Patent Application No. 2018-138691 filed on July 24, 2018. , All of its disclosures are taken here.
The scope of the claims
[Claim 1]
　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 (B) derived from a cyclic olefin having an aromatic ring ( C) and
a cyclic olefin copolymer.
[Claim 2]
　The cyclic olefin-based copolymer according to claim 1
　, wherein the total content of the structural unit (A), the structural unit (B) and the structural unit (C) in the cyclic olefin-based copolymer is 100 mol. %, the content of the structural unit (A) in the cyclic olefin-based copolymer is 10 mol% or more and 80 mol% or less.
[Claim 3]
　In the cyclic olefin-based copolymer according to claim 1 or 2, when
　the total content of the structural unit (B) and the structural unit (C) in the cyclic olefin-based copolymer is 100 mol%, A cyclic olefin-based copolymer in which the content of the structural unit (C) in the cyclic olefin-based copolymer is 5 mol% or more and 95 mol% or less.
[Claim 4]
　The cyclic olefin copolymer according to any one of claims 1 to 3,
　wherein the cyclic olefin having no aromatic ring contains a compound represented by the following formula (B-1). Coalescing.
[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 to R 18 and R a and R are b is independently a hydrogen atom, a halogen atom or a hydrocarbon group which may be substituted with a halogen atom, and R 15 to R 18 may be bonded to each other to form a monocyclic ring or a polycyclic ring. , And the monocycle or polycycle may have a double bond, and R 15 and R 16 or R 17 and R 18 may form an alkylidene group. Does not contain aromatic rings.)
[Claim 5]
　The cyclic olefin-based copolymer according to any one of claims 1 to 4,
　wherein the cyclic olefin having an aromatic ring is a compound represented by the following formula (C-1) or a compound represented by the following formula (C-2). A cyclic olefin-based copolymer containing one or more compounds selected from the group consisting of the compounds represented by the formula (C-3):
[In the

formula (C-1), n ​​and q are each independently 0, 1 or 2, and R 1 to R 17 are each independently a hydrogen atom, a halogen atom other than a fluorine atom, or optionally substituted with a halogen atom other than fluorine atom a hydrocarbon group which may carbon atoms 1 ~ 20, R 10 ~ R 17 one of is a bond, and R when q = 0 10 and R 11 , R 11 and R 12 , R 12 and R 13 , R 13 and R 14 , R 14 and R 15, R 15 and R 10 may be bonded to each other to form a monocyclic or polycyclic ring, and when q=1 or 2, R 10 and R 11 , R 11 and R 17 , R 17 and R 17 , R 17 and R 12 , R 12 and R 13 , R 13 and R 14 , R 14 and R 15 , R 15 and R 16 , R 16 and R 16 , R 16 and R 10.May be bonded to each other to form a monocycle or a polycycle, and the monocycle or the polycycle may have a double bond, and the monocycle or the polycycle is an aromatic ring. It may be. )
[Formula 3]

in (above formula (C-2), n and m are each independently 0, 1 or 2, q is 1, 2 or 3, R 18 ~ R 31 are each independently, A hydrogen atom, a halogen atom excluding a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom excluding a fluorine atom, and when q=1, R 28 , R 29 and R 29 and R 30 , R 30 and R 31 may be bonded to each other to form a monocyclic or polycyclic ring, and when q=2 or 3, R 28 and R 28 , R 28 and R 29 , R 29 And R 30 and R 30 and R 31 , R 31 and R 31 may be bonded to each other to form a monocyclic or polycyclic ring, the monocyclic ring or the polycyclic ring may have a double bond, and the monocyclic ring or the polycyclic ring may be formed. The polycycle may be an aromatic ring. )
[Formula 4]

in (above formula (C-3), q is 1, 2 or 3, R 32 ~ R 39 except each independently, a hydrogen atom, a halogen atom except fluorine atom or a fluorine atom, It is a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom, and when q = 1, R 36 and R 37 , R 37 and R 38 , and R 38 and R 39 are bonded to each other. It may form a monocyclic ring or a polycyclic ring, and when q=2 or 3, R 36 and R 36 , R 36 and R 37 , R 37 and R 38, R 38 and R 39 , R 39 and R 39 may be coupled to each other to form a monocyclic or polycyclic, and the monocyclic or polycyclic may have a double bond. The monocyclic ring or the polycyclic ring may be an aromatic ring. )
[Claim 6]
　The cyclic olefin-based copolymer according to any one of claims 1 to 5,
　when an injection-molded sheet made of the cyclic olefin-based copolymer and having a thickness of 1.0 mm is produced, the Abbe of the injection-molded sheet is used. A cyclic olefin-based copolymer having a number (ν) of 35 or more and 55 or less.
[Claim 7]
　The cycloolefin copolymer according to any one of claims 1 to 6
　, wherein a glass transition temperature (Tg) of the cycloolefin copolymer measured by a differential scanning calorimeter (DSC) is 120°C. A cyclic olefin-based copolymer having a temperature of 180° C. or higher.
[Claim 8]
　The cyclic olefin-based copolymer according to any one of claims 1 to 7, wherein the
　intrinsic viscosity [η] measured in decalin at 135°C is 0.05 dl/g or more and 5.0 dl/g or less. Olefin-based copolymer.
[Claim 9]
　The cyclic olefin-based copolymer according to any one of claims 1 to 8,
　when an injection-molded sheet having a thickness of 1.0 mm made of the cyclic olefin-based copolymer is produced, A cyclic olefin-based copolymer having a refraction of 1 nm or more and 200 nm or less.
[Claim 10]
　The cyclic olefin-based copolymer according to any one of claims 1 to 9,
　wherein the cyclic olefin having an aromatic ring includes at least one selected from benzonorbornadiene, indenenorbornene, and methylphenylnorbornene. Copolymer.
[Claim 11]
　A cyclic olefin-based copolymer composition comprising the cyclic olefin-based copolymer according to any one of claims 1 to 10.
[Claim 12]
　The cyclic olefin-based copolymer composition according to claim 11, further comprising a hydrophilic stabilizer.
[Claim 13]
　A molded product comprising the cyclic olefin-based copolymer according to any one of claims 1 to 10 or the cyclic olefin-based copolymer composition according to claim 11 or 12.
[Claim 14]
　The molded body according to claim 13, which is an optical lens.
[Claim 15]
　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 (B) derived from a cyclic olefin having an aromatic ring (
A medical container comprising a cyclic olefin-based copolymer having C) .
[Claim 16]
　In the medical container according to claim 15,
　the total content of the structural unit (A), the structural unit (B) and the structural unit (C) in the cyclic olefin copolymer was set to 100 mol%. At this time, the medical container in which the content of the structural unit (C) in the cyclic olefin-based copolymer is 0.1 mol% or more and 50 mol% or less.
[Claim 17]
　In the medical container according to claim 15 or 16, when
　the total content of the structural unit (B) and the structural unit (C) in the cyclic olefin copolymer is 100 mol%, the cyclic olefin A medical container in which the content of the structural unit (C) in the copolymer is 5 mol% or more and 95 mol% or less.
[Claim 18]
　The medical container according to any one of claims 15 to 17
　, wherein a total content of the structural unit (A), the structural unit (B) and the structural unit (C) in the cyclic olefin-based copolymer is included. A medical container in which the content of the structural unit (A) in the cyclic olefin-based copolymer is 10 mol% or more and 80 mol% or less, when the amount is 100 mol%.
[Claim 19]
　The medical container according to any one of claims 15 to 18,
　wherein the cyclic olefin having no aromatic ring contains a compound represented by the following formula (B-1).
[In the

above formula [B-1], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and R 1 to R 18 and R a and R are b is a hydrocarbon group which may be independently substituted with a hydrogen atom, a halogen atom or a halogen atom, and R 15 to 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 may form an alkylidene group , or R 17 and R 18 may form an alkylidene group. Does not contain aromatic rings.)
[Claim 20]
　The medical container according to any one of claims 15 to 19,
　wherein the cyclic olefin having an aromatic ring is a compound represented by the following formula (C-1) or a compound represented by the following formula (C-2). And a medical container containing one or more selected from the group consisting of compounds represented by the following formula (C-3):
[Chemical bond 6]

(In the above formula (C-1), n ​​and q are 0, 1 or 2, respectively, and R 1 to R 17 are independently, a hydrogen atom, a halogen atom excluding a fluorine atom, or It is a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom other than a fluorine atom, one of R 10 to 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 10 may combine with each other to form a monocyclic ring or a polycyclic ring, and when q=1 or 2, R 10 and R 11 , R 11 and R 17 , R 17 and R 17 , R 17 And R 12 , R 12 and R 13 , R 13 and R 14 , R 14 and R 15 , R 15 and R 16 , R 16 and R 16 , R 16 and R 10May be bonded to each other to form a monocycle or a polycycle, and the monocycle or the polycycle may have a double bond, and the monocycle or the polycycle is an aromatic ring. It may be. )
[Chemical Formula 7]

in (above formula (C-2), n and m are each independently 0, 1 or 2, q is 1, 2 or 3, R 18 ~ R 31 are each independently, A hydrogen atom, a halogen atom excluding a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom excluding a fluorine atom, and when q=1, R 28 , R 29 and R 29 and R 30 , R 30 and R 31 may be coupled to each other to form a monocyclic or polycyclic ring, and when q = 2 or 3, R 28 and R 28 , R 28 and R 29 , R 29. And R 30 , R 30 and R 31 , R 31 and R 31 may be bonded to each other to form a monocyclic or polycyclic ring, the monocyclic ring or the polycyclic ring may have a double bond, and the monocyclic ring or the polycyclic ring may be formed. The polycycle may be an aromatic ring. )
[Formula 8]

in (above formula (C-3), q is 1, 2 or 3, R 32 ~ R 39 except each independently, a hydrogen atom, a halogen atom except fluorine atom or a fluorine atom, It is a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom, and when q=1, R 36 and R 37 , R 37 and R 38 , R 38 and R 39 are bonded to each other. It may form a monocyclic ring or a polycyclic ring, and when q=2 or 3, R 36 and R 36 , R 36 and R 37 , R 37 and R 38, R 38 and R 39 , R 39 and R 39 may be coupled to each other to form a monocyclic or polycyclic, and the monocyclic or polycyclic may have a double bond. The monocyclic ring or the polycyclic ring may be an aromatic ring. )
[Claim 21]
　In the medical container according to any one of claims 15 to 20,
　the glass transition temperature (Tg) of the cyclic olefin copolymer measured by a differential scanning calorimeter (DSC) is 120 ° C. or higher and 180 ° C. The following medical containers.
[Claim 22]
　The medical container according to any one of claims 15 to 21,
　wherein an intrinsic viscosity [η] of the cyclic olefin-based copolymer measured in decalin at 135°C is 0.05 dl/g or more and 5.0 dl/g. Medical container of g or less.
[Claim 23]
　The medical container according to any one of claims 15 to 22,
　wherein the cyclic olefin having an aromatic ring contains at least one selected from benzonorbornadiene, indenenorbornene, and methylphenylnorbornene.
[Claim 24]
　The medical container according to any one of claims 15 to 23, which is a
　syringe or a chemical storage container.Specification
Title of invention: Cyclic olefin copolymer, cyclic olefin copolymer composition, molded article and medical container
Technical field
[0001]
　The present invention relates to a cyclic olefin copolymer, a cyclic olefin copolymer composition, a molded article and a medical container.
Background technology
[0002]
　A cyclic olefin polymer is used for optical lenses such as an imaging lens, an fθ lens, and a pickup lens. Cyclic olefin-based polymers used in molded articles such as optical lenses are required to have characteristics such as high transparency, excellent dimensional stability, and excellent heat resistance.
　Further, for example, image pickup lenses used in smartphones, digital cameras, and the like are required to further improve the refractive index while keeping the value of birefringence low in order to reduce the size and thickness.
[0003]
　Examples of the technology relating to the cyclic olefin polymer used for such an optical lens include those described in Patent Document 1 (JP-A-10-287713) and Patent Document 2 (JP-A-2010-235719). Can be mentioned.
[0004]
　Patent Document 1 discloses (A) a linear or branched α-olefin having 2 to 20 carbon atoms, (B) a cyclic olefin represented by a predetermined chemical formula, and (C) an aromatic vinyl compound. The ultimate viscosity [η] is in the range of 0.1 to 10 dl / g, and is derived from the content ratio of the structural unit derived from the above (B) cyclic olefin and the above (C) aromatic vinyl compound. It describes a cyclic olefin-based copolymer that satisfies a specific relationship with the content ratio of constituent units.
[0005]
　In Patent Document 2, 30 to 70 mol% of a structural unit (A) derived from ethylene or an α-olefin having 3 to 20 carbon atoms, a structural unit (B) derived from a cyclic olefin represented by a predetermined chemical formula (B) 20% to 50 mol %, and 0.1 to 20 mol% of the structural unit (C) derived from an aromatic vinyl compound, and the intrinsic viscosity [η], 1 H-NMR and glass transition temperature satisfy predetermined requirements. A cyclic olefin polymer characterized by the above is described.
[0006]
　Further, the cyclic olefin resin has an excellent performance balance such as transparency and chemical resistance. Therefore, for example, it is being studied to be used as a material for forming a molded product such as a medical container. Examples of the technique relating to the resin composition containing such a cyclic olefin resin include those described in Patent Document 3 and Patent Document 4.
[0007]
　Patent Document 3 describes a cyclic olefin resin composition containing two specific cyclic olefin resins. It is described that the composition provides a molded article having improved slip properties, excellent transparency, surface gloss, and hygiene.
[0008]
　Patent Document 4 discloses that 60 to 90 parts by weight of a cyclic olefin resin, an aromatic vinyl/conjugated diene block copolymer having a number average molecular weight of 75,000 to 500,000 and/or a hydrogenated product of 10 to 40 thereof. A cyclic olefin resin composition consisting of parts by weight is described. Then, it is described that the composition provides a molded article having excellent impact strength and moisture resistance.
Prior art documents
Patent literature
[0009]
Patent Document 1: Japanese Patent Application Laid-Open No. 10-287713
Patent Document 2: Japanese Patent Application Laid-Open No. 2010-235719
Patent Document 3: Japanese Patent Application Laid-Open No. 2001-26693
Patent Document 4: Japanese Patent Application Laid-Open No. 8-277353
Summary of the invention
Problems to be Solved by the Invention
[0010]
　According to a study by the present inventors, in applications such as optical lenses, a resin material whose Abbe number can be adjusted to be lower than that of a conventional resin material is used for the purpose of improving image quality and improving the degree of freedom in designing an optical lens. It became clear that there was a demand.
　The first invention of the present invention has been made in view of the above circumstances, and provides a cyclic olefin copolymer having a high refractive index and capable of adjusting the Abbe number to be lower than that of a conventional resin material. ..
[0011]
　A medical container such as a syringe or a drug solution storage container is usually filled with the contents after sterilization. During this sterilization, the container may be irradiated with electron beams or gamma rays.
　According to the study by the present inventors, it has become clear that discoloration may occur in a conventional medical container using a cyclic olefin resin due to electron beam or gamma ray irradiation.
[0012]
　The second invention of the present case has been made in view of such circumstances. That is, the second invention of the present application is to provide a medical container which has little discoloration due to electron beam or gamma ray irradiation and is excellent in transparency.
Means for solving the problem
[0013]
　The present inventors have diligently studied to solve the above-mentioned problems of the first invention of the present invention. As a result, a constitutional unit derived from ethylene, bicyclo[2.2.1]-2-heptene and tetracyclo[4.4.0.1 2,5 . Higher by using a cyclic olefin-based copolymer having a structural unit derived from at least one compound selected from 1 7,10 ]-3-dodecene and a structural unit derived from a cyclic olefin having an aromatic ring. The inventors have found that the Abbe number can be adjusted to be lower than that of a conventional resin material while having a refractive index, and have completed the first invention of the present case.
[0014]
　That is, according to the first invention of the present case, the following cyclic olefin copolymer, cyclic olefin copolymer composition and molded article are provided.
[0015]
[1]
　Derived from 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 cyclic olefin having an aromatic ring.
A cyclic olefin-based copolymer having a structural unit (C) .
[2] In
　the cyclic olefin-based copolymer according to the above [1],
　a total content of the structural unit (A), the structural unit (B) and the structural unit (C) in the cyclic olefin-based copolymer. A cyclic olefin-based copolymer in which the content of the structural unit (A) in the cyclic olefin-based copolymer is 10 mol% or more and 80 mol% or less when the amount is 100 mol %.
[3] In
　the cyclic olefin-based copolymer according to the above [1] or [2],
　the total content of the structural unit (B) and the structural unit (C) in the cyclic olefin-based copolymer is 100. A cyclic olefin copolymer in which the content of the structural unit (C) in the cyclic olefin copolymer is 5 mol% or more and 95 mol% or less, when defined as mol %.
[4] In
　the cyclic olefin-based copolymer according to any one of the above [1] to [3], the cyclic olefin
　having no aromatic ring is a compound represented by the following formula (B-1). A cyclic olefin-based copolymer containing.
[Chemical 1]

(In the above formula [B-1], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and R 1 to R 18 and R a and R b are respectively Independently, it is a hydrogen atom, a halogen atom or a hydrocarbon group which may be substituted with a halogen atom, and R 15 to R 18 may be bonded to each other to form a monocycle or a polycycle, and The monocycle or polycycle may have a double bond, and R 15 and R 16 or R 17 and R 18 may form an alkylidene group, provided that an aromatic ring is included. no.)
[5]
　in the cycloolefin-based copolymer according to any one of the above [1] to [4],
　cyclic olefins having the aromatic ring is a compound represented by the following formula (C-1) A cyclic olefin-based copolymer containing one or more selected from the group consisting of a compound represented by the following formula (C-2) and a compound represented by the following formula (C-3).
[Chemical 2]

(In the formula (C-1), n ​​and q are each independently 0, 1 or 2, and R 1 to R 17 are independently hydrogen atom, a halogen atom excluding a fluorine atom, or a fluorine atom is excluded. It is a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom, one of R 10 to 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 , and R 15 and R 10 may be bonded to each other to form a monocyclic or polycyclic ring, and q=1 Or when it is 2, R 10 and R 11 , R 11And R 17 , R 17 and R 17 , R 17 and R 12 , R 12 and R 13 , R 13 and R 14 , R 14 and R 15 , R 15 and R 16 , R 16 and R 16 , R 16 and R. 10 may be bonded to each other to form a monocycle or a polycycle, and the monocycle or the polycycle may have a double bond, and the monocycle or the polycycle is an aromatic ring. It may be. )
[Formula 3]

in (above formula (C-2), n and m are each independently 0, 1 or 2, q is 1, 2 or 3, R 18 ~ R 31Each independently represents a hydrogen atom, a halogen atom excluding a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom excluding a fluorine atom, and when q=1, R 28 And R 29 , R 29 and R 30 , R 30 and R 31 may be coupled to each other to form a monocyclic or polycyclic, 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 , and R 31 and R 31 may be bonded to each other to form a monocycle or a polycycle, and the monocycle or the polycycle forms a double bond. It may have, and the monocycle or polycycle may be an aromatic ring. )
[Chemical 4]

(In the above formula (C-3), q is 1, 2 or 3, and R 32 to R 39 are independently substituted with hydrogen atom, halogen atom excluding fluorine atom, or halogen atom excluding fluorine atom, respectively. Which is a hydrocarbon group having 1 to 20 carbon atoms, and when q=1, R 36 and R 37 , R 37 and R 38 , and R 38 and R 39 are bonded to each other to form a monocyclic or polycyclic ring. And when q = 2 or 3, R 36 and R 36 , R 36 and R 37 , R 37 and R 38 , R 38 and R 39 , R 39 and R 39.May be bonded to each other to form a monocyclic or polycyclic ring, the monocyclic or polycyclic ring may have a double bond, and the monocyclic or polycyclic ring is an aromatic ring. It may be. )
[6]
　above [1] to the cyclic olefin copolymer according to any one of [5],
　when fabricated injection molded sheet having a thickness of 1.0mm made of the cyclic olefin copolymer , A cyclic olefin-based copolymer in which the Abbe number (ν) of the injection-molded sheet is 35 or more and 55 or less.
[7]
　The
　glass transition temperature of the cyclic olefin-based copolymer according to any one of [1] to [6], which is measured by a differential scanning calorimeter (DSC). A cyclic olefin-based copolymer having a (Tg) of 120° C. or higher and 180° C. or lower.
[8] In
　the cyclic olefin copolymer according to any one of the above [1] to [7], the
　ultimate viscosity [η] measured in decalin at 135 ° C. is 0.05 dl / g or more and 5.0 dl or more. /G or less cyclic olefin-based copolymer.
[9] In
　the cyclic olefin-based copolymer according to any one of [1] to [8]
　above, when a 1.0 mm-thick injection-molded sheet made of the cyclic olefin-based copolymer is prepared, A cyclic olefin copolymer having a birefringence of 1 nm or more and 200 nm or less of the injection-molded sheet.
[10]
　In the cyclic olefin-based copolymer according to any one of [1] to [9], the cyclic olefin
　having an aromatic ring includes at least one selected from benzonorbornadiene, indenenorbornene, and methylphenylnorbornene. Cyclic olefin copolymer.
[11]
　A cyclic olefin-based copolymer composition containing the cyclic olefin-based copolymer according to any one of the above [1] to [10].
[12]
　The cyclic olefin-based copolymer composition according to the above [11], which further contains a hydrophilic stabilizer.
[13]
　A molded product containing the cyclic olefin-based copolymer described in any one of [1] to [10] above or the cyclic olefin-based copolymer composition described in [11] or [12] above.
[14]
　The molded product according to the above [13], which is an optical lens.
[0016]
　Further, the inventors of the present invention have made extensive studies in order to solve the above problems related to the second invention of the present case. As a result, as a resin constituting a medical container, a cyclic olefin system containing a structural unit derived from α-olefin, a structural unit derived from a cyclic olefin having no aromatic ring, and a structural unit derived from a cyclic olefin having an aromatic ring. It has been found that the above problems can be solved by using a copolymer. Then, the second invention shown below was completed.
[0017]
　That is, according to the second aspect of the present invention, the following medical container and cyclic olefin copolymer composition for a medical container are provided.
[0018]
[15]
　Derived from 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 cyclic olefin having an aromatic ring.
A medical container comprising a cyclic olefin-based copolymer having the structural unit (C) .
[16] In
　the medical container according to [15],
　the total content of the structural unit (A), the structural unit (B) and the structural unit (C) in the cyclic olefin copolymer is 100. The medical container in which the content of the structural unit (C) in the cyclic olefin-based copolymer is 0.1 mol% or more and 50 mol% or less when defined as mol %.
[17] In
　the medical container according to [15] or [16],
　the total content of the structural unit (B) and the structural unit (C) in the cyclic olefin-based copolymer is 100 mol%. A medical container in which the content of the structural unit (C) in the cyclic olefin copolymer is 5 mol% or more and 95 mol% or less.
[18] In
　the medical container according to any one of [15] to [17], the
　structural unit (A), the structural unit (B), and the structural unit in the cyclic olefin-based copolymer. A medical container in which the content of the structural unit (A) in the cyclic olefin-based copolymer is 10 mol% or more and 80 mol% or less, when the total content of (C) is 100 mol %.
[19] In
　the medical container according to any one of the above [15] to [18], the
　cyclic olefin having no aromatic ring contains a compound represented by the following formula (B-1) for medical use. container.
[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 to R 18 and R a and R are b is each independently a hydrogen atom, a halogen atom or a hydrocarbon group which may be substituted with a halogen atom, and R 15 to R 18 may be bonded to each other to form a monocyclic or polycyclic ring. , And the monocycle or polycycle may have a double bond, and R 15 and R 16 or R 17 and R 18 may form an alkylidene group. It does not contain an aromatic ring.)
[20]
　The medical container according to any one of [15] to [19] above,
　The cyclic olefin having an aromatic ring is 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). A medical container containing one or more of the following.
[In the

formula (C-1), n ​​and q are each independently 0, 1 or 2, and R 1 to R 17 are each independently a hydrogen atom, a halogen atom other than a fluorine atom, or It is a hydrocarbon group having 1 to 20 carbon atoms which may be substituted by a halogen atom other than a fluorine atom, one of R 10 to 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 10.May combine with each other to form a monocyclic ring or a polycyclic ring, and when q=1 or 2, R 10 and R 11 , R 11 and R 17 , R 17 and R 17 , R 17 and R 12 , R 12 and R 13 , R 13 and R 14 , R 14 and R 15 , R 15 and R 16 , R 16 and R 16 , and R 16 and R 10 combine with each other to form a monocyclic or polycyclic. Also, the monocycle or the polycycle may have a double bond, and the monocycle or the polycycle may be an aromatic ring. )
[In the

formula (C-2), n and m are each independently 0, 1 or 2, q is 1, 2 or 3, and R 18 to R 31 are independently hydrogen. Atom, a halogen atom excluding a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom excluding a fluorine atom, and when q=1, R 28 , R 29 , and R 29 And R 30 and R 30 and R 31 may be bonded to each other to form a monocyclic or polycyclic ring, and when q=2 or 3, R 28 and R 28 , R 28 and R 29 , R 29 and R 30 , R 30 and R 31 , R 31 and R 31May be bonded to each other to form a monocyclic or polycyclic ring, the monocyclic or polycyclic ring may have a double bond, and the monocyclic or polycyclic ring is an aromatic ring. There may be. )
[Formula 8]

in (above formula (C-3), q is 1, 2 or 3, R 32 ~ R 39 except each independently, a hydrogen atom, a halogen atom except fluorine atom or a fluorine atom, It is a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom, and when q=1, R 36 and R 37 , R 37 and R 38 , R 38 and R 39 are bonded to each other. It may form a monocyclic ring or a polycyclic ring, and when q=2 or 3, R 36 and R 36 , R 36 and R 37 , R 37 and R 38 , R 38 and R 39., R 39 and R 39 may be coupled to each other to form a monocyclic or polycyclic, the monocyclic or polycyclic may have a double bond, and the monocyclic or polycyclic. The ring may be an aromatic ring. )
[21]
　In the medical container according to any one of the above [15] to [20],
　are measured by differential scanning calorimetry (DSC), wherein the cycloolefin copolymer a glass transition temperature (Tg ) 120°C or higher and 180°C or lower.
[22] In
　the medical container according to any one of [15] to [21], the
　intrinsic viscosity [η] of the cyclic olefin-based copolymer measured in decalin at 135° C. is 0.05 dl/ A medical container having a weight of not less than g and not more than 5.0 dl/g.
[23] In
　the medical container according to any one of [15] to [22], the
　cyclic olefin having an aromatic ring contains at least one selected from benzonorbornadiene, indenenorbornene, and methylphenylnorbornene. Medical container.
[24] In
　the medical container according to any one of the above [15] to [23]
　, a medical container which is a syringe or a chemical storage container.
[25]
　A cyclic olefin-based copolymer composition for forming a medical container,
　comprising a structural unit (A) derived from an α-olefin having 2 to 20 carbon atoms and a
　cyclic olefin having no aromatic ring. A cyclic olefin-based copolymer composition for a medical container
　,
which comprises a cyclic olefin-based copolymer having a structural unit (B) to be obtained and a structural unit (C) derived from a cyclic olefin having an aromatic ring .
[26]
　The cyclic olefin-based copolymer composition for medical container according to the above [25], wherein the
　structural unit (A), the structural unit (B) and the structural unit in the cyclic olefin-based copolymer are included. For a medical container in which the content of the structural unit (C) in the cyclic olefin-based copolymer is 0.1 mol% or more and 50 mol% or less, when the total content of (C) is 100 mol %. Cyclic olefin copolymer composition.
[27] In the
　cycloolefin copolymer composition for a medical container according to the above [25] or [26], the
　structural unit (A) and the structural unit (B) in the cyclic olefin copolymer. And medical composition in which the content of the structural unit (A) in the cyclic olefin-based copolymer is 10 mol% or more and 80 mol% or less, when the total content of the structural unit (C) is 100 mol %. A cyclic olefin-based copolymer composition for a container.
[28]
　The cycloolefin copolymer composition for a medical container according to any one of [25] to [27 ] above,
　A cyclic olefin-based copolymer composition for a medical container, wherein the cyclic olefin having no aromatic ring contains a compound represented by the following formula (B-1).
[In the

above formula [B-1], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and R 1 to R 18 and R a and R are b is a hydrocarbon group which may be independently substituted with a hydrogen atom, a halogen atom or a halogen atom, and R 15 to R 18 may be bonded to each other to form a monocyclic or polycyclic ring. , And the monocycle or polycycle may have a double bond, and R 15 and R 16 or R 17 and R 18 may form an alkylidene group. It does not contain an aromatic ring.)
[29]
　The cyclic olefin-based copolymer composition for a medical container according to any one of [25] to [28 ] above,
　The cyclic olefin having an aromatic ring is 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). A cyclic olefin copolymer composition for a medical container containing one or more of the following compounds.
[Chemical

formula 10] (In the above formula (C-1), n ​​and q are 0, 1 or 2, respectively, and R 1 to R 17 are independently each of a hydrogen atom, a halogen atom excluding a fluorine atom, or optionally substituted with a halogen atom other than fluorine atom a hydrocarbon group which may carbon atoms 1 ~ 20, R 10 ~ R 17 one of is a bond, and R when q = 0 10 and R 11 , R 11 and R 12 , R 12 and R 13 , R 13 and R 14 , R 14 and R 15 , R 15 and R 10 may be bonded to each other to form a monocyclic or polycyclic ring, and when q=1 or 2, R 10 and R 11 , R 11 and R 17 , R 17 and R 17 , R 17 and R 12 , R 12 and R 13 , R 13 and R 14 , R 14 and R 15 , R 15 and R 16 , R 16 and R 16 , R 16 and R 10.May be bonded to each other to form a monocycle or a polycycle, and the monocycle or the polycycle may have a double bond, and the monocycle or the polycycle is an aromatic ring. There may be. )
[Chemical

formula 11] (In the above formula (C-2), n and m are 0, 1 or 2, respectively, q is 1, 2 or 3, and R 18 to R 31 are independent, respectively. A hydrogen atom, a halogen atom excluding a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom excluding a fluorine atom, and when q=1, R 28 , R 29 and R 29 and R 30 , R 30 and R 31 may be coupled to each other to form a monocyclic or polycyclic ring, and when q = 2 or 3, R 28 and R 28 , R 28 and R 29 , R 29. And R 30 and R 30 and R 31 , R 31 and R 31 may be bonded to each other to form a monocycle or a polycycle, the monocycle or the polycycle may have a double bond, and the monocycle or the above The polycycle may be an aromatic ring. )
[Formula 12]

in (above formula (C-3), q is 1, 2 or 3, R 32 ~ R 39 except each independently, a hydrogen atom, a halogen atom except fluorine atom or a fluorine atom, It is a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom, and when q=1, R 36 and R 37 , R 37 and R 38 , R 38 and R 39 are bonded to each other. It may form a monocyclic ring or a polycyclic ring, and when q=2 or 3, R 36 and R 36 , R 36 and R 37 , R 37 and R 38, R 38 and R 39 , R 39 and R 39 may be bonded to each other to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring may have a double bond. The monocycle or polycycle may be an aromatic ring. )
[30]
　in the above-mentioned [25] to a medical container cycloolefin copolymer composition according to any one of [29],
　are measured by differential scanning calorimetry (DSC), the cyclic olefin-based A cyclic olefin copolymer composition for a medical container in which the glass transition temperature (Tg) of the copolymer is 120 ° C. or higher and 180 ° C. or lower.
[31] In the
　cyclic olefin copolymer composition for medical containers according to any one of [25] to [30], the
　limit of the cyclic olefin copolymer measured in decalin at 135°C. A cycloolefin copolymer composition for a medical container, which has a viscosity [η] of 0.05 dl/g or more and 5.0 dl/g or less.
[32] In the
　cyclic olefin-based copolymer composition for medical containers according to any one of the above [25] to [31], the
　cyclic olefin having an aromatic ring is benzonorbornadiene, indennorbornene and methylphenyl. A cyclic olefin-based copolymer composition for a medical container, containing at least one selected from norbornene.
[33]
　The cyclic olefin-based copolymer composition for a medical container according to any one of [25] to [32], wherein the
　medical container is a syringe or a drug solution storage container. Olefin-based copolymer composition.
Effect of the invention
[0019]
　According to the first aspect of the present invention, it is possible to provide a cyclic olefin-based copolymer that has a high refractive index and can be adjusted to have a lower Abbe number than conventional resin materials.
[0020]
　According to the second aspect of the present invention, it is possible to provide a medical container which has little discoloration due to electron beam or gamma ray irradiation and is excellent in transparency.
MODE FOR CARRYING OUT THE INVENTION
[0021]
　Hereinafter, the present invention will be described based on embodiments. In the present embodiment, “A to B” indicating a numerical range represents A or more and B or less unless otherwise specified.
[0022]
1. First Invention
[Cyclic Olefin Copolymer]
　First, the cyclic olefin copolymer (P) of the embodiment according to the first invention will be described.
　The cyclic olefin-based copolymer (P) according to the present embodiment is a structural unit (A) derived from an α-olefin having 2 to 20 carbon atoms and a structural unit derived from a cyclic olefin having no aromatic ring. It has (B) and a structural unit (C) derived from a cyclic olefin having an aromatic ring.
[0023]
　The cyclic olefin-based copolymer (P) according to the present embodiment has a structural unit (A) derived from an α-olefin having 2 to 20 carbon atoms and a structural unit derived from a cyclic olefin having no aromatic ring (a structural unit (A). By including the structural unit (C) derived from B) and a cyclic olefin having an aromatic ring, the Abbe number can be adjusted to a lower level while satisfying the high refractive index required for optical lenses and the like.
　From the above, according to the cyclic olefin copolymer (P) according to the present embodiment, it is possible to obtain a molded product having a high refractive index and a lower Abbe number than the conventional resin material.
[0024]
(Structural Unit (A) Derived from Ethylene) The structural unit (A) according to
　this embodiment is a structural unit derived from an α-olefin having 2 to 20 carbon atoms.
　Here, the α-olefin having 2 to 20 carbon atoms may be linear or branched, and may be ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, Linear α-olefins having 2 to 20 carbon atoms such as 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene; 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- Examples thereof include branched α-olefins having 4 to 20 carbon atoms such as 1-hexene and 3-ethyl-1-hexene. Among these, linear α-olefins having 2 to 4 carbon atoms are preferable, and ethylene is particularly preferable. Such linear or branched α-olefins may be used alone or in combination of two or more.
[0025]
　When the total content of the structural unit (A), the structural unit (B) and the structural unit (C) in the cyclic olefin-based copolymer (P) according to the present embodiment is 100 mol%, the present embodiment The content of the structural unit (A) in the cyclic olefin copolymer (P) according to the embodiment is preferably 10 mol% or more and 80 mol% or less, more preferably 30 mol% or more and 75 mol% or less, further preferably Is 40 mol% or more and 70 mol% or less.
　When the content of the structural unit (A) is at least the lower limit value described above, the heat resistance and dimensional stability of the obtained molded article can be improved. Further, when the content of the structural unit (A) is not more than the upper limit value, the transparency and the like of the obtained molded product can be improved.
　In this embodiment, the content of the structural unit (A) can be measured by , for example, 1 1 H-NMR or 13 C-NMR.
[0026]
(Constituent Unit (B) Derived from Cyclic Olefin) The structural unit (B) according to the
　present embodiment is a structural unit derived from a cyclic olefin having no aromatic ring. The structural unit (B) according to this embodiment preferably contains a structural unit derived from the compound represented by the following formula (B-1) from the viewpoint of further improving the refractive index of the obtained molded product.
[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 to R 18 and R a and R are b is independently a hydrogen atom, a halogen atom or a hydrocarbon group which may be substituted with a halogen atom, and R 15 to R 18 may be bonded to each other to form a monocyclic ring or a polycyclic ring. , And the monocycle or polycycle may have a double bond, and R 15 and R 16 or R 17 and R 18 may form an alkylidene group. Does not contain aromatic rings.)
　Among these, the structural unit (B) according to the present embodiment is a structural unit derived from bicyclo [2.2.1] -2-heptene, tetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene constitutional unit derived from and hexacyclo [6,6,1,1 3,6 , 1 10,13 , 0 2,7 , 0 9,14 ] heptadecene -4 constituent units derived from such It is preferable to include at least one structural unit selected from the group consisting of bicyclo[2.2.1]-2-heptene-derived structural units and tetracyclo[4.4.0.1 2,5 . It is more preferable to contain at least one structural unit selected from the structural units derived from 1 7,10 ]-3-dodecene, and tetracyclo[4.4.0.1 2,5 . It is particularly preferable to include a structural unit derived from 1 7,10 ]-3-dodecene.
[0027]
(
　Structural Unit (C) Derived from Cyclic Olefin Having Aromatic Ring) The structural unit (C) according to the present embodiment is a structural unit derived from a cyclic olefin having an aromatic ring.
　Examples of the cyclic olefin having an aromatic ring according to the present embodiment include 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). Examples include compounds. The cyclic olefins having these aromatic rings may be used alone or in combination of two or more.
[0028]
[Chemical 14]

[0029]
　In the above formula (C-1), n ​​and q are 0, 1 or 2, respectively. n is preferably 0 or 1, and more preferably 0. q is preferably 0 or 1, more preferably 0.
　R 1 ~ R 17 are each independently a hydrocarbon group of a hydrogen atom, a halogen atom or by optionally 1 carbon atoms also be ~ 20 substituted by a halogen atom other than fluorine atom, except fluorine atom, R 10 - It is preferable that one of R 17 is a bond and R 15 is a bond.
　R 1 to R 17 are preferably each 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 may be bonded to each other to form a monocyclic or polycyclic ring, and when q=1 or 2, R 10 and R 11 , R 11 and R 17 are combined. , R 17 and R 17 , R 17 and R 12 , R 12 and R 13 , R 13 and R 14 , R 14 and R 15 , R 15 and R 16 , R 16 and R 16, R 16 and R 10 may be bonded to each other to form a monocyclic or polycyclic, or the monocyclic or polycyclic may have a double bond, the monocyclic or polycyclic. The ring may be an aromatic ring.
　Of the above formula (C-1), the compound represented by the following formula (C-1A) is preferable.
[0030]
[Chemical 15]

[0031]
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 to R 31 are hydrocarbon groups having 1 to 20 carbon atoms which may be independently substituted with a hydrogen atom, a halogen atom excluding a fluorine atom, or a halogen atom excluding a fluorine atom.
　R 18 to R 31 are preferably each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrogen atom.
　Further, when q=1, R 28 and R 29 , R 29 and R 30 , and R 30 and R 31 may be bonded to each other to form a monocyclic or polycyclic ring, and when q=2 or 3, R 28 and R 28, R 28 and R 29 , R 29 and R 30 , R 30 and R 31 , and R 31 and R 31 may be bonded to each other to form a monocyclic or polycyclic, and the monocyclic or polycyclic is formed. It may have a double bond, and the monocycle or polycycle may be an aromatic ring.
[0032]
In the

　above formula (C-3), q is 1, 2 or 3, preferably 1 or 2, and more preferably 1.
　R 32 to R 39 are each independently a hydrogen atom, a halogen atom excluding a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom excluding a fluorine atom.
　R 32 to R 39 are preferably each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrogen atom.
　When q=1, R 36 and R 37 , R 37 and R 38 , R 38 and R 39 may be bonded to each other to form a monocyclic or polycyclic ring, and when q=2 or 3, R 36 and R 37 may be combined. 36 and R 36 , R 36 and R 37 , R 37 and R 38 , R 38 and R 39 , and R 39 and R 39 may be bonded to each other to form a monocycle or a polycycle, and the monocycle or the polycycle has a double bond. Also, the monocycle or polycycle may be an aromatic ring.
[0033]
　In addition, examples of the hydrocarbon group having 1 to 20 carbon atoms include, for example, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, and an aromatic hydrocarbon group, each independently. To be More specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group and an octadecyl group, and the cycloalkyl group includes cyclohexyl. Examples of the aromatic hydrocarbon group include an aryl group such as a phenyl group, a tolyl group, a naphthyl group, a benzyl group and a phenylethyl group, or an aralkyl group. These hydrocarbon groups may be substituted with a halogen atom other than a fluorine atom.
[0034]
　Among these, the cyclic olefin having an aromatic ring according to the present embodiment is preferably one having one aromatic ring, and for example, at least one selected from benzonorbornadiene, indenenorbornene and methylphenylnorbornene is preferable. ..
[0035]
　Examples of the cyclic olefin having an aromatic ring according to the present embodiment include a compound represented by the following formula (C-1'), a compound represented by the following formula (C-2'), and the following formula (C-3). The compound etc. which are shown by') are also mentioned. The cyclic olefins having these aromatic rings may be used alone or in combination of two or more.
[0036]
[Chemical 18]

[0037]
[Chemical 19]

[0038]
[Chemical 20]

[0039]
　In the above formula (C-1′), formula (C-2′) and formula (C-3′), m and n are 0, 1 or 2, and R 1 to R 36 are each independently a hydrogen atom. , a halogen atom or a hydrocarbon group which have ~ 1 carbon atoms and optionally 20 substituted by a halogen atom other than fluorine atom, except fluorine atom, R 10 and R 11 , R 11 and R 12 , R 12 and R 13 , R 13 and R 14 , R 25 and R 26 , R 26 and R 27 , R 27 and R 28 , R 33 and R 34 , R 34 and R 35, R 35 and R 36 may be bonded to each other to form a single ring, and the single ring may have a double bond.
[0040]
　Further, in the above formula (C-1′), formula (C-2′) and formula (C-3′), m is preferably 0 or 1, and more preferably 1. n is preferably 0 or 1, more preferably 0. R 1 to R 36 are preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrogen atom.
[0041]
　In addition, examples of the hydrocarbon group having 1 to 20 carbon atoms include, for example, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, and an aromatic hydrocarbon group, each independently. To be More specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group and an octadecyl group, and the cycloalkyl group includes cyclohexyl. Examples of the aromatic hydrocarbon group include an aryl group such as a phenyl group, a tolyl group, a naphthyl group, a benzyl group and a phenylethyl group, or an aralkyl group. These hydrocarbon groups may be substituted with a halogen atom other than a fluorine atom.
[0042]
　Among these, the cyclic olefin having an aromatic ring according to the present embodiment is preferably one having one aromatic ring, and for example, at least one selected from benzonorbornadiene, indenenorbornene and methylphenylnorbornene is preferable. ..
[0043]
　When the total content of the structural unit (B) and the structural unit (C) in the cyclic olefin copolymer (P) according to the present embodiment is 100 mol%, the cyclic olefin copolymer according to the present embodiment The content of the structural unit (C) in the polymer (P) is preferably 5 mol% or more and 95 mol% or less, more preferably 10 mol% or more and 90 mol% or less, still more preferably 20 mol% or more and 80 mol% or less. Below, it is even more preferably 30 mol% or more and 80 mol% or less, and even more preferably 40 mol% or more and 78 mol% or less.
　When the content of the structural unit (C) is at least the lower limit value described above, it is possible to further reduce the Abbe number in the obtained molded product while maintaining a high refractive index. Further, when the content of the structural unit (C) is not more than the upper limit value, the balance between the refractive index and the Abbe number of the obtained molded product can be improved.
　In the present embodiment, the content of the structural unit (B) and the structural unit (C) can be measured by , for example, 1 H-NMR or 13 C-NMR.
[0044]
　The copolymerization type of the cyclic olefin-based copolymer (P) according to this embodiment is not particularly limited, but examples thereof include a random copolymer and a block copolymer. In the present embodiment, as the cyclic olefin-based copolymer (P) according to the present embodiment, a molded product having excellent optical properties such as transparency, Abbe number, refractive index and birefringence can be obtained. It is preferably a random copolymer.
[0045]
　The cyclic olefin-based copolymer (P) according to the present embodiment is disclosed in, for example, JP-A-60-168708, JP-A-61-120816, JP-A-61-115912, and JP-A-61- No. 115916, No. 61-271308, No. 61-272216, No. 62-252406, No. 62-252407, No. 2007-314806, No. 2007-314806. It can be produced by appropriately selecting the conditions according to the method disclosed in 2010-241932.
[0046]
　In the cyclic olefin-based copolymer (P) according to the present embodiment, when an injection-molded sheet having a thickness of 1.0 mm made of the cyclic olefin-based copolymer (P) is produced, it is measured according to ASTM D542. The refractive index (nd) of the injection molded sheet at a wavelength of 589 nm is preferably 1.545 or more, preferably 1.550 or more, and more preferably 1.555 or more. The upper limit of the refractive index (nd) is not particularly limited, but is, for example, 1.580 or less.
　When the refractive index is within the above range, the molded product obtained by using the cyclic olefin-based copolymer (P) according to the present embodiment can have a thinner thickness while maintaining good optical characteristics.
[0047]
　In addition, in the cyclic olefin-based copolymer (P) according to the present embodiment, from the viewpoint of further improving the transparency of the obtained molded product, injection of the cyclic olefin-based copolymer (P) having a thickness of 1.0 mm When a molded sheet is produced, the haze of the injection molded sheet measured according to JIS K7136 is preferably less than 5%.
[0048]
　Further, in the cyclic olefin copolymer (P) according to the present embodiment, the cyclic olefin copolymer (P) is composed of the cyclic olefin copolymer (P) from the viewpoint of adjusting the Abbe number (ν) of the obtained molded product to a more suitable range. When an injection-molded sheet having a thickness of 1.0 mm is produced, the Abbe number (ν) of the injection-molded sheet is preferably 35 or more and 55 or less, more preferably 40 or more and 50 or less, and further preferably 43 or more and 47 or less. .
　The Abbe number (ν) of the injection-molded sheet can be calculated from the refractive index of the injection-molded sheet at 23° C. at wavelengths of 486 nm, 589 nm and 656 nm using the following formula.
　ν=(nD-1)/(nF-nC)
　nD: Refractive index at wavelength 589 nm
　nC: Refractive index at
　wavelength 656 nm nF: Refractive index at wavelength 486 nm
[0049]
　Further, in the cyclic olefin copolymer (P) according to the present embodiment, from the viewpoint of adjusting the birefringence of the obtained molded product to a more suitable range, the thickness 1 made of the cyclic olefin copolymer (P) is 1. When an injection-molded sheet having a thickness of 0.0 mm is produced, the birefringence of the injection-molded sheet is preferably 1 nm or more and 200 nm or less.
　In the present embodiment, the birefringence of the injection-molded sheet is an average value of the phase difference of 20 to 35 mm from the gate direction, which is measured at a measurement wavelength of 650 nm using KOBRA CCD manufactured by Oji Scientific Instruments.
[0050]
　The glass transition temperature (Tg) of the cyclic olefin-based copolymer (P) according to the present embodiment, which is measured by a differential scanning calorimeter (DSC), is the transparency, haze, Abbe number, and birefringence of the obtained molded product. From the viewpoint of further improving heat resistance while maintaining good refractive index and the like, the temperature is preferably 120 ° C. or higher and 180 ° C. or lower, more preferably 130 ° C. or higher and 170 ° C. or lower, and further preferably 140 ° C. or higher and 160 ° C. or lower. is there.
[0051]
　The intrinsic viscosity [η] (in 135 ° C. decalin) of the cyclic olefin copolymer (P) according to the present 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.
[0052]
[Cyclic olefin-based copolymer composition]
　The cyclic olefin-based copolymer composition according to the present embodiment contains the cyclic olefin-based copolymer (P) according to the present embodiment, and is optionally based on the cyclic olefin-based copolymer. Other components other than the copolymer (P) may be included. In addition, in this embodiment, the case where the cyclic olefin-based copolymer composition according to this embodiment contains only the cyclic olefin-based copolymer (P) is also referred to as a cyclic olefin-based copolymer composition.
[0053]
　The cyclic olefin-based copolymer composition according to this embodiment may further contain a hydrophilic stabilizer. It is more preferable to include the hydrophilic stabilizer, because the deterioration of the optical performance under high temperature and high humidity conditions can be suppressed.
　The hydrophilic stabilizer is preferably a fatty acid ester of a fatty acid and a polyhydric alcohol. A fatty acid ester of a fatty acid and a polyhydric alcohol having one or more ether groups is more preferable.
[0054]
　Examples of the fatty acid ester include monoglycerin fatty acid ester, diglycerin fatty acid ester, triglycerin fatty acid ester, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate and the like.
　The 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. The ether group of the polyhydric alcohol does not include the ether group in the ester group.
　Examples of the polyhydric alcohol having one or more ether groups include monoglycerin, diglycerin, triglycerin, tetraglycerin and sorbitan.
　In the present embodiment, the fatty acid ester preferably contains a monoglycerin fatty acid ester, a diglycerin fatty acid ester, and a triglycerin fatty acid ester. The diglycerin fatty acid ester is one in which at least one of the four hydroxy groups contained in diglycerin is esterified with a fatty acid.
[0055]
　Fatty acids include butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and other saturated fatty acids; crotonic acid, myristoleic acid, palmitoleic acid. , Unsaturated acids such as sapienoic acid, oleic acid, elaidic acid, gadoleic acid, eicosenoic acid; diunsaturated fatty acids such as linoleic acid, eicosadienoic acid, docosadienoic acid; Examples thereof include tri-unsaturated fatty acids such as enoic acid; tetra-unsaturated fatty acids such as stearidonic acid, arachidonic acid, and eicosatetraenoic acid.
[0056]
　Diglycerin fatty acid esters include diglycerin monocaprelate, diglycerin dicaprelate, diglycerin monocaplate, diglycerin dicaplate, diglycerin monolaurate, diglycerin dilaurate, diglycerin monomillistate, and diglycerin dimylystate. , Diglycerin monopalmitate, diglycerin dipalmitate, diglycerin monostearate, diglycerin distearate, diglycerin monobehenate, diglycerin dibehenate, etc. diglycerin saturated fatty acid ester; diglycerin monooleate, di Examples thereof include diglycerin unsaturated fatty acid ester such as glycerin diolate; and the like, and one kind or a combination of two or more kinds selected from these can be used.
　In this embodiment, the diglycerin fatty acid ester is preferably an ester of diglycerin and a saturated or unsaturated fatty acid having 12 to 18 carbon atoms selected from the above.
[0057]
　From the viewpoint of the effect of the present embodiment, it is preferable to include diglycerin unsaturated fatty acid ester as a main component, and it is more preferable to include diglycerin monooleate as a main component. Since the diglycerin skeleton has hydrophilicity and the fatty acid improves the compatibility with the resin, transparency is maintained and moisture resistance is excellent.
[0058]
　The cyclic olefin-based copolymer composition according to the present embodiment can contain at least one diglycerin fatty acid ester. Preferred embodiments of the at least one diglycerin fatty acid ester include monoester alone or a combination of monoester and diester.
[0059]
　Triglycerin fatty acid ester is an ester of fatty acid and triglycerin.
　The triglycerin fatty acid ester according to the present embodiment is one in which at least one of the five hydroxy groups contained in triglycerin is esterified with a fatty acid.
[0060]
　The triglycerin fatty acid ester, 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, Triglycerin tripalmitate, Triglycerin monostearate, Triglycerin Triglycerin saturated fatty acid ester such as distearate, triglycerin tristearate, triglycerin monobehenate, triglycerin dibehenate, triglycerin tribehenate; triglycerin monooleate, triglycerin dioleate, triglycerin trioleate And triglycerin unsaturated fatty acid ester; and the like, and one or more selected from these can be used in combination.
　The triglycerin fatty acid ester according to the present embodiment preferably contains an ester of triglycerin and a saturated or unsaturated fatty acid having 8 to 24 carbon atoms, and triglycerin and a saturated or unsaturated fatty acid having 12 to 18 carbon atoms. More preferably, the ester of
[0061]
　Examples of the triglycerin fatty acid ester according to the present embodiment include monoester alone, a mixture of monoester and diester, a mixture of monoester, diester and triester, and the like.
　As such triglycerin fatty acid ester, for example, compounds described in JP-A 2006-232714, JP-A 2002-275308, JP-A 10-165152 and the like can be used.
　Examples of commercial products of the hydrophilic stabilizer according to the present embodiment include Riquemal DO-100 (manufactured by Riken Vitamin Co., Ltd.) and Exepar PE-MS (manufactured by Kao Co.).
　In the cyclic olefin-based copolymer composition according to the present embodiment, the lower limit of the content of the hydrophilic stabilizer is 0.05 parts by mass or more based on 100 parts by mass of the cyclic olefin-based copolymer (P). It is preferably 0.4 parts by mass or more, and more preferably 0.4 parts by mass or more. The upper limit of the content of the hydrophilic stabilizer is preferably 3.0 parts by mass or less, and more preferably 2.5 parts by mass or less with respect to 100 parts by mass of the cyclic olefin copolymer (P). More preferably, it is 1.2 parts by mass or less.
[0062]
[Molded product]
　The molded product according to the present embodiment is a molded product containing the cyclic olefin-based copolymer (P) or the cyclic olefin-based copolymer composition according to the present embodiment.
　Since the molded product according to the present embodiment contains the cyclic olefin copolymer (P) according to the present embodiment, it has an excellent balance of heat resistance, transparency, haze, birefringence, chemical resistance, low moisture absorption and the like. At the same time, it has a higher refractive index and a lower Abbe number than conventional resin materials. Therefore, it is suitable for applications of optical lenses.
[0063]
　Since the molded product according to this embodiment has excellent optical characteristics, it can be suitably used as an optical lens such as a spectacle lens, an fθ lens, a pickup lens, an imaging lens, a sensor lens, a prism, a light guide plate, and a vehicle camera lens. Since it has a high refractive index and exhibits an Abbe number lower than that of a conventional resin material, it can be particularly suitably used as an imaging lens.
　The unit of the imaging lens is composed of a plurality of lenses having different Abbe numbers and refractive indexes, and generally, a lens having a large Abbe number and a lens having a small Abbe number are combined. The molded body according to the present embodiment can be suitably used as a lens corresponding to an intermediate region between a high Abbe number and a low Abbe number, and the degree of freedom in designing a lens unit can be improved.
[0064]
　In addition, the content of the cyclic olefin-based copolymer (P) in the molded product according to the present embodiment is more suitable for improving the performance balance of transparency, haze, birefringence, Abbe number and refractive index. When the whole body is 100% by mass, it is preferably 50% by mass or more and 100% by mass or less, more preferably 70% by mass or more and 100% by mass or less, and further preferably 80% by mass or more and 100% by mass or less. And particularly preferably 90% by mass or more and 100% by mass or less.
[0065]
　The molded product according to the present embodiment can be obtained by molding a resin composition containing the cyclic olefin copolymer (P) into a predetermined shape. The method of molding the resin composition containing the cyclic olefin-based copolymer (P) to obtain a molded product is not particularly limited, and a known method can be used. Depending on its application and shape, for example, extrusion molding, injection molding, compression molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, vacuum molding, powder slush molding, calender molding, foam molding, etc. Is applicable. Among these, the injection molding method is preferable from the viewpoint of moldability and productivity. The molding conditions are appropriately selected depending on the purpose of use or the molding method. For example, the resin temperature in injection molding is usually 150 ° C. to 400 ° C., preferably 200 ° C. to 350 ° C., more preferably 230 ° C. to 330 ° C. It is appropriately selected in the range.
[0066]
　The molded body according to this embodiment can be used in various forms such as a lens shape, a spherical shape, a rod shape, a plate shape, a column shape, a cylindrical shape, a tube shape, a fiber shape, a film shape or a sheet shape.
[0067]
　The molded product or the cyclic olefin-based copolymer composition according to the present embodiment, if necessary, contains a known additive as an optional component within a range that does not impair the good physical properties of the molded product according to the present embodiment. Can be made Examples of the additives include phenolic stabilizers, higher fatty acid metal salts, antioxidants, ultraviolet absorbers, hindered amine light stabilizers, hydrochloric acid absorbers, metal deactivators, antistatic agents, antifogging agents, and lubricants. , A slip agent, a nucleating agent, a plasticizer, a flame retardant, a phosphorus-based stabilizer and the like can be blended to such an extent that the object of the present invention is not impaired, and the blending ratio is an appropriate amount.
[0068]
　The optical lens according to the present embodiment may be combined with an optical lens different from the above optical lens to form an optical lens system.
　That is, the optical lens system according to the present embodiment is different from the first optical lens configured by the molded body containing the cyclic olefin-based copolymer (P) according to the present embodiment, and the first optical lens. A second optical lens;
[0069]
　The second optical lens is not particularly limited, but for example, an optical lens made of at least one resin selected from polycarbonate resin and polyester resin can be used.
[0070]
　Although the embodiments of the first invention have been described above, these are merely examples of the first invention, and various configurations other than the above may be adopted.
　Further, the first invention is not limited to the above-described embodiment, and modifications, improvements, etc. within a range in which the object of the first invention can be achieved are included in the first invention.
[0071]
2. Second Invention
[Cyclic Olefin Copolymer]
　First, the cyclic olefin copolymer (P) of the embodiment according to the second invention will be described.
　The cyclic olefin-based copolymer (P) according to the present embodiment is a structural unit (A) derived from an α-olefin having 2 to 20 carbon atoms and a structural unit derived from a cyclic olefin having no aromatic ring. It has (B) and a structural unit (C) derived from a cyclic olefin having an aromatic ring.
[0072]
　The cyclic olefin-based copolymer (P) according to the present embodiment includes a structural unit (A) derived from an α-olefin having 2 to 20 carbon atoms and a structural unit (A) derived from a cyclic olefin having no aromatic ring. By containing the structural unit (C) derived from B) and a cyclic olefin having an aromatic ring, the radiation resistance of the medical container can be improved while maintaining good transparency.
　From the above, according to the cyclic olefin copolymer (P) according to the present embodiment, it is possible to obtain a medical container that is less discolored by electron beam or gamma ray irradiation and has excellent transparency.
[0073]
(Structural Unit (A) Derived from Ethylene) The structural unit (A) according to
　this embodiment is a structural unit derived from an α-olefin having 2 to 20 carbon atoms.
　Here, the α-olefin having 2 to 20 carbon atoms may be linear or branched, and may be ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, Linear α-olefins having 2 to 20 carbon atoms such as 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene; 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- Examples thereof include branched α-olefins having 4 to 20 carbon atoms such as 1-hexene and 3-ethyl-1-hexene. Among these, linear α-olefins having 2 to 4 carbon atoms are preferable, and ethylene is particularly preferable. Such linear or branched α-olefins may be used alone or in combination of two or more.
[0074]
　When the total content of the structural unit (A), the structural unit (B) and the structural unit (C) in the cyclic olefin-based copolymer (P) according to the present embodiment is 100 mol%, the present embodiment The content of the structural unit (A) in the cyclic olefin copolymer (P) according to the embodiment is preferably 10 mol% or more and 80 mol% or less, more preferably 30 mol% or more and 75 mol% or less, further preferably Is 40 mol% or more and 70 mol% or less.
　When the content of the structural unit (A) is at least the above lower limit, heat resistance and dimensional stability of the medical container can be improved. Further, when the content of the structural unit (A) is not more than the upper limit value, the moldability and the like of the obtained medical container can be improved.
　In this embodiment, the content of the structural unit (A) can be measured by , for example, 1 1 H-NMR or 13 C-NMR.
[0075]
(Constituent Unit (B) Derived from Cyclic Olefin) The structural unit (B) according to the
　present embodiment is a structural unit derived from a cyclic olefin having no aromatic ring. From the viewpoint of further improving the refractive index of the medical container, the structural unit (B) according to this embodiment preferably contains a structural unit derived from a compound represented by the following formula (B-1).
[In the

above formula [B-1], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and R 1 to R 18 and R a and R. b is a hydrocarbon group which may be independently substituted with a hydrogen atom, a halogen atom or a halogen atom, and R 15 to R 18 may be bonded to each other to form a monocyclic or polycyclic ring. , And the monocycle or polycycle may have a double bond, and R 15 and R 16 or R 17 and R 18 may form an alkylidene group. Does not contain aromatic rings.)
　Among these, the structural unit (B) according to the present embodiment is a structural unit derived from bicyclo [2.2.1] -2-heptene, tetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene constitutional unit derived from and hexacyclo [6,6,1,1 3,6 , 1 10,13 , 0 2,7 , 0 9,14 ] heptadecene -4 constituent units derived from such It is preferable to include at least one structural unit selected from the group consisting of bicyclo[2.2.1]-2-heptene-derived structural units and tetracyclo[4.4.0.1 2,5 . It is more preferable to contain at least one structural unit selected from the structural units derived from 1 7,10 ]-3-dodecene, and tetracyclo[4.4.0.1 2,5 . It is particularly preferable to include a structural unit derived from 1 7,10 ]-3-dodecene.
[0076]
　When the total content of the structural unit (A), the structural unit (B) and the structural unit (C) in the cyclic olefin copolymer (P) according to the present embodiment is 100 mol %, the cyclic olefin is The content of the structural unit (B) in the system 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 further preferably 15 mol% or more 45. It is not more than mol %.
　In this embodiment, the content of the structural unit (B) can be measured by , for example, 1 1 H-NMR or 13 C-NMR.
[0077]
(
　Structural Unit (C) Derived from Cyclic Olefin Having Aromatic Ring) The structural unit (C) according to the present embodiment is a structural unit derived from a cyclic olefin having an aromatic ring.
　Examples of the cyclic olefin having an aromatic ring according to the present embodiment include 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). Examples include compounds. The cyclic olefins having these aromatic rings may be used alone or in combination of two or more.
[0078]
[Chemical 22]

[0079]
　In the above formula (C-1), n ​​and q are 0, 1 or 2, respectively. n is preferably 0 or 1, and more preferably 0. q is preferably 0 or 1, more preferably 0.
　R 1 ~ R 17 are each independently a hydrocarbon group of a hydrogen atom, a halogen atom or by optionally 1 carbon atoms also be ~ 20 substituted by a halogen atom other than fluorine atom, except fluorine atom, R 10 - It is preferable that one of R 17 is a bond and R 15 is a bond.
　R 1 to R 17 are preferably each 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 may be bonded to each other to form a monocyclic or polycyclic ring, and when q=1 or 2, R 10 and R 11 , R 11 and R 17 are combined. , R 17 and R 17 , R 17 and R 12 , R 12 and R 13 , R 13 and R 14 , R 14 and R 15 , R 15 and R 16 , R 16 and R 16, R 16 and R 10 may be bonded to each other to form a monocyclic or polycyclic, or the monocyclic or polycyclic may have a double bond, the monocyclic or polycyclic. The ring may be an aromatic ring.
　Of the above formula (C-1), the compound represented by the following formula (C-1A) is preferable.
[0080]
[Chemical 23]

[0081]
[Chemical

　formula 24] In the above formula (C-2), n and m are independently 0, 1 or 2, and q is 1, 2 or 3, respectively. 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 to R 31 are hydrocarbon groups having 1 to 20 carbon atoms which may be independently substituted with a hydrogen atom, a halogen atom excluding a fluorine atom, or a halogen atom excluding a fluorine atom.
　R 18 to R 31 are preferably each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrogen atom.
　Further, when q=1, R 28 and R 29 , R 29 and R 30 , and R 30 and R 31 may be bonded to each other to form a monocyclic or polycyclic ring, and when q=2 or 3, R 28 and R 28, R 28 and R 29 , R 29 and R 30 , R 30 and R 31 , and R 31 and R 31 may be bonded to each other to form a monocyclic or polycyclic, and the monocyclic or polycyclic is formed. It may have a double bond, and the monocycle or polycycle may be an aromatic ring.
[0082]
In the

　above formula (C-3), q is 1, 2 or 3, preferably 1 or 2, and more preferably 1.
　R 32 to R 39 are each independently a hydrogen atom, a halogen atom excluding a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom excluding a fluorine atom.
　R 32 to R 39 are preferably each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrogen atom.
　When q=1, R 36 and R 37 , R 37 and R 38 , R 38 and R 39 may be bonded to each other to form a monocyclic or polycyclic ring, and when q=2 or 3, R 36 and R 37 may be combined. 36 and R 36 , R 36 and R 37 , R 37 and R 38 , R 38 and R 39 , and R 39 and R 39 may be bonded to each other to form a monocycle or a polycycle, and the monocycle or the polycycle has a double bond. Also, the monocycle or polycycle may be an aromatic ring.
[0083]
　In addition, examples of the hydrocarbon group having 1 to 20 carbon atoms include, for example, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, and an aromatic hydrocarbon group, each independently. To be More specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group and an octadecyl group, and the cycloalkyl group includes cyclohexyl. Examples of the aromatic hydrocarbon group include an aryl group such as a phenyl group, a tolyl group, a naphthyl group, a benzyl group and a phenylethyl group, or an aralkyl group. These hydrocarbon groups may be substituted with a halogen atom other than a fluorine atom.
[0084]
　Among these, as the cyclic olefin having an aromatic ring according to this embodiment, for example, at least one selected from benzonorbornadiene, indenenorbornene, and methylphenylnorbornene is preferable.
[0085]
　When the total content of the structural unit (A), the structural unit (B) and the structural unit (C) in the cyclic olefin copolymer (P) according to the present embodiment is 100 mol %, the cyclic olefin is The content of the structural unit (C) in the system copolymer (P) is preferably 0.1 mol% or more and 50 mol% or less, more preferably 1 mol% or more, still more preferably 3 mol% or more. , And more preferably 40 mol% or less, further preferably 30 mol% or less, further preferably 25 mol% or less, and particularly preferably 20 mol% or less.
　In the present embodiment, the content of the structural unit (C) can be measured by , for example, 1 H-NMR or 13 C-NMR.
[0086]
　When the total content of the structural unit (B) and the structural unit (C) in the cyclic olefin-based copolymer (P) according to this embodiment is 100 mol %, the cyclic olefin-based copolymer according to this embodiment is The content of the structural unit (C) in the polymer (P) is preferably 5 mol% or more and 95 mol% or less, more preferably 5 mol% or more and 70 mol% or less, still more preferably 5 mol% or more and 50 mol% or less. It is the following.
　In the present embodiment, the content of the structural unit (B) and the structural unit (C) can be measured by , for example, 1 H-NMR or 13 C-NMR.
[0087]
　The copolymerization type of the cyclic olefin-based copolymer (P) according to this embodiment is not particularly limited, but examples thereof include a random copolymer and a block copolymer. In the present embodiment, the cyclic olefin copolymer (P) according to the present embodiment is preferably a random copolymer from the viewpoint of obtaining a medical container having excellent transparency and heat resistance.
[0088]
　The cyclic olefin-based copolymer (P) according to the present embodiment is disclosed in, for example, JP-A-60-168708, JP-A-61-120816, JP-A-61-115912, and JP-A-61- No. 115916, No. 61-271308, No. 61-272216, No. 62-252406, No. 62-252407, No. 2007-314806, No. 2007-314806. It can be produced by appropriately selecting the conditions according to the method disclosed in 2010-241932.
[0089]
　The glass transition temperature (Tg) of the cyclic olefin-based copolymer (P) according to the present embodiment, which is measured by a differential scanning calorimeter (DSC), is excellent in heat resistance while maintaining good transparency of the obtained medical container. From the viewpoint of further improving the property, the temperature is preferably 120°C or higher and 180°C or lower, more preferably 125°C or higher and 170°C or lower, and further preferably 130°C or higher and 165°C or lower.
[0090]
　The intrinsic viscosity [η] (in 135 ° C. decalin) of the cyclic olefin copolymer (P) according to the present 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.
　When the intrinsic viscosity [η] is at least the above lower limit, the mechanical strength of the medical container can be improved. Further, when the intrinsic viscosity [η] is not more than the above upper limit value, the moldability can be improved.
[0091]
[Cyclic Olefin Copolymer Composition]
　The cyclic olefin copolymer composition according to the present embodiment is a cyclic olefin copolymer composition for forming a medical container, and the cyclic olefin copolymer composition according to the present embodiment. The olefin-based copolymer (P) may be contained, and if necessary, other components other than the cyclic olefin-based copolymer (P) may be contained. In addition, in this embodiment, the case where the cyclic olefin-based copolymer composition according to this embodiment contains only the cyclic olefin-based copolymer (P) is also referred to as a cyclic olefin-based copolymer composition.
[0092]
　Further, the content of the cyclic olefin-based copolymer (P) in the cyclic olefin-based copolymer composition according to the present embodiment is determined by the transparency of the obtained medical container and the performance of gamma ray resistance or electron beam resistance performance. From the viewpoint of further improving the balance, when the total amount of the cyclic olefin copolymer composition is 100% by mass, it is preferably 50% by mass or more and 100% by mass or less, and more preferably 70% by mass or more and 100% by mass. Or less, more preferably 80% by mass or more and 100% by mass or less, and particularly preferably 90% by mass or more and 100% by mass or less.
　The cyclic olefin-based copolymer composition according to the present embodiment contains the cyclic olefin-based copolymer (P) in the above-mentioned ratio, so that the resulting medical container has good transparency required for the medical container. The gamma ray resistance or electron beam resistance can be further improved while satisfying the above.
[0093]
(Other components)
　The cyclic olefin-based copolymer composition according to the present embodiment, if necessary, a weather resistance stabilizer, a heat resistance stabilizer, an antioxidant, a metal deactivator, a hydrochloric acid absorbent, an antistatic agent. Agents, flame retardants, slip agents, anti-blocking agents, anti-fog agents, lubricants, natural oils, synthetic oils, waxes, organic or inorganic fillers and the like can be added to such an extent that the object of the present invention is not impaired. The mixing ratio is an appropriate amount.
[0094]
　The cyclic olefin-based copolymer composition according to the present embodiment may contain a hindered amine-based compound [D], if necessary.
　As the hindered amine compound [D] (hereinafter, also simply referred to as compound [D] or [D]), a hindered amine structure (specifically, a partial structure represented by the following formula (b1)) is used. A compound having one or two or more can be appropriately used.
　In formula (b1), * represents a bond with another chemical structure.
[0095]
[Chemical 26]

[0096]
　Specific examples of the compound [D] include compounds known as known hindered amine light stabilizers (abbreviated as HALS).
[0097]
　Examples of the compound [D] include hindered amine compounds described in paragraphs 0058 to 0082 of WO 2006/112434, hindered amine compounds described in paragraphs 0124 to 0186 of WO 2008/047468, and international publications. Examples thereof include the piperidine derivatives or salts thereof described in paragraphs 0187 to 0226 of 2008/047468, and the polyamine derivatives or salts thereof described in JP-A-2006-321793.
[0098]
　In addition, Chimassorb 2020, Chimassorb 944, Tinuvin 622, Tinuvin PA144 Tinuvin 765, Tinuvin
　770 (above, manufactured by BASF), Cyasorb UV-3853, Cyasorb UV-3529, Cyasorb UV-3529, C ADEKA STAB LA-52, ADEKA STAB LA-57, ADEKA STAB LA-63P, ADEKA STAB LA-68, ADEKA STAB LA-72, ADEKA STAB LA-77Y, ADEKA STAB LA-81, ADEKA STAB LA-82, ADEKA STAB LA-87 (or more). Commercially available products such as those manufactured by ADEKA) can be used.
[0099]
　In this embodiment, the compound [D] is preferably a compound having a structural unit represented by the following general formula (b2).
　This compound is typically a polymer or oligomer. It is considered that by using the compound [D] which is a polymer or an oligomer such as this compound, the compatibility with the cyclic olefin copolymer (P) can be enhanced and the composition can be made more uniform. .. In addition, it is considered that the structure is unlikely to change into a structure having characteristic absorption upon irradiation. It is considered that this makes it possible to further reduce discoloration due to electron beam or gamma ray irradiation, and to reduce generation of radicals due to electron beam or gamma ray irradiation.
[0100]
[Chemical 27]

[0101]
　In the general formula (b2), X 1 and X 2 each independently represent a divalent linking group. Examples of the divalent linking group for
　X 1 and X 2 include an alkylene group, a cycloalkylene group, an arylene group, and a group in which these groups are linked. Among these, an alkylene group is preferable, an alkylene group having 1 to 6 carbon atoms is more preferable, and an alkylene group having 1 to 4 carbon atoms is more preferable.
　As the compound having the structural unit represented by the general formula (b2), a commercially available product may be used, or the compound may be obtained by polycondensing a corresponding diol, dicarboxylic acid or the like.
[0102]
　About compound [D], only 1 type may be used and 2 or more types may be used.
　The content of the compound [D] in the composition is, for example, 0.01 to 2.0 parts by mass, preferably 0.05 to 0.05 part, when the content of the cyclic olefin copolymer (P) is 100 parts by mass. The amount is 1.5 parts by mass, more preferably 0.10 to 1.0 parts by mass. Within this range, it is possible to effectively reduce discoloration due to electron beam or gamma ray irradiation, generation of radicals, etc. while maintaining other performances (for example, moldability and mechanical strength).
[0103]
　The cyclic olefin-based copolymer composition according to the present embodiment may contain a phosphorus-based compound [E], if necessary.
　There are no particular restrictions on the phosphorus-based compound [E] that can be used (hereinafter, it may be simply referred to as compound [E] or [E]). For example, a known phosphorus-based antioxidant can be used.
[0104]
　The phosphorus-based antioxidant is not particularly limited, and conventionally known phosphorus-based antioxidants (for example, phosphite-based antioxidants) can be used.
　Specifically, triphenylphosphite, diphenylisodecylphosphite, phenyldiisodecylphosphite, 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)octylphosphite, 9 ,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(3,5-di-t-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10- Monophosphite compounds such as phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene; 4,4′-butylidene-bis(3-methyl-6-) t-butylphenyl-di-tridecylphosphite), 4,4′-isopropylidene-bis(phenyl-di-alkyl(C12-C15)phosphite), 4,4′-isopropylidene-bis(diphenylmonoalkyl) (C12-C15) phosphite), 1,1,3-tris(2-methyl-4-di-tridecylphosphite-5-t-butylphenyl)butane, tetrakis(2,4-di-t-butyl) Phenyl)-4,4'-biphenylenediphosphite, cyclic neopentanetetraylbis(isodecylphosphite), cyclic neopentanetetraylbis(nonylphenylphosphite), cyclic neopentanetetraylbis(2 ,4-di-t-butylphenylphosphite), cyclic neopentanetetraylbis(2,4-dimethylphenylphosphite), cyclic neopentanetetraylbis(2,6-di-t-butylphenylphosphite) And a diphosphite compound such as phyto).
[0105]
　The preferably used compound [E] is a trivalent organophosphorus compound. More specifically, the compound [E] is a compound having a structure in which three hydrogen atoms of phosphorous acid (P(OH) 3 ) are substituted with the same or different organic groups.
　More specifically, the compound [E] is preferably a compound represented by the following general formula (c1), (c2) or (c3).
[0106]
[Chemical 28]

[0107]
　In the general formulas (c1), (c2) and (c3),
　R 1 independently represents an alkyl group when a plurality of R 1 are present, and
　R 2 independently represents an aromatic group when a plurality of R 2 is present;
　R 3 represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, and
　X represents a single bond or a divalent linking group.
[0108]
The alkyl group of 　R 1 preferably has 1 to 10 carbon atoms, and more preferably a t-butyl group. Examples of the aromatic group of
　R 2 include a phenyl group, a naphthyl group, a group in which these are substituted with an alkyl group and the like. The carbon number of
　R 3 is preferably 1 to 30, more preferably 3 to 20, and further preferably 6 to 18.
　R 3 is preferably an aryl group or an aralkyl group, and more preferably an aralkyl group. These aryl groups or aralkyl groups may be further substituted with a substituent (for example, an alkyl group having 1 to 6 carbon atoms or a hydroxy group).
　When X is a divalent linking group, specific examples thereof include an alkylene group (such as a methylene group) and an ether group (—O—). As X, it is preferably a single bond.
[0109]
　About compound [E], only 1 type may be used and 2 or more types may be used.
　The content of the compound [E] in the composition is, for example, 0.01 to 1.5 parts by mass, preferably 0.02 to 1 when the amount of the cyclic olefin copolymer (P) is 100 parts by mass. 0.0 parts by mass, more preferably 0.05 to 0.5 parts by mass. Within this range, it is possible to effectively reduce discoloration due to electron beam or gamma ray irradiation, generation of radicals, etc. while maintaining other performances (for example, moldability and mechanical strength).
[0110]
　On the other hand, as another viewpoint, when the amount of the cyclic olefin copolymer (P) is 100 parts by mass, the content of the phosphorus compound [E] is preferably less than 0.05 parts by mass, more preferably 0. It is 03 parts by mass or less, and more preferably 0.02 parts by mass or less.
[0111]
　The cyclic olefin-based copolymer composition according to the present embodiment is a method of melt-kneading the cyclic olefin-based copolymer (P) and other components using a known kneading device such as an extruder and a Banbury mixer; A method in which the olefin copolymer (P) and other components are dissolved in a common solvent and then the solvent is evaporated; It can be obtained by a method such as;
[0112]
[Medical Container]
　Next, a medical container according to an embodiment of the present invention will be described.
　The medical container according to the present embodiment contains the cyclic olefin-based copolymer (P) or the cyclic olefin-based copolymer composition according to the present embodiment.
　Since the medical container according to the present embodiment contains the cyclic olefin-based copolymer (P), it is excellent in transparency and performance balance of gamma ray resistance or electron beam resistance performance. This medical container is less discolored by electron beam or gamma ray irradiation.
　Here, according to another study by the present inventors, it has been clarified that the conventional medical container may generate radicals by irradiation with an electron beam or a gamma ray. As a result, there is a risk that the contents may deteriorate after being filled in the medical container.
　On the other hand, the medical container according to the present embodiment can reduce the amount of radicals generated by electron beam or gamma ray irradiation. Therefore, according to the medical container according to the present embodiment, it is possible to reduce the risk of deterioration of the contents.
[0113]
　Further, the content of the cyclic olefin-based copolymer (P) in the medical container according to the present embodiment is 100% for the entire medical container from the viewpoint of further improving the performance balance of radiation resistance and transparency. When it is defined as mass%, it is preferably 50 mass% or more and 100 mass% or less, more preferably 70 mass% or more and 100 mass% or less, further preferably 80 mass% or more and 100 mass% or less, and particularly preferably It is 90% by mass or more and 100% by mass or less.
[0114]
　The method for molding the cyclic olefin-based copolymer (P) according to the present embodiment or the cyclic olefin-based copolymer composition according to the present embodiment to obtain a medical container is not particularly limited, and is known. Any method 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, calendar molding, foam molding and the like can be applied. Is. Among these, the injection molding method is preferable from the viewpoint of moldability and productivity. The molding conditions are appropriately selected depending on the purpose of use or the molding method. For example, the resin temperature in injection molding is usually 150 ° C. to 400 ° C., preferably 200 ° C. to 350 ° C., more preferably 230 ° C. to 330 ° C. It is appropriately selected in the range.
[0115]
　Further, for example, by irradiating the medical container produced above with a gamma ray or an electron beam, a gamma ray or electron beam irradiation object (a medical container irradiated with a gamma ray or an electron beam) of the medical container can be obtained. it can. This medical container is sterilized or sterilized by irradiation, so that it is clean and discoloration and generation of radicals are suppressed. The irradiation dose is not particularly limited, but is usually 5 to 100 kilogray (kGy), preferably 10 to 80 kilogray.
[0116]
　Examples of the medical container include a syringe used for an outer cylinder (hereinafter referred to as a syringe) of a syringe and an injection cylinder (hereinafter also referred to as a prefilled syringe) filled with a drug solution or a drug, and a drug solution or a drug filled therein. A storage container (hereinafter, also referred to as a chemical liquid storage container) used for the storage container formed as described below and the like.
[0117]
　Here, the prefilled syringe is a syringe-shaped formulation in which a drug solution or drug is pre-filled, and a single chamber type that is filled with one type of liquid and a double chamber type that is filled with two types of drugs. There is. Most prefilled syringes are single-chamber type, but double-chamber type includes liquid/powder type formulation consisting of powder and its solution, and liquid/liquid type formulation consisting of two types of liquid. An example of a single chamber type internal solution is a heparin solution or the like. Examples of the syringe used for the syringe and the prefilled syringe include a prefillable syringe, a vaccine prefilled syringe, an anticancer drug prefilled syringe, and a needleless syringe.
[0118]
　Examples of the drug solution storage container include a wide-mouth bottle, a narrow-mouth bottle, a drug bottle, a vial bottle, an infusion bottle, a bulk container, a petri dish, a test tube, and an analysis cell. More specifically, liquid, powder or solid drug containers such as ampoules, press-through packages, infusion bags, drip containers, eye drop containers; sampling tubes for blood tests, blood collection tubes, specimens Sample containers such as containers; analysis containers such as UV inspection cells; sterilization containers for medical instruments such as scalpels, forceps, gauze and contact lenses; medical devices such as disposable syringes and prefilled syringes; beakers, vials, ampoules, test tube flasks, etc. Experimental equipment; housing of artificial organs and the like.
[0119]
　The medical container according to this embodiment has good transparency. Transparency is evaluated by internal haze.
　It is also preferable that the light transmittance is good. The light transmittance is defined by the spectral light transmittance or the total light transmittance depending on the application.
[0120]
　When it is expected to be used in all light rays or in a plurality of wavelength regions, it is necessary that the total light transmittance is good, and the total light transmittance is preferably 85% or more when the antireflection film is not provided on the surface. Is 88 to 93%. If the total light transmittance is 85% or more, a required amount of light can be secured. A known method can be applied to the method for measuring the total light transmittance, and the measuring device and the like are not limited. And the total light transmittance of the sheet obtained by molding the cyclic olefin-based copolymer composition according to the present embodiment using a haze meter.
[0121]
　Further, the medical container according to the present embodiment is excellent in light transmittance of light having a wavelength of 450 nm to 800 nm.
　The light transmittance can be further improved by providing a known antireflection film on the surface.
[0122]
　The embodiments of the second invention have been described above, but these are examples of the second invention, and various configurations other than the above can be adopted.
　Further, the second invention is not limited to the above-described embodiment, and modifications, improvements, etc. within the scope of achieving the object of the second invention are included in the present invention.
[0123]
　Although the embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than the above may be adopted.
　Further, the present invention is not limited to the above-described embodiment, and modifications, improvements, etc. within the scope of achieving the object of the present invention are included in the present invention.
　In addition, as a matter of course, the present inventions described above can be combined within a range in which the contents do not conflict with each other.
Example
[0124]
Hereinafter, the first invention of the present invention will be specifically described based on examples, but the first invention of the present invention is not limited to these examples.
[0125]

[Production Example 1]
　Nitrogen as an inert gas was passed for 30 minutes at a flow rate of 100 Nl/hr in a glass reaction vessel having a volume of 500 ml equipped with a stirrer, and then cyclohexane and tetracyclo were used. [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene (40 mmol, hereinafter also referred to as tetracyclododecene.), And benzonorbornadiene (88 mmol, hereinafter also referred to as BNBD.) Was added. Next, the solvent temperature was raised to 50° C. while stirring the polymerization solvent at a rotation speed of 600 rpm. After the solvent temperature reached a predetermined temperature, the flow gas was switched from nitrogen to ethylene, ethylene was passed through the reaction vessel at a feed rate of 50 Nl/hr and hydrogen at a feed rate of 2.0 Nl/hr, and after 10 minutes, PMAO (1.8 mmol) and the catalyst (0.0030 mmol) prepared by the method described in paragraph 0112 of JP 2010-241932 A were added to a glass reaction vessel to initiate polymerization.
　After 10 minutes, 5 ml of isobutyl alcohol was added to terminate the polymerization to obtain a polymerization solution containing a copolymer of ethylene, tetracyclododecene and BNBD. Then, the polymerization solution was transferred to a separately prepared beaker having a volume of 2 L, 5 ml of concentrated hydrochloric acid and a stirrer were added, and the mixture was contacted for 2 hours under strong stirring for deashing operation. The decalcified polymerization solution was added with stirring to a beaker containing about 3 times the volume of this polymerization solution with acetone to precipitate a copolymer, and the precipitated copolymer was separated from the filtrate by filtration. The polymer containing the solvent obtained was dried under reduced pressure at 130° C. for 10 hours to obtain 4.58 g of an ethylene/tetracyclododecene/BNBD copolymer in the form of a white powder.
　In this way, a cyclic olefin-based copolymer (P-1) was obtained.
[0126]
[Production Examples 2 to 12] The same
　operations as in Production Example 1 were carried out except that the content of each structural unit constituting the cyclic olefin copolymer was adjusted to the value shown in Table 1. The cyclic olefin copolymers (P-2) to (P-11) shown in Table 1 were obtained.
　Further, the cycloolefin copolymer (P-10) and the cycloolefin copolymer (P-11) were mixed at a mass ratio of 1:1 to prepare a cycloolefin copolymer (P-12). (Production Example 12).
　Here, BNBD in Table 1 means benzonorbornadiene represented by the following formula (1), and IndNB means indene norbornene represented by the following formula (2). MePhNB means methylphenyl norbornene represented by the following formula (3).
[0127]
[Chemical 29]

[0128]
[Chemical 30]

[Chemical 31]

[0129]
[table 1]

[0130]
[Table 2]

[0131]
In
　each Example and Comparative Example, various physical properties were measured or evaluated by the following methods, and the obtained results are shown in Table 2.
[0132]
[Measurement Method of Content of Each Structural Unit Constituting Cyclic Olefin Copolymer]
　Ethylene, tetracyclo[4.4.0.1 2,5 . The content of 1 7,10 ]-3-dodecene and the cyclic olefin having an aromatic ring was measured by using an “ECA500 type” nuclear magnetic resonance apparatus manufactured by JEOL Ltd. under the following conditions.
　Solvent: heavy tetrachloroethane
　Sample concentration: 50 to 100 g/l-solvent
　pulse repetition time: 5.5 seconds
　Number of integrations: 6000 to 16000 times
　Measurement temperature: 120° C. 13 C-NMR spectrum
　measured under the above conditions The compositions of ethylene, tetracyclododecene and cyclic olefin having an aromatic ring were quantified respectively.
[0133]
[Glass Transition Temperature Tg (° C.)] The glass transition temperature Tg of the cyclic olefin-based copolymer was measured under
　N 2 (nitrogen) atmosphere using DSC-6220 manufactured by Shimadzu Science . The cyclic olefin copolymer was heated from room temperature to 200 ° C. at a heating rate of 10 ° C./min and then held for 5 minutes, and then cooled to −20 ° C. at a temperature lowering rate of 10 ° C./min and then held for 5 minutes. .. Then, the glass transition point (Tg) of the cyclic olefin copolymer was determined from the endothermic curve when the temperature was raised to 200 ° C. at a heating rate of 10 ° C./min.
[0134]
[Intrinsic Viscosity [η]] A
　moving viscometer (type VNR053U, manufactured by Rikyu Co., Ltd.) was used to dissolve 0.25 to 0.30 g of the cyclic olefin copolymer in 25 ml of decalin as a sample. According to ASTM J1601, the specific viscosity of the cyclic olefin-based copolymer was measured at 135° C., and the ratio of the specific viscosity to the concentration was extrapolated to 0 to determine the intrinsic viscosity [η] of the cyclic olefin-based copolymer.
[0135]
[Micro-Compounder Molding]
　The cyclic olefin-based copolymers of Production Examples 1 to 10 and 12 were kneaded using a small kneader manufactured by Xplore Instruments Co., at a kneading temperature of 280° C. and 50 rpm for 5 minutes, and then manufactured by Xplore Instruments Co. The injection molding machine was used to perform 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. to prepare injection molded sheets each having a thickness of 1.0 mm.
[0136]
[Internal Haze]
　Using an injection-molded sheet of 30 mm×30 mm×thickness of 1.0 mm formed by a micro compounder, benzyl alcohol was used, and measurement was performed according to JIS K7136. Then, the internal haze was evaluated according to the following criteria.
◯: Less than 5%
×: 5% or more
[0137]
[Birefringence]
　A 30 mm×30 mm×1.0 mm thick injection-molded sheet molded with a micro compounder was measured with a KOBRA CCD manufactured by Oji Scientific Instruments at a measurement wavelength of 650 nm and a phase difference of 20 to 35 mm from the gate direction. The average value of was calculated.
　Next, the birefringence was evaluated according to the following criteria.
A: Average value of retardation is less than 30 nm.
O: Average value of retardation is 30 nm or more and less than 40 nm.
X: Average value of retardation is 40 nm or more.
[0138]
[Refractive index]
　Refractive index (nd) of an injection-molded sheet of 30 mm × 30 mm × thickness 1.0 mm molded with a microcompound using a refractive index meter (KPR200 manufactured by Shimadzu Science Co., Ltd.) at a wavelength of 589 nm according to ASTM D542. ) Was measured respectively.
[0139]
[Abbe number (ν)] With
　respect to an injection-molded sheet of 30 mm×30 mm×thickness of 1.0 mm formed by a micro compounder, the Abbe refractometer was used to measure the refractive index at wavelengths of 486 nm, 589 nm and 656 nm at 23° C. The Abbe number (ν) was calculated using the following formula.
ν=(nD-1)/(nF-nC)
nD: Refractive index at wavelength 589 nm
nC: Refractive index at
wavelength 656 nm nF: Refractive index at wavelength 486 nm
[0140]
As a
　hydrophilic stabilizer, triglycerin fatty acid ester (triglycerin oleate which is an ester of triglycerin and oleic acid (mixture of monoester, diester and triester, ester ratio 41% monoester, diester 49 %, triester 10%)) in a molten state heated at 100° C. for 4 hours, and directly loaded into the extruder in an amount of 0.6 part by mass relative to 100 parts by mass of the cyclic olefin copolymer (P-1). Then, a resin composition containing a cyclic olefin copolymer (P-1), a distilled product of an ester of triglycerin and oleic acid was obtained.
　Specifically, using a twin-screw extruder with co-rotation, a screw diameter of 12 mmφ, and an L/D=48 having a vent hole at a position L/D=34 from the resin charging part, a cyclic olefin-based copolymer ( P-1) was charged from the resin charging part, then the above triglycerin fatty acid ester which was heated and melted at 80 to 120° C. was charged from the vent hole, and the screw rotation speed was 150 rpm and the motor power was 2.2 kW. The resin composition was obtained by melt-kneading under the conditions.
　The glass transition temperature and the intrinsic viscosity [η] of the obtained resin composition were measured in the same manner as in Example 1. The results are shown in Table 3.
[0141]
As shown in
　Table 3, the same as in Example 10 except that the 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 copolymer (P-1). A resin composition was prepared in the same manner.
　With respect to the obtained resin composition, the glass transition temperature and the ultimate viscosity [η] were measured by the same method as in Example 1. The results are shown in Table 3.
[0142]
As shown in
　Table 3, the same as in Example 10 except that the triglycerin fatty acid ester was used in an amount of 1.0 part by mass with respect to 100 parts by mass of the cyclic olefin copolymer (P-1). A resin composition was prepared in the same manner.
　With respect to the obtained resin composition, the glass transition temperature and the ultimate viscosity [η] were measured by the same method as in Example 1. The results are shown in Table 3.
[0143]
As shown in
　Table 3, a cyclic olefin copolymer using Riquemar DO-100 (manufactured by RIKEN Vitamin, the main component is diglycerin monooleate) instead of triglycerin fatty acid ester as a hydrophilic stabilizer. A resin composition was prepared in the same manner as in Example 10 except that the amount of (P-1) was 0.6 parts by mass relative to 100 parts by mass.
　With respect to the obtained resin composition, the glass transition temperature and the ultimate viscosity [η] were measured by the same method as in Example 1. The results are shown in Table 3.
[0144]
As shown in
　Table 3, 1.0 mass by mass of Riquemar DO-100 was changed to triglycerin fatty acid ester as a hydrophilic stabilizer with respect to 100 parts by mass of the cyclic olefin copolymer (P-1). A resin composition was prepared in the same manner as in Example 10 except that the resin composition was used in the amount of parts.
　With respect to the obtained resin composition, the glass transition temperature and the ultimate viscosity [η] were measured by the same method as in Example 1. The results are shown in Table 3.
[0145]
As shown in
　Table 3, a cyclic olefin copolymer using Exepearl PE-MS (manufactured by Kao Corporation, the main component is pentaerythritol monostearate) instead of triglycerin fatty acid ester as a hydrophilic stabilizer. (P-1) A resin composition was prepared in the same manner as in Example 10 except that it was used in an amount of 1.8 parts by mass with respect to 100 parts by mass.
　With respect to the obtained resin composition, the glass transition temperature and the ultimate viscosity [η] were measured by the same method as in Example 1. The results are shown in Table 3.
[0146]
As shown in
　Table 3, 2.4 parts by mass of Exepearl PE-MS was used as a hydrophilic stabilizer in place of triglycerin fatty acid ester based on 100 parts by mass of the cyclic olefin copolymer (P-1). A resin composition was prepared in the same manner as in Example 10 except that the resin composition was used in the amount of parts.
　With respect to the obtained resin composition, the glass transition temperature and the ultimate viscosity [η] were measured by the same method as in Example 1. The results are shown in Table 3.
[0147]
As shown in
　Table 3, the same procedure as in Example 10 except that the cyclic olefin copolymer (P-5) was used instead of the cyclic olefin copolymer (P-1). A resin composition was prepared.
　With respect to the obtained resin composition, the glass transition temperature and the ultimate viscosity [η] were measured by the same method as in Example 1. The results are shown in Table 3.
[0148]
As
　described in Table 3, the procedure of Example 12 was repeated except that the cyclic olefin copolymer (P-1) was replaced with the cyclic olefin copolymer (P-5). A resin composition was prepared.
　With respect to the obtained resin composition, the glass transition temperature and the ultimate viscosity [η] were measured by the same method as in Example 1. The results are shown in Table 3.
[0149]
As shown in
　Table 3, the same procedure as in Example 10 except that the cyclic olefin copolymer (P-8) was used instead of the cyclic olefin copolymer (P-1). A resin composition was prepared.
　With respect to the obtained resin composition, the glass transition temperature and the ultimate viscosity [η] were measured by the same method as in Example 1. The results are shown in Table 3.
[0150]
As
　described in Table 3, the procedure of Example 12 was repeated except that the cyclic olefin copolymer (P-1) was replaced with the cyclic olefin copolymer (P-8). A resin composition was prepared.
With respect to the obtained resin composition, the glass transition temperature and the ultimate viscosity [η] were measured by the same method as in Example 1. The results are shown in Table 3.
[0151]

( Method for producing molded body
　) A resin composition was prepared using an injection molding machine (Micro-2 manufactured by Mayho Co., Ltd.) at a cylinder temperature of 320°C. Was injection-molded to prepare a molded body (test piece) of 25 mm×25 mm×thickness 2 mmt. The mold temperature was set to 135°C.
[0152]
[Refractive index/Abbe number] Using a
　refractometer (KPR3000 manufactured by Shimadzu Science Co., Ltd.), the refractive index at a wavelength of 486 nm, 589 nm and 656 nm of a molded test piece of 25 mm×25 mm×thickness 2 mmt according to ASTM D542 (nd ) Was measured. Furthermore, the Abbe number (ν) was calculated using the following formula. The results are shown in Table 2.
ν=(nD-1)/(nF-nC)
nD: Refractive index at wavelength 589 nm
nC: Refractive index at
wavelength 656 nm nF: Refractive index at wavelength 486 nm
[0153]
[Internal Haze] The internal haze of the
　molded product was measured according to JIS K-7136 using benzyl alcohol. Then, the internal haze was evaluated according to the following criteria. The results are shown in Table 2.
○: Less than 5%
×: 5% or more
[0154]
[Birefringence] With
　respect to the molded test piece of 25 mm×25 mm×thickness of 2 mmt, an average value of the phase difference of 20 to 35 mm from the gate direction was determined at a measurement wavelength of 650 nm using a KOBRA CCD manufactured by Oji Scientific Instruments. The results are shown in Table 2.
　Next, the birefringence was evaluated according to the following criteria.
⊚: Average value of retardation is less than 10 nm
◯: Average value of retardation is 10 nm or more and less than 20 nm
×: Average value of retardation is 20 nm or more
[0155]
[Appearance after Environmental Test] A
　molded test piece of 25 mm×25 mm×thickness of 2 mmt was left for 48 hours in an atmosphere of a temperature of 85° C. and a relative humidity of 85%. After that, the film was taken out and left for 48 hours in an atmosphere having a temperature of 23° C. and a relative humidity of 50%, and then the haze was measured. The results are shown in Table 2.
The amount of change obtained by subtracting the haze before the environmental test from the haze after the environmental test (hereinafter, Δhaze) was evaluated according to the following criteria.
◎: Less than 5%
○: 5% or more
[0156]
[Table 3]

[0157]
　As described above, the optical lenses obtained in the examples had a high refractive index and a lower Abbe number than the optical lens obtained in Comparative Example 1. That is, the optical lenses obtained in the examples showed a high refractive index and a low Abbe number while satisfying various characteristics required for the optical lens. On the other hand, the optical lens of Comparative Example 1 using the cyclic olefin-based copolymer that does not contain the structural unit (C) derived from the cyclic olefin having an aromatic ring has a high Abbe number, and the intended optical lens cannot be obtained. .. The optical lens of Comparative Example 2 had a bad internal haze and was inferior in optical characteristics.
[0158]
Hereinafter, the second invention of the present invention will be specifically described based on examples, but the second invention of the present invention is not limited to these examples.
[0159]

[Production Example 13]
　Nitrogen as an inert gas was passed for 30 minutes at a flow rate of 100 Nl/hr in a glass reaction vessel having a volume of 500 ml equipped with a stirrer, and then cyclohexane and tetracyclo were used. [4.4.0.1 2,5 . 1 7,10 ]-3-dodecene (19 mmol, hereinafter also referred to as tetracyclododecene) and indene norbornene (8.0 mmol, hereinafter also referred to as IndNB) were added. Next, the solvent temperature was raised to 50° C. while stirring the polymerization solvent at a rotation speed of 600 rpm. After the solvent temperature reached a predetermined temperature, the flow gas was switched from nitrogen to ethylene, and ethylene was passed through the reaction vessel at a feed rate of 50 Nl/hr and hydrogen at 0.5 Nl/hr, and after 10 minutes, MMAO was passed. (Modified Methylaluminoxane) (0.9 mmol) and the catalyst (0.0030 mmol) prepared by the method described in paragraph 0112 of JP 2010-241932 A were added to a glass reaction vessel to initiate polymerization.
　After 10 minutes, 5 ml of isobutyl alcohol was added to terminate the polymerization to obtain a polymerization solution containing a copolymer of ethylene, tetracyclododecene and IndNB. Thereafter, the polymerization solution was transferred to a separately prepared beaker having a volume of 2 L, 5 ml of concentrated hydrochloric acid and a stirrer were added, and the mixture was contacted for 2 hours under strong stirring for deashing operation. The decalcified polymerization solution was added with stirring to a beaker containing about 3 times the volume of this polymerization solution with acetone to precipitate a copolymer, and the precipitated copolymer was separated from the filtrate by filtration. The polymer containing the obtained solvent was dried under reduced pressure at 130° C. for 10 hours to obtain 0.58 g of a white powdery ethylene/tetracyclododecene/indene norbornene copolymer.
　As described above, a cyclic olefin-based copolymer (P-13) was obtained.
[0160]
[Production Examples 14 to 21] The same
　operation as in Production Example 13 was carried out except that the content value of each structural unit constituting the cyclic olefin copolymer was adjusted to be the value shown in Table 4. The cyclic olefin copolymers (P-14) to (P-21) shown in Table 4 were obtained.
　Here, BNBD in Table 4 means benzonorbornadiene represented by the following formula (1), and IndNB means indene norbornene represented by the following formula (2). MePhNB means methylphenyl norbornene represented by the following formula (3).
[0161]
[Chemical 32]

[0162]
[Chemical 33]

[0163]
[Chemical 34]

[0164]
In
　each of the Examples and Comparative Examples, various physical properties were measured or evaluated by the following methods, and the obtained results are shown in Table 4.
[0165]
[Measurement Method of Content of Each Structural Unit Constituting Cyclic Olefin Copolymer]
　Ethylene, tetracyclo[4.4.0.1 2,5 . The content of 1 7,10 ]-3-dodecene and the cyclic olefin having an aromatic ring was measured by using an “ECA500 type” nuclear magnetic resonance apparatus manufactured by JEOL Ltd. under the following conditions.
　Solvent: heavy tetrachloroethane
　Sample concentration: 50 to 100 g/l-solvent
　pulse repetition time: 5.5 seconds
　Number of integrations: 6000 to 16000 times
　Measurement temperature: 120° C. 13 C-NMR spectrum
　measured under the above conditions The compositions of ethylene, tetracyclododecene and cyclic olefin having an aromatic ring were quantified respectively.
[0166]
[Glass Transition Temperature Tg (° C.)] The glass transition temperature Tg of the cyclic olefin-based copolymer was measured under
　N 2 (nitrogen) atmosphere using DSC-6220 manufactured by Shimadzu Science . The cyclic olefin copolymer was heated from room temperature to 200 ° C. at a heating rate of 10 ° C./min and then held for 5 minutes, and then cooled to −20 ° C. at a temperature lowering rate of 10 ° C./min and then held for 5 minutes. .. Then, the glass transition point (Tg) of the cyclic olefin copolymer was determined from the endothermic curve when the temperature was raised to 200 ° C. at a heating rate of 10 ° C./min.
[0167]
[Intrinsic Viscosity [η]] A
　moving viscometer (type VNR053U, manufactured by Rikyu Co., Ltd.) was used to dissolve 0.25 to 0.30 g of the cyclic olefin copolymer in 25 ml of decalin as a sample. According to ASTM J1601, the specific viscosity of the cyclic olefin-based copolymer was measured at 135° C., and the ratio of the specific viscosity to the concentration was extrapolated to 0 to determine the intrinsic viscosity [η] of the cyclic olefin-based copolymer.
[0168]
(Evaluation of Cyclic Olefin Copolymer Composition)
[Press Molding]
　The powders obtained in the above Production Examples 13 to 21 were press molded at 250° C. using a hand press manufactured by Toyo Seiki Co., Ltd. A square plate test piece having a thickness of 2 mm was produced.
[0169]
[Gamma Ray Irradiation]
　The 2 mm thick square plate test piece obtained above was irradiated with gamma rays of 20 kGy or 50 kGy.
[0170]
[Transparency]
　The internal haze of the obtained square plate test piece having a thickness of 2 mm and the test piece immediately after gamma ray irradiation was measured, and the transparency was evaluated according to the following criteria.
　The internal haze was measured in benzyl alcohol using a haze meter (NDH-20D manufactured by Nippon Denshoku Kogyo Co., Ltd.).
　◯: Internal haze is less than 6.0%
　×: The test piece is visually opaque, or the internal haze is 6.0% or more.
[0171]
[Evaluation: Hue immediately after gamma ray irradiation]
　Test pieces immediately after gamma ray irradiation were stacked on white paper with a thickness of 20 mm. The hue and lightness at this time were visually evaluated.
　The hue was based on the Munsell color system. The evaluation criteria are as follows.
　Good (good): The lightness is 7 to 9.5 and the hue is between 5.0 GY and 10 GY.
　Δ (normal): The lightness is 5 to 9.5 and the hue is between 5Y and 5GY. However, the case where the above ○ (good) is applicable is excluded.
　X (bad): The brightness is 0 or more and less than 5, and / or the hue is between 2.5Y and 5Y. However, the case corresponding to the above △ (normal) is excluded.
[0172]
　A supplementary note about the above evaluation criteria.
　As for the brightness, the larger the value, the closer to white, and it is clear that discoloration is suppressed.
　Regarding the hue, in consideration of use as a medical container in particular, yellow is avoided because it gives a patient an unclean impression, and thus green is preferable to yellow.
[0173]
[Evaluation: Radical amount
　after 5 days and 1 month after gamma ray irradiation ] The radical amount of the sample after 5 days and 1 month after gamma ray irradiation was measured by an electron spin resonance method (Electron Spin Rssonance (ESR)).
　Specifically, about 6 mg of a test piece after 5 days and 1 month after irradiation with gamma rays having doses of 20 kGy and 50 kGy was cut out, put into a test tube (details below), and ESR spectrum was measured under the following conditions. ..
[0174]
-Device: electron spin resonance device JES-TE200 manufactured by JEOL
-Resonance frequency: 9.2 GHz
-Microwave input: 1 mW
-Central magnetic field: 326.5 mT
-Sweep width: ±15 mT
-Modulation frequency: 100 kHz
-Sweep time: 8 min.
・Time constant: 0.1 sec
・Amplification degree: 25
・Sample tube: Sample tube of quartz at the tip corresponding to X band
・External aim: Mn 2+ standard sample supported on magnesium oxide
・External standard memory: 0, 700
・Measurement Temperature: Room temperature
/Measurement atmosphere: Atmosphere
[0175]
　The normalized value shown in the following formula was used for the relative comparison of the amount of radicals generated.
[0176]
[Number 1]

[0177]
　The baseline of the ESR spectrum was corrected based on Mn 2+ (second signal).
　Usually, in the relative comparison of the amount of radicals, Mn 2+ (third signal) is used as the area of the reference Mn 2+ -derived signal . However, since the spectrum of radicals derived from organic radicals and Mn 2+ (third signal) overlap, Mn 2+ (second signal) was used in all measurements this time (external standard memory=700). 　When the organic radical-derived signal overlapped with Mn 2+ (third signal), it was calculated using the ESR spectrum of external standard memory = 0.
[0178]
[Table 4]

[0179]
　As described above, the molded products (sheets) composed of the cyclic olefin-based copolymer compositions obtained in Examples 21 to 28 were excellent in transparency and gamma ray resistance performance balance. On the other hand, Comparative Example 3 using a cyclic olefin-based copolymer that does not contain a structural unit (C) derived from a cyclic olefin having an aromatic ring was inferior in the performance balance of transparency and gamma ray resistance.
[0180]
　This application claims priority based on Japanese Patent Application No. 2017-228675 filed on November 29, 2017 and Japanese Patent Application No. 2018-138691 filed on July 24, 2018. , All of its disclosures are taken here.
The scope of the claims
[Claim 1]
　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 (B) derived from a cyclic olefin having an aromatic ring ( C) and
a cyclic olefin copolymer.
[Claim 2]
　The cyclic olefin-based copolymer according to claim 1
　, wherein the total content of the structural unit (A), the structural unit (B) and the structural unit (C) in the cyclic olefin-based copolymer is 100 mol. %, the content of the structural unit (A) in the cyclic olefin-based copolymer is 10 mol% or more and 80 mol% or less.
[Claim 3]
　In the cyclic olefin-based copolymer according to claim 1 or 2, when
　the total content of the structural unit (B) and the structural unit (C) in the cyclic olefin-based copolymer is 100 mol%, A cyclic olefin-based copolymer in which the content of the structural unit (C) in the cyclic olefin-based copolymer is 5 mol% or more and 95 mol% or less.
[Claim 4]
　The cyclic olefin copolymer according to any one of claims 1 to 3,
　wherein the cyclic olefin having no aromatic ring contains a compound represented by the following formula (B-1). Coalescing.
[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 to R 18 and R a and R are b is independently a hydrogen atom, a halogen atom or a hydrocarbon group which may be substituted with a halogen atom, and R 15 to R 18 may be bonded to each other to form a monocyclic ring or a polycyclic ring. , And the monocycle or polycycle may have a double bond, and R 15 and R 16 or R 17 and R 18 may form an alkylidene group. Does not contain aromatic rings.)
[Claim 5]
　The cyclic olefin-based copolymer according to any one of claims 1 to 4,
　wherein the cyclic olefin having an aromatic ring is a compound represented by the following formula (C-1) or a compound represented by the following formula (C-2). A cyclic olefin-based copolymer containing one or more compounds selected from the group consisting of the compounds represented by the formula (C-3):
[In the

formula (C-1), n ​​and q are each independently 0, 1 or 2, and R 1 to R 17 are each independently a hydrogen atom, a halogen atom other than a fluorine atom, or optionally substituted with a halogen atom other than fluorine atom a hydrocarbon group which may carbon atoms 1 ~ 20, R 10 ~ R 17 one of is a bond, and R when q = 0 10 and R 11 , R 11 and R 12 , R 12 and R 13 , R 13 and R 14 , R 14 and R 15, R 15 and R 10 may be bonded to each other to form a monocyclic or polycyclic ring, and when q=1 or 2, R 10 and R 11 , R 11 and R 17 , R 17 and R 17 , R 17 and R 12 , R 12 and R 13 , R 13 and R 14 , R 14 and R 15 , R 15 and R 16 , R 16 and R 16 , R 16 and R 10.May be bonded to each other to form a monocycle or a polycycle, and the monocycle or the polycycle may have a double bond, and the monocycle or the polycycle is an aromatic ring. It may be. )
[Formula 3]

in (above formula (C-2), n and m are each independently 0, 1 or 2, q is 1, 2 or 3, R 18 ~ R 31 are each independently, A hydrogen atom, a halogen atom excluding a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom excluding a fluorine atom, and when q=1, R 28 , R 29 and R 29 and R 30 , R 30 and R 31 may be bonded to each other to form a monocyclic or polycyclic ring, and when q=2 or 3, R 28 and R 28 , R 28 and R 29 , R 29 And R 30 and R 30 and R 31 , R 31 and R 31 may be bonded to each other to form a monocyclic or polycyclic ring, the monocyclic ring or the polycyclic ring may have a double bond, and the monocyclic ring or the polycyclic ring may be formed. The polycycle may be an aromatic ring. )
[Formula 4]

in (above formula (C-3), q is 1, 2 or 3, R 32 ~ R 39 except each independently, a hydrogen atom, a halogen atom except fluorine atom or a fluorine atom, It is a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom, and when q = 1, R 36 and R 37 , R 37 and R 38 , and R 38 and R 39 are bonded to each other. It may form a monocyclic ring or a polycyclic ring, and when q=2 or 3, R 36 and R 36 , R 36 and R 37 , R 37 and R 38, R 38 and R 39 , R 39 and R 39 may be coupled to each other to form a monocyclic or polycyclic, and the monocyclic or polycyclic may have a double bond. The monocyclic ring or the polycyclic ring may be an aromatic ring. )
[Claim 6]
　The cyclic olefin-based copolymer according to any one of claims 1 to 5,
　when an injection-molded sheet made of the cyclic olefin-based copolymer and having a thickness of 1.0 mm is produced, the Abbe of the injection-molded sheet is used. A cyclic olefin-based copolymer having a number (ν) of 35 or more and 55 or less.
[Claim 7]
　The cycloolefin copolymer according to any one of claims 1 to 6
　, wherein a glass transition temperature (Tg) of the cycloolefin copolymer measured by a differential scanning calorimeter (DSC) is 120°C. A cyclic olefin-based copolymer having a temperature of 180° C. or higher.
[Claim 8]
　The cyclic olefin-based copolymer according to any one of claims 1 to 7, wherein the
　intrinsic viscosity [η] measured in decalin at 135°C is 0.05 dl/g or more and 5.0 dl/g or less. Olefin-based copolymer.
[Claim 9]
　The cyclic olefin-based copolymer according to any one of claims 1 to 8,
　when an injection-molded sheet having a thickness of 1.0 mm made of the cyclic olefin-based copolymer is produced, A cyclic olefin-based copolymer having a refraction of 1 nm or more and 200 nm or less.
[Claim 10]
　The cyclic olefin-based copolymer according to any one of claims 1 to 9,
　wherein the cyclic olefin having an aromatic ring includes at least one selected from benzonorbornadiene, indenenorbornene, and methylphenylnorbornene. Copolymer.
[Claim 11]
　A cyclic olefin-based copolymer composition comprising the cyclic olefin-based copolymer according to any one of claims 1 to 10.
[Claim 12]
　The cyclic olefin-based copolymer composition according to claim 11, further comprising a hydrophilic stabilizer.
[Claim 13]
　A molded product comprising the cyclic olefin-based copolymer according to any one of claims 1 to 10 or the cyclic olefin-based copolymer composition according to claim 11 or 12.
[Claim 14]
　The molded body according to claim 13, which is an optical lens.
[Claim 15]
　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 (B) derived from a cyclic olefin having an aromatic ring (
A medical container comprising a cyclic olefin-based copolymer having C) .
[Claim 16]
　In the medical container according to claim 15,
　the total content of the structural unit (A), the structural unit (B) and the structural unit (C) in the cyclic olefin copolymer was set to 100 mol%. At this time, the medical container in which the content of the structural unit (C) in the cyclic olefin-based copolymer is 0.1 mol% or more and 50 mol% or less.
[Claim 17]
　In the medical container according to claim 15 or 16, when
　the total content of the structural unit (B) and the structural unit (C) in the cyclic olefin copolymer is 100 mol%, the cyclic olefin A medical container in which the content of the structural unit (C) in the copolymer is 5 mol% or more and 95 mol% or less.
[Claim 18]
　The medical container according to any one of claims 15 to 17
　, wherein a total content of the structural unit (A), the structural unit (B) and the structural unit (C) in the cyclic olefin-based copolymer is included. A medical container in which the content of the structural unit (A) in the cyclic olefin-based copolymer is 10 mol% or more and 80 mol% or less, when the amount is 100 mol%.
[Claim 19]
　The medical container according to any one of claims 15 to 18,
　wherein the cyclic olefin having no aromatic ring contains a compound represented by the following formula (B-1).
[In the

above formula [B-1], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and R 1 to R 18 and R a and R are b is a hydrocarbon group which may be independently substituted with a hydrogen atom, a halogen atom or a halogen atom, and R 15 to 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 may form an alkylidene group , or R 17 and R 18 may form an alkylidene group. Does not contain aromatic rings.)
[Claim 20]
　The medical container according to any one of claims 15 to 19,
　wherein the cyclic olefin having an aromatic ring is a compound represented by the following formula (C-1) or a compound represented by the following formula (C-2). And a medical container containing one or more selected from the group consisting of compounds represented by the following formula (C-3):
[Chemical bond 6]

(In the above formula (C-1), n ​​and q are 0, 1 or 2, respectively, and R 1 to R 17 are independently, a hydrogen atom, a halogen atom excluding a fluorine atom, or It is a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom other than a fluorine atom, one of R 10 to 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 10 may combine with each other to form a monocyclic ring or a polycyclic ring, and when q=1 or 2, R 10 and R 11 , R 11 and R 17 , R 17 and R 17 , R 17 And R 12 , R 12 and R 13 , R 13 and R 14 , R 14 and R 15 , R 15 and R 16 , R 16 and R 16 , R 16 and R 10May be bonded to each other to form a monocycle or a polycycle, and the monocycle or the polycycle may have a double bond, and the monocycle or the polycycle is an aromatic ring. It may be. )
[Chemical Formula 7]

in (above formula (C-2), n and m are each independently 0, 1 or 2, q is 1, 2 or 3, R 18 ~ R 31 are each independently, A hydrogen atom, a halogen atom excluding a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom excluding a fluorine atom, and when q=1, R 28 , R 29 and R 29 and R 30 , R 30 and R 31 may be coupled to each other to form a monocyclic or polycyclic ring, and when q = 2 or 3, R 28 and R 28 , R 28 and R 29 , R 29. And R 30 , R 30 and R 31 , R 31 and R 31 may be bonded to each other to form a monocyclic or polycyclic ring, the monocyclic ring or the polycyclic ring may have a double bond, and the monocyclic ring or the polycyclic ring may be formed. The polycycle may be an aromatic ring. )
[Formula 8]

in (above formula (C-3), q is 1, 2 or 3, R 32 ~ R 39 except each independently, a hydrogen atom, a halogen atom except fluorine atom or a fluorine atom, It is a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom, and when q=1, R 36 and R 37 , R 37 and R 38 , R 38 and R 39 are bonded to each other. It may form a monocyclic ring or a polycyclic ring, and when q=2 or 3, R 36 and R 36 , R 36 and R 37 , R 37 and R 38, R 38 and R 39 , R 39 and R 39 may be coupled to each other to form a monocyclic or polycyclic, and the monocyclic or polycyclic may have a double bond. The monocyclic ring or the polycyclic ring may be an aromatic ring. )
[Claim 21]
　In the medical container according to any one of claims 15 to 20,
　the glass transition temperature (Tg) of the cyclic olefin copolymer measured by a differential scanning calorimeter (DSC) is 120 ° C. or higher and 180 ° C. The following medical containers.
[Claim 22]
　The medical container according to any one of claims 15 to 21,
　wherein an intrinsic viscosity [η] of the cyclic olefin-based copolymer measured in decalin at 135°C is 0.05 dl/g or more and 5.0 dl/g. Medical container of g or less.
[Claim 23]
　The medical container according to any one of claims 15 to 22,
　wherein the cyclic olefin having an aromatic ring contains at least one selected from benzonorbornadiene, indenenorbornene, and methylphenylnorbornene.
[Claim 24]
　The medical container according to any one of claims 15 to 23, which is a
　syringe or a chemical storage container.