JP7309461B2 - Molded articles and medical containers - Google Patents

Description

The present invention relates to molded articles and medical containers.

Cyclic olefin resins have an excellent balance of properties such as transparency and chemical resistance. Therefore, for example, use as a material for forming molded articles such as medical containers is being studied. Techniques related to resin compositions containing such cyclic olefin resins include those described in Patent Document 1 and Patent Document 2, for example.

Patent Document 1 describes a cyclic olefin resin composition containing two types of specific cyclic olefin resins. It also describes that the composition has improved slip properties, excellent transparency, excellent surface gloss, and excellent hygienic properties.

In Patent Document 2, 60 to 90 parts by weight of a cyclic olefin resin and an aromatic vinyl/conjugated diene block copolymer having a number average molecular weight of 75,000 to 500,000 and/or hydrogenated products thereof of 10 to 40 A cyclic olefin resin composition consisting of parts by weight is described. It also describes that the composition provides a molded article having excellent impact strength and moisture resistance.

JP-A-2001-26693 JP-A-8-277353

Medical containers such as syringes and medicinal solution storage containers are usually filled with contents after being sterilized. During this sterilization, the container may be irradiated with electron beams or gamma rays.
According to studies by the present inventors, it has become clear that in some cases, medical containers using conventional cyclic olefin-based resins may undergo discoloration due to irradiation with electron beams or gamma rays.

The present invention has been made in view of such circumstances. In other words, the present invention provides a molded article and a medical container that are less discolored by electron beam or gamma ray irradiation and have excellent transparency.

The present inventors have made extensive studies to solve the above-described problems related to the present invention. As a result, a cyclic olefin copolymer comprising a structural unit derived from an α-olefin and a structural unit derived from a cyclic olefin having an aromatic ring and a cyclic olefin copolymer containing a stabilizer was found to be a resin constituting a molded article, particularly a medical container. We have found that the above problems can be solved by using an olefin copolymer composition. And the present invention shown below was completed.

That is, according to the present invention, the molded article and medical container shown below are provided.

（上記式（Ｃ－２）中、ｎおよびｍはそれぞれ独立に０、１または２であり、ｑは１、２または３であり、Ｒ^１８～Ｒ^３１はそれぞれ独立に、水素原子、フッ素原子を除くハロゲン原子、またはフッ素原子を除くハロゲン原子で置換されていてもよい炭素原子数１～２０の炭化水素基であり、またｑ＝１のときＲ^２８とＲ^２９、Ｒ^２９とＲ^３０、Ｒ^３０とＲ^３１は互いに結合して単環または多環を形成していてもよく、またｑ＝２または３のときＲ^２８とＲ^２８、Ｒ^２８とＲ^２９、Ｒ^２９とＲ^３０、Ｒ^３０とＲ^３１、Ｒ^３１とＲ^３１は互いに結合して単環または多環を形成していてもよく、上記単環または上記多環が二重結合を有していてもよく、また上記単環または上記多環が芳香族環であってもよい。）

（上記式（Ｃ－３）中、ｑは１、２または３であり、Ｒ^３２～Ｒ^３９はそれぞれ独立に、水素原子、フッ素原子を除くハロゲン原子、またはフッ素原子を除くハロゲン原子で置換されていてもよい炭素原子数１～２０の炭化水素基であり、またｑ＝１のときＲ^３６とＲ^３７、Ｒ^３７とＲ^３８、Ｒ^３８とＲ^３９は互いに結合して単環または多環を形成していてもよく、またｑ＝２または３のときＲ^３６とＲ^３６、Ｒ^３６とＲ^３７、Ｒ^３７とＲ^３８、Ｒ^３８とＲ^３９、Ｒ^３９とＲ^３９は互いに結合して単環または多環を形成していてもよく、上記単環または上記多環が二重結合を有していてもよく、また上記単環または上記多環が芳香族環であってもよい。）
［６］
上記［１］乃至［５］のいずれか一つに記載の成形体において、
示差走査熱量計（ＤＳＣ）で測定される、上記環状オレフィン系共重合体組成物（Ｑ）のガラス転移温度（Ｔｇ）が０℃以上１８０℃以下である成形体。
［７］
上記［１］乃至［６］のいずれか一つに記載の成形体において、
上記環状オレフィン系共重合体組成物（Ｑ）の１３５℃デカリン中で測定される極限粘度［η］が０．０５ｄｌ／ｇ以上６．０ｄｌ／ｇ以下である成形体。
［８］
上記［１］乃至［７］のいずれか一つに記載の成形体において、
上記芳香環を有する環状オレフィンが、ベンゾノルボルナジエンおよびインデンノルボルネンから選択される少なくとも一種を含む成形体。
［９］
上記［１］乃至［８］のいずれか一つに記載の成形体からなる医療用容器。
［１０］
上記［９］に記載の医療用容器において、
シリンジまたは薬液保存容器である医療用容器。 [1]
A cyclic olefin copolymer (P) having a structural unit (A) derived from an α-olefin having 2 to 20 carbon atoms and a structural unit (C) derived from a cyclic olefin having an aromatic ring, and a stabilizer ( A molded article made of a cyclic olefin copolymer composition (Q) containing B),
The content of the stabilizer (B) is 0.0001 parts by mass or more and 0.3 parts by mass or less with respect to 100 parts by mass of the cyclic olefin copolymer (P),
A molded article in which the total content of the structural unit (A) and the structural unit (C) in the cyclic olefin copolymer (P) is 93 mol% or more.
[2]
In the molded article described in [1] above,
A molded article having a radical amount of 5.0×10 ¹² spins/mg or less after 5 days of irradiation with 50 kGy of gamma rays.
[3]
In the molded article according to [1] or [2] above,
A molded article in which the stabilizer (B) contains at least one selected from the group consisting of phenol compounds, phosphorus compounds and hindered amine compounds.
[4]
In the molded article according to any one of [1] to [3] above,
The content of the structural unit (A) in the cyclic olefin copolymer (P) is 40 mol% or more and 99.5 mol% or less, and the content of the structural unit (C) is 0.5 mol%. A compact having a content of 60 mol % or more.
[5]
In the molded article according to any one of [1] to [4] above,
A molded article in which the cyclic olefin having an aromatic ring is one or more selected from the group consisting of compounds represented by the following formula (C-2) and compounds represented by the following formula (C-3).

(In formula (C-2) above, n and m are each independently 0, 1 or 2, q is 1, 2 or 3, R ¹⁸ to R ³¹ are each independently a hydrogen atom, a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms optionally 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 combine with each other to form a monocyclic or polycyclic ring, and when q=2 or 3, R ²⁸ and R ²⁸ , R ²⁸ and R ²⁹ , R ²⁹ and R ³⁰ , R ³⁰ and R ³¹ , R ³¹ and R ³¹ may be bonded to each other to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring may have a double bond, or the monocyclic The ring or said polycycle may be an aromatic ring.)

(In formula (C-3) above, q is 1, 2 or 3, and R ³² to R ³⁹ are each independently substituted with a hydrogen atom, a halogen atom excluding a fluorine atom, or a halogen atom excluding a fluorine atom. a hydrocarbon group having 1 to 20 carbon atoms which may be substituted, and when q=1, R ³⁶ and R ³⁷ , R ³⁷ and R ³⁸ , R ³⁸ and R ³⁹ are bonded to each other to form a monocyclic or polycyclic 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 are} bonded to each other It may form a monocyclic ring or a polycyclic ring, the monocyclic ring or the polycyclic ring may have a double bond, and the monocyclic ring or the polycyclic ring may be an aromatic ring. )
[6]
In the molded article according to any one of [1] to [5] above,
A molded article in which the cyclic olefin copolymer composition (Q) has a glass transition temperature (Tg) of 0° C. or higher and 180° C. or lower as measured by a differential scanning calorimeter (DSC).
[7]
In the molded article according to any one of [1] to [6] above,
A molded product, wherein the intrinsic viscosity [η] of the cyclic olefin copolymer composition (Q) measured in decalin at 135°C is 0.05 dl/g or more and 6.0 dl/g or less.
[8]
In the molded article according to any one of [1] to [7] above,
A molded article in which the cyclic olefin having an aromatic ring contains at least one selected from benzonorbornadiene and indenenorbornene.
[9]
A medical container comprising the molded article according to any one of [1] to [8] above.
[10]
In the medical container according to [9] above,
A medical container that is a syringe or a drug storage container.

ADVANTAGE OF THE INVENTION According to this invention, the molded object and medical container which are excellent in transparency with little discoloration by electron beam or gamma-ray irradiation can be provided.

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described below based on embodiments. In this embodiment, "A to B" indicating a numerical range represents from A to B unless otherwise specified.

[Cyclic olefin copolymer (P)]
First, the cyclic olefin copolymer (P) of the embodiment according to the present invention will be described.
The cyclic olefin 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 derived from a cyclic olefin having an aromatic ring (C ), and the total content of the structural unit (A) and the structural unit (C) in the cyclic olefin copolymer (P) is 93 mol% or more, preferably 95 mol% or more, more preferably 98 mol % or more, more preferably 99 mol % or more, and preferably 100 mol % or less.

The cyclic olefin 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 (C) derived from a cyclic olefin having an aromatic ring. By containing, it is possible to improve the radiation resistance of the molded article while maintaining good transparency.
As described above, according to the cyclic olefin-based copolymer (P) according to the present embodiment, it is possible to obtain a molded article that is less discolored by electron beam or gamma ray irradiation and has excellent transparency.

(Structural unit (A) derived from α-olefin having 2 to 20 carbon atoms)
The structural unit (A) according to the present 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 includes 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- Branched α-olefins having 4 to 20 carbon atoms such as 1-hexene and 3-ethyl-1-hexene are included. Among these, linear α-olefins having 2 to 4 carbon atoms are preferred, and ethylene is particularly preferred. Such linear or branched α-olefins can be used singly or in combination of two or more.

When the total content of the structural unit (A) 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 (A) in the polymer (P) is preferably 40 mol% or more and 99.5 mol% or less, more preferably 50 mol% or more and 90 mol% or less.
When the content of the structural unit (A) is at least the above lower limit, the heat resistance and dimensional stability of the molded article can be improved. In addition, when the content of the structural unit (A) is equal to or less than the upper limit, the moldability of the obtained medical container can be improved.
In this embodiment, the content of the structural unit (A) can be measured, for example, by ¹ H-NMR or ¹³ C-NMR.

(Structural Unit (C) Derived from a Cyclic Olefin Having an Aromatic Ring)
The structural unit (C) according to this embodiment is a structural unit derived from a cyclic olefin having an aromatic ring.
Examples of the cyclic olefin having an aromatic ring according to the present embodiment include compounds represented by the following formula (C-2) and compounds represented by the following formula (C-3). These aromatic ring-containing cyclic olefins may be used singly or in combination of two or more.

上記式（Ｃ－２）中、ｎおよびｍはそれぞれ独立に０、１または２であり、ｑは１、２または３である。ｍは０または１であることが好ましく、１であることがより好ましい。ｎは０または１であることが好ましく、０であることがより好ましい。ｑは１または２であることが好ましく、１であることがより好ましい。
Ｒ^１８～Ｒ^３１はそれぞれ独立に、水素原子、フッ素原子を除くハロゲン原子、またはフッ素原子を除くハロゲン原子で置換されていてもよい炭素原子数１～２０の炭化水素基である。
Ｒ^１８～Ｒ^３１はそれぞれ独立に水素原子または炭素原子数１～２０の炭化水素基であることが好ましく、水素原子であることがより好ましい。
またｑ＝１のときＲ^２８とＲ^２９、Ｒ^２９とＲ^３０、Ｒ^３０とＲ^３１は互いに結合して単環または多環を形成していてもよく、またｑ＝２または３のときＲ^２８とＲ^２８、Ｒ^２８とＲ^２９、Ｒ^２９とＲ^３０、Ｒ^３０とＲ^３１、Ｒ^３１とＲ^３１は互いに結合して単環または多環を形成していてもよく、上記単環または上記多環が二重結合を有していてもよく、また上記単環または上記多環が芳香族環であってもよい。

In formula (C-2) above, n and m are each independently 0, 1 or 2, and q is 1, 2 or 3. m is preferably 0 or 1, more preferably 1. n is preferably 0 or 1, more preferably 0. q is preferably 1 or 2, more preferably 1.
Each of R ¹⁸ to R ³¹ is independently a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom other than a fluorine atom.
Each of R ¹⁸ to R ³¹ is preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrogen atom.
When q=1, R ²⁸ and R ²⁹ , R ²⁹ and R ³⁰ , R ³⁰ and R ³¹ may be bonded together 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 together to form a monocyclic or polycyclic ring, and the monocyclic or The polycyclic ring may have a double bond, and the monocyclic or polycyclic ring may be an aromatic ring.

上記式（Ｃ－３）中、ｑは１、２または３であり、１または２であることが好ましく、１であることがより好ましい。
Ｒ^３２～Ｒ^３９はそれぞれ独立に、水素原子、フッ素原子を除くハロゲン原子、またはフッ素原子を除くハロゲン原子で置換されていてもよい炭素原子数１～２０の炭化水素基である。
Ｒ^３２～Ｒ^３９はそれぞれ独立に水素原子または炭素原子数１～２０の炭化水素基であることが好ましく、水素原子であることがより好ましい。
またｑ＝１のときＲ^３６とＲ^３７、Ｒ^３７とＲ^３８、Ｒ^３８とＲ^３９は互いに結合して単環または多環を形成していてもよく、またｑ＝２または３のときＲ^３６とＲ^３６、Ｒ^３６とＲ^３７、Ｒ^３７とＲ^３８、Ｒ^３８とＲ^３９、Ｒ^３９とＲ^３９は互いに結合して単環または多環を形成していてもよく、上記単環または上記多環が二重結合を有していてもよく、また上記単環または上記多環が芳香族環であってもよい。

In formula (C-3) above, q is 1, 2 or 3, preferably 1 or 2, more preferably 1.
Each of R ³² to R ³⁹ is independently a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom other than a fluorine atom.
Each of R ³² to R ³⁹ is preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, 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 ³⁶ , R ³⁶ and R ³⁷ , R ³⁷ and R ³⁸ , R ³⁸ and R ³⁹ , R ³⁹ and R ³⁹ may be bonded together to form a monocyclic or polycyclic ring, and The polycyclic ring may have a double bond, and the monocyclic or polycyclic ring may be an aromatic ring.

The hydrocarbon groups having 1 to 20 carbon atoms each independently include, for example, alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 15 carbon atoms, and aromatic hydrocarbon groups. be done. More specifically, alkyl groups include methyl group, ethyl group, propyl group, isopropyl group, amyl group, hexyl group, octyl group, decyl group, dodecyl group and octadecyl group, and cycloalkyl groups include cyclohexyl Examples of aromatic hydrocarbon groups include aryl groups such as phenyl, tolyl, naphthyl, benzyl, and phenylethyl groups, and aralkyl groups. These hydrocarbon groups may be substituted with halogen atoms other than fluorine atoms.

Among these, at least one selected from, for example, benzonorbornadiene and indene norbornene is preferable as the cyclic olefin having an aromatic ring according to the present embodiment.

When the total content of the structural unit (A) and the structural unit (C) in the cyclic olefin copolymer (P) according to the present embodiment is 100 mol%, the cyclic olefin copolymer (P) The content of the structural unit (C) in the polymer is preferably 0.5 mol% or more and 60 mol% or less, more preferably 10 mol% or more, and more preferably 50 mol% or less.
In this embodiment, the content of the structural unit (C) can be measured, for example, by ¹ H-NMR or ¹³ C-NMR.

Although the copolymerization type of the cyclic olefin copolymer (P) according to the present embodiment is not particularly limited, examples thereof include random copolymers and block copolymers. 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.

The cyclic olefin copolymer (P) according to the present embodiment is, for example, JP-A-60-168708, JP-A-61-120816, JP-A-61-115912, JP-A-61- 115916, JP-A-61-271308, JP-A-61-272216, JP-A-62-252406, JP-A-62-252407, JP-A-2007-314806, JP-A It can be produced by appropriately selecting conditions according to the method disclosed in Japanese Patent Application Laid-Open No. 2010-241932.

The glass transition temperature (Tg) of the cyclic olefin copolymer (P) according to the present embodiment, measured with a differential scanning calorimeter (DSC), is preferably 0°C or higher and 180°C or lower. From the viewpoint of further improving heat resistance while maintaining good transparency of the resulting medical container, the temperature is more preferably 100° C. or higher and 180° C. or lower, and still more preferably 110° C. or higher and 165° C. or lower.

The intrinsic viscosity [η] (in decalin at 135°C) of the cyclic olefin copolymer (P) according to the present embodiment is, for example, 0.05 to 6.0 dl/g, preferably 0.2 to 4.0 dl. /g, more preferably 0.3 to 2.0 dl/g, particularly preferably 0.3 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. Moreover, moldability can be improved as intrinsic viscosity [(eta)] is below the said upper limit.

[Stabilizer (B)]
The stabilizer (B) of the embodiment according to the present invention will be explained.
The content of the stabilizer (B) in the cyclic olefin-based copolymer composition (Q) according to the present embodiment is 0.00% when the content of the cyclic olefin-based copolymer (P) is 100 parts by mass. 3 parts by mass or less, preferably 0.2 parts by mass or less, more preferably 0.1 parts by mass or less, 0.0001 parts by mass or more, preferably 0.0002 parts by mass or more, more preferably 0.0005 parts by mass That's it. By setting the content of the stabilizer (B) in the cyclic olefin-based copolymer composition (Q) according to the present embodiment within the above range, the transparency of the molded body can be maintained satisfactorily while the electron beam or gamma ray Discoloration and generation of radicals due to irradiation can be effectively reduced.
When the content of the stabilizer (B) is equal to or less than the above upper limit, the amount of radicals generated by electron beam or gamma ray irradiation can be effectively suppressed in the obtained molded article. When the content of the stabilizer (B) is at least the above lower limit, discoloration due to deterioration of the resin during molding can be suppressed, and the obtained molded article can have good transparency.
The stabilizer (B) is preferably at least one selected from the group consisting of hindered amine compounds, phosphorus compounds and phenol compounds, more preferably hindered amine compounds and phosphorus compounds.

As the hindered amine compound [D] (hereinafter simply referred to as compound [D] or [D]), a hindered amine structure (specifically, a partial structure represented by the following formula (b1)) can be used as appropriate.
In formula (b1), * represents a bond with another chemical structure.

Specifically, compounds known as Hindered Amine Light Stabilizers (abbreviated as HALS) can be used as the compound [D].

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 WO 2008/047468. Examples include piperidine derivatives or salts thereof described in paragraphs 0187 to 0226 of 2008/047468, and polyamine derivatives or salts thereof described in JP-A-2006-321793.

Also, Chimassorb 2020, Chimassorb 944, Tinuvin 622, Tinuvin PA144 Tinuvin 765, Tinuvin
770 (manufactured by BASF), Cyasorb UV-3853, Cyasorb UV-3529, Cyasorb UV-3346, Cyasorb UV-531 (manufactured by Cytec), Adekastab LA-52, Adekastab LA-57, Adekastab 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 (manufactured by ADEKA) and the like can be used.

In the present embodiment, compound [D] is preferably a compound having a structural unit represented by general formula (b2) below.
This compound is typically a polymer or oligomer. By using the compound [D], which is a polymer or oligomer such as this compound, it is believed that 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 due to irradiation. As a result, it is believed that discoloration due to electron beam or gamma ray irradiation can be further reduced, and radical generation due to electron beam or gamma ray irradiation can be further reduced.

In 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 groups in which these groups are linked. Among these, an alkylene group is preferred, an alkylene group having 1 to 6 carbon atoms is more preferred, and an alkylene group having 1 to 4 carbon atoms is more preferred.
As for the compound having the structural unit represented by general formula (b2), a commercially available product may be used, or it may be obtained by polycondensation of the corresponding diol and dicarboxylic acid.

About compound [D], only 1 type may be used and 2 or more types may be used.

There are no particular restrictions on the phosphorus compound [E] (hereinafter sometimes simply referred to as compound [E] or [E]). For example, a known phosphorus antioxidant can be used.

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- Phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene, 6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy ]-2,4,8,10-tetrakis-t-butyldibenzo[d,f][1.3.2]monophosphite compounds such as dioxaphosphepin; 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(diphenyl monoalkyl (C12-C15) phosphite), 1,1,3-tris(2-methyl-4-di-tridecylphosphite-5-t-butylphenyl)butane, tetrakis(2,4 -di-t-butylphenyl)-4,4'-biphenylenediphosphite, cyclic neopentanetetraylbis(isodecylphosphite), cyclic neopentanetetraylbis(nonylphenylphosphite), cyclic neo Pentanetetraylbis(2,4-di-t-butylphenylphosphite), cyclic neopentanetetraylbis(2,4-dimethylphenylphosphite), cyclic neopentanetetraylbis(2,6-di -t-butylphenyl phosphite) and other diphosphite compounds.

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

In general formulas (c1), (c2) and (c3),
R ¹ , when there are more than one, each independently represents an alkyl group,
R ² , when there are more than one, each independently represents an aromatic group,
R ³ represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group,
X represents a single bond or a divalent linking group.

The alkyl group for R ¹ preferably has 1 to 10 carbon atoms, more preferably a t-butyl group.
Examples of the aromatic group for R ² include a phenyl group, a naphthyl group, and a group obtained by substituting these with an alkyl group or the like.
The carbon number of R ³ is preferably 1-30, more preferably 3-20, still more preferably 6-18.
R ³ is preferably an aryl group or an aralkyl group, more preferably an aralkyl group. These aryl groups or aralkyl groups may be further substituted with a substituent (eg, an alkyl group having 1 to 6 carbon atoms, a hydroxy group, etc.).
When X is a divalent linking group, specific examples include an alkylene group (such as a methylene group) and an ether group (--O--). X is preferably a single bond.
Commercially available products include Irgafos 168 (manufactured by BASF), Sumilizer-GP (manufactured by Sumitomo Chemical Co.) and the like.

About compound [E], only 1 type may be used and 2 or more types may be used.

Phenolic compound [F] (hereinafter simply referred to as compound [F] or [F]) is, for example, 2-t-6-(3-t-2-hydroxy-5 -methylbenzyl)-4-methylphenyl acrylate, 2,4-di-tertiary-amyl-6-(1-(3,5-di-tertiary-amyl-2-hydroxyphenyl)ethyl)phenyl acrylate and the like. Acrylate-based phenol compounds described in JP-A-63-179953 and JP-A-1-168643; 2,6-di-t-4-methylphenol, 2,6-di-t-4-ethylphenol, Octadecyl-3-(3,5-di-t-4-hydroxyphenyl)propionate, 2,2′-methylene-bis(4-methyl-6-t-phenol), 4,4′-butylidene-bis(6 -tm-cresol), 4,4′-thiobis(3-methyl-6-t-phenol), bis(3-cyclohexyl-2-hydroxy-5-methylphenyl)methane, 3,9-bis(2 -(3-(3-t-4-hydroxy-5-methylphenyl)propionyloxy)-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane, 1, 1,3-tris(2-methyl-4-hydroxy-5-t-phenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-4-hydroxybenzyl ) benzene, tetrakis(methylene-3-(3′,5′-di-t-4′-hydroxyphenylpropionate)methane [i.e., pentaerythrimethyl-tetrakis(3-(3,5-di-t- 4-hydroxyphenylpropionate)], triethylene glycol bis (3-(3-t-4-hydroxy-5-methylphenyl)propionate), alkyl-substituted phenol compounds such as tocophenol; 6-(4-hydroxy- 3,5-di-t-anilino)-2,4-bisoctylthio-1,3,5-triazine, 6-(4-hydroxy-3,5-dimethylanilino)-2,4-bisoctylthio -1,3,5-triazine, 6-(4-hydroxy-3-methyl-5-t-anilino)-2,4-bisoctylthio-1,3,5-triazine, 2-octylthio-4,6 -Bis-(3,5-di-t-4-oxyanilino)-1,3,5-triazine group-containing phenol compounds; 6-[3-(3-t-butyl-4-hydroxy-5 -methylphenyl)propoxy]-2,4,8,10-tetrakis-t-butyldibenzo[d,f][1.3.2]dioxaphosphepin and the like can be used.
Commercially available products include Irganox 1010, Irganox 1035, Irganox 1076, Irganox 1098, Irganox 1135, Irganox 1330, Irganox 1520L, Irganox 245, Irganox 259, Irganox 3 144, Irganox 565 (manufactured by BASF), Sumilizer-GP , Sumilizer GS (F) (manufactured by Sumitomo Chemical Co., Ltd.) and the like.

About compound [F], only 1 type may be used and 2 or more types may be used.

[Cyclic olefin copolymer composition (Q)]
The cyclic olefin copolymer composition (Q) according to the present embodiment is a cyclic olefin copolymer composition for forming a molded article, particularly a medical container. It contains a polymer (P) and a stabilizer (B), and if necessary, may contain other components.

In addition, the content of the cyclic olefin copolymer (P) in the cyclic olefin copolymer composition (Q) according to the present embodiment is determined by the transparency of the resulting molded product and the resistance to gamma rays or electron rays. From the viewpoint of further improving the performance balance of the cyclic olefin copolymer composition (Q), when the entire cyclic olefin copolymer composition (Q) 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 mass % or less, more preferably 80 mass % or more and 100 mass % or less, and particularly preferably 90 mass % or more and 100 mass % or less.
The cyclic olefin-based copolymer composition (Q) according to the present embodiment contains the cyclic olefin-based copolymer (P) in the above ratio, so that the obtained medical container has the properties required for medical containers. It is possible to further improve gamma ray resistance or electron ray resistance performance while satisfying good transparency.

The glass transition temperature (Tg) of the cyclic olefin copolymer composition (Q) according to the present embodiment, measured with a differential scanning calorimeter (DSC), is preferably 0°C or higher and 180°C or lower. The temperature is preferably 100° C. or higher and 180° C. or lower, more preferably 110° C. or higher and 165° C. or lower, from the viewpoint of further improving heat resistance while maintaining good transparency of the obtained molded article and medical container.

The intrinsic viscosity [η] (in decalin at 135°C) of the cyclic olefin copolymer composition (Q) according to the present embodiment is, for example, 0.05 to 6.0 dl/g, preferably 0.2 to 4. 0 dl/g, more preferably 0.3 to 2.0 dl/g, particularly preferably 0.3 to 1.0 dl/g.
When the intrinsic viscosity [η] is at least the above lower limit, the mechanical strength of the resulting molded article and medical container can be improved. Moreover, moldability can be improved as intrinsic viscosity [(eta)] is below the said upper limit.

(other ingredients)
The cyclic olefin copolymer composition (Q) according to the present embodiment may optionally contain an antioxidant, a metal deactivator, a hydrochloric acid absorbent, an antistatic agent, a flame retardant, a slip agent, and an antiblocking agent. agents, anti-fogging agents, lubricants, natural oils, synthetic oils, waxes, organic or inorganic fillers, resins other than the cyclic olefin copolymer (P), etc. may be blended to the extent that the objects of the present invention are not impaired. can be used, and the mixing ratio thereof is an appropriate amount.

The cyclic olefin copolymer composition (Q) according to the present embodiment is prepared by mixing the cyclic olefin copolymer (P), the stabilizer (B) and other components with a known kneading device such as an extruder and a Banbury mixer. A method of melt-kneading using a; A method of dissolving the cyclic olefin copolymer (P), the stabilizer (B) and other components in a common solvent and then evaporating the solvent; A method of adding a solution of the polymer (P), the stabilizer (B) and other components to cause precipitation; and the like.

[Molded body]
Next, a molded article according to an embodiment of the present invention will be described.
The molded article according to this embodiment contains the cyclic olefin copolymer composition (Q) according to this embodiment.
Since the molded article according to the present embodiment contains the cyclic olefin copolymer composition (Q) according to the present embodiment, it has an excellent performance balance between transparency and resistance to gamma rays or electron rays. This molded article is little discolored by electron beam or gamma ray irradiation.
Here, according to another study by the present inventors, it has become clear that radicals may be generated in conventional molded articles by electron beam or gamma ray irradiation. As a result, there is a concern that there is a risk that the content will deteriorate after filling the compact with the content.
In contrast, the molded product according to the present embodiment can reduce the amount of radicals generated by electron beam or gamma ray irradiation. Therefore, according to the molded article according to the present embodiment, it is possible to reduce the risk of deterioration of the contents.

The method for obtaining a molded product by molding the cyclic olefin copolymer (P) according to the present embodiment or the cyclic olefin copolymer composition (Q) according to the present embodiment is not particularly limited. A known 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, etc. can be applied. is. Among these, the injection molding method is preferable from the viewpoint of moldability and productivity. 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 selected appropriately within the range.

Further, by irradiating the molded article produced above with gamma rays or electron beams, a gamma-ray or electron beam-irradiated molded article (a medical container irradiated with gamma rays or electron rays) can be obtained. This compact is sterilized or sterilized by irradiation, so it is clean, and discoloration and generation of radicals are suppressed. Although the irradiation dose is not particularly limited, it is usually 5 to 100 kilograys (kGy), preferably 10 to 80 kilograys.
The amount of radicals generated after irradiating the compact produced above with 50 kilograys of gamma rays is preferably 5.0×10 ¹² spins/mg or less.
The amount of radicals generated after gamma ray irradiation is measured by an electron spin resonance (ESR) method.
After 5 days of irradiation with a dose of 50 kGy of gamma rays, a test piece is cut out, placed in a test tube (details below), and the ESR spectrum is measured under the following conditions.
・Apparatus: Electron spin resonance apparatus JES-TE200 manufactured by JEOL Ltd.
・Resonance frequency: 9.2 GHz
・Microwave input: 0.1 to 2.0 mW
・Sweep range: 30mT
・Modulation amplitude: 1mT
・ Standard sample: TEMPOL Free Radical (manufactured by Tokyo Chemical Industry Co., Ltd.)
・Measurement temperature: room temperature ・Measurement atmosphere: air The amount of radicals is measured under the above conditions, and a calibration curve prepared from the ESR spectrum of a standard sample (TEMPOL Free Radical) of known concentration is used to determine the amount of organic radicals per 1 mg of the test piece. (spins/mg) can be determined.

The medical container according to this embodiment is made of the molded product according to this embodiment.
Examples of medical containers include syringes used in syringe barrels (hereinafter referred to as syringes) and syringes filled with drug solutions and drugs (hereinafter also referred to as prefilled syringes), and filled with drug solutions and drugs. A storage container (hereinafter also referred to as a drug solution storage container) used for a storage container formed by

Here, the prefilled syringe is a syringe-shaped formulation that is pre-filled with a drug solution or drug, and includes a single-chamber type filled with one type of liquid and a double-chamber type filled with two types of drugs. There is Most prefilled syringes are of the single-chamber type, but the double-chamber type includes liquid/powder type preparations consisting of powder and its solution and liquid/liquid type preparations consisting of two types of liquids. Examples of the single chamber type internal solution include heparin solution and the like. Syringes used for syringes and prefilled syringes include, for example, prefillable syringes, prefilled syringes for vaccines, prefilled syringes for anticancer drugs, needleless syringes, and the like.

Examples of medicinal solution storage containers include wide-mouthed bottles, narrow-mouthed bottles, medicine bottles, vials, infusion bottles, bulk containers, petri dishes, test tubes, and analysis cells. More specifically, liquid, powder or solid medicine containers such as ampoules, press-through packages, bags for infusion solutions, drip containers, eye drops containers; sampling test tubes for blood tests, blood collection tubes, specimens Sample containers such as containers; Analysis containers such as ultraviolet inspection cells; Sterile containers for medical instruments such as scalpels, forceps, gauze, and contact lenses; laboratory equipment; artificial organ housings, and the like.

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

When it is assumed to be used for all light rays or multiple wavelength ranges, it is necessary that the total light transmittance is good. is 88-93%. If the total light transmittance is 85% or more, the required amount of light can be secured. A known method can be applied to measure the total light transmittance, and the measuring device is not limited. Examples include a method of forming a 3 mm sheet and measuring the total light transmittance of the sheet obtained by forming the cyclic olefin copolymer composition (Q) according to the present embodiment using a haze meter.

In addition, the medical container according to this embodiment has excellent light transmittance for light with a wavelength of 450 nm to 800 nm.
The light transmittance can be further improved by providing a known antireflection film on the surface.

Although the embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than those described above can also be adopted.
Moreover, the present invention is not limited to the above-described embodiments, and includes modifications, improvements, etc. within the scope of achieving the object of the present invention.

EXAMPLES The present invention will be specifically described below based on Examples, but the present invention is not limited to these Examples.

<Production of cyclic olefin copolymer (P)>
[Production Example 1]
After circulating nitrogen as an inert gas at a flow rate of 100 Nl/hr for 30 minutes in a 500 ml glass reaction vessel equipped with a stirrer, cyclohexane and benzonorbornadiene (27.0 mmol, hereinafter also referred to as BNBD) were added. rice field. Then, the temperature of the solvent 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 a feed rate of 0.5 Nl/hr. (Modified MethylAluminoxane) (1.25 mmol) and a catalyst (0.00050 mmol) prepared by the method described in paragraph 0112 of JP-A-2010-241932 were added to a glass reactor to initiate polymerization.
After 10 minutes had passed, 5 ml of isobutyl alcohol was added to terminate the polymerization to obtain a polymerization solution containing a copolymer of ethylene and BNBD. 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 brought into contact with the mixture for 2 hours under strong stirring to perform demineralization. The deashed polymerization solution was added to a beaker containing acetone about three times the volume of the polymerization solution with stirring to precipitate a copolymer, and the precipitated copolymer was separated from the filtrate by filtration. The solvent-containing polymer thus obtained was dried under reduced pressure at 130° C. for 10 hours to obtain 0.60 g of a white powdery ethylene/benzonorbornadiene copolymer.
As described above, a cyclic olefin copolymer was obtained.
0.01 parts by mass of Irganox 1010 as a phenolic stabilizer [F] was added to 100 parts by mass of the obtained cyclic olefin copolymer. Next, using a twin-screw extruder KZW12 (screw diameter 12 mmφ, L/D = 45) manufactured by Technobell Co., Ltd., granulation was performed under the conditions of a set temperature of 270 ° C., a resin extrusion rate of 30 g / min and a screw rotation speed of 200 rpm, and cyclic olefin A system copolymer composition (Q-1) was obtained.

[Production Examples 2 to 9]
In the same manner as in Production Example 1, except that the content of each structural unit constituting the cyclic olefin copolymer (P) and the type and blending amount of the stabilizer were adjusted to the values shown in Table 1. Operations were carried out to obtain cyclic olefin copolymer compositions (Q-2) to (Q-9) shown in Table 1, respectively.
Here, BNBD in Table 1 means benzonorbornadiene represented by the following formula (1), and IndNB means indene norbornene represented by the following formula (2).

Various physical properties of the obtained cyclic olefin copolymer compositions (Q-1) to (Q-9) were measured or evaluated by the following methods, and the obtained results are shown in Table 1.

[Method for Measuring Content of Each Structural Unit Constituting Cyclic Olefin-Based Copolymer (P)]
The content of ethylene and cyclic olefin having an aromatic ring was measured by using a nuclear magnetic resonance apparatus "ECA500 type" manufactured by JEOL Ltd. under the following conditions.
Solvent: Heavy tetrachloroethane Sample concentration: 50-100g/l-solvent
Pulse repetition time: 5.5 seconds Accumulation times: 6000 to 16000 times Measurement temperature: 120°C
From the ¹³ C-NMR spectrum measured under the above conditions, the compositions of ethylene and cyclic olefins having aromatic rings were quantified.

[Glass transition temperature Tg (°C)]
Using DSC-6220 manufactured by Shimadzu Science Co., Ltd., the glass transition temperature Tg of the cyclic olefin copolymer composition (Q) was measured under an N ₂ (nitrogen) atmosphere. The cyclic olefin-based copolymer composition (Q) was heated from room temperature to 200°C at a temperature increase rate of 10°C/min, held for 5 minutes, and then cooled to -20°C at a temperature decrease rate of 10°C/min. Hold for 5 minutes afterwards. Then, the glass transition point (Tg) of the cyclic olefin copolymer composition (Q) was obtained from the endothermic curve when the temperature was raised to 200°C at a temperature elevation rate of 10°C/min.

[Intrinsic viscosity [η]]
Using a kinematic viscometer (type VNR053U manufactured by Rigosha), a sample was prepared by dissolving 0.25 to 0.30 g of the cyclic olefin copolymer composition (Q) in 25 ml of decalin. The specific viscosity of the cyclic olefin copolymer composition (Q) is measured at 135° C. according to ASTM J1601, and the ratio of this to the concentration is extrapolated to the concentration of 0 to obtain the cyclic olefin copolymer composition (Q). The intrinsic viscosity [η] of was obtained.

<Method for manufacturing molded body>
[Press molding]
The pellets obtained in Production Examples 1 to 9 above were press-molded at 250° C. using a hand press machine manufactured by Toyo Seiki Co., Ltd. to prepare square plate test pieces having a thickness of 2 mm.
Various physical properties of the molded article containing the obtained cyclic olefin copolymer composition were measured or evaluated by the following methods, and the obtained results are shown in Table 2.

[Gamma ray irradiation]
The 2 mm-thick square plate test piece obtained above was irradiated with 50 kGy of gamma rays.

[transparency]
The internal haze of the obtained square plate test piece having a thickness of 2 mm and the test piece after 5 days of gamma ray irradiation were 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 Industries Co., Ltd.).
○: Internal haze is less than 5.0% ×: The test piece is visually cloudy, or the internal haze is 5.0% or more

[Evaluation: hue immediately after gamma ray irradiation]
The test piece immediately after gamma ray irradiation was piled up on white paper with a thickness of 20 mm. The hue and brightness at this time were visually evaluated.
The hue conformed to the Munsell color system. The evaluation criteria were as follows.
◯ (Good): Brightness is 7 to 9.5 and hue is between 5.0 GY to 10 GY.
Δ (Normal): Brightness is 5 to 9.5 and hue is between 5Y and 5GY. However, this does not apply to cases that correspond to the above ○ (good).
x (bad): the brightness is 0 or more and less than 5 and/or the hue is between 2.5Y and 5Y. However, this does not apply to cases falling under △ (normal) above.

I would like to supplement the above evaluation criteria.
As for the lightness, it is clear that the larger the value, the closer to white, and the less the discoloration.
As for the hue, green is preferable to yellow because yellow gives an unclean impression to patients and is avoided, especially when it is used as a medical container.

[Evaluation: Amount of radicals after 5 days and 1 month after gamma ray irradiation]
The amount of radicals in the samples 5 days and 1 month after gamma ray irradiation was measured by electron spin resonance (ESR).
Specifically, 5 days and 1 month after irradiation with a dose of 50 kGy gamma rays, a test piece was cut out, placed in a test tube (details below), and the ESR spectrum was measured under the following conditions.

・Apparatus: Electron spin resonance apparatus JES-TE200 manufactured by JEOL Ltd.
・Resonance frequency: 9.2 GHz
・Microwave input: 0.1 to 2.0 mW
・Sweep range: 30mT
・Modulation amplitude: 1mT
・ Standard sample: TEMPOL Free Radical (manufactured by Tokyo Chemical Industry Co., Ltd.)
・Measurement temperature: room temperature ・Measurement atmosphere: air The amount of radicals is measured under the above conditions, and a calibration curve prepared from the ESR spectrum of a standard sample (TEMPOL Free Radical) of known concentration is used to determine the amount of organic radicals per 1 mg of the test piece. (spins/mg) was determined.

As described above, the molded articles (sheets) composed of the cyclic olefin copolymer compositions (Q) obtained in Examples 1 to 7 had an excellent balance of transparency and gamma ray resistance. On the other hand, Comparative Example 1 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 performance balance between transparency and gamma ray resistance. Moreover, Comparative Example 2, in which the content of the stabilizer was 0.4 parts by mass with respect to 100 parts by mass of the cyclic olefin copolymer, was inferior in performance balance between transparency and gamma ray resistance.

Claims (8)

A cyclic olefin copolymer (P) having a structural unit (A) derived from an α-olefin having 2 to 20 carbon atoms and a structural unit (C) derived from a cyclic olefin having an aromatic ring, and a stabilizer ( A molded article made of a cyclic olefin copolymer composition (Q) containing B),
The stabilizer (B) contains a phenolic compound, and the content of the stabilizer ( B ) is 0.001 part by mass or more and 0.01 part by mass with respect to 100 parts by mass of the cyclic olefin copolymer (P). and
The total content of the structural unit (A) and the structural unit (C) in the cyclic olefin copolymer (P) is 93 mol% or more,
The content of the structural unit (A) in the cyclic olefin copolymer (P) is 40 mol% or more and 99.5 mol% or less, and the content of the structural unit (C) is 0.5 mol%. 60 mol% or less,
A molded article having a radical amount of 5.0×10 ¹² spins/mg or less after 5 days of irradiation with 50 kGy of gamma rays . A cyclic olefin copolymer (P) having a structural unit (A) derived from an α-olefin having 2 to 20 carbon atoms and a structural unit (C) derived from a cyclic olefin having an aromatic ring, and a stabilizer ( A molded article made of a cyclic olefin copolymer composition (Q) containing B),
The stabilizer (B) contains a phosphorus compound and a hindered amine compound, and the content of the stabilizer (B) is 0.0001 parts by mass or more based on 100 parts by mass of the cyclic olefin copolymer (P). .3 parts by mass or less,
The total content of the structural unit (A) and the structural unit (C) in the cyclic olefin copolymer (P) is 93 mol% or more,
The content of the structural unit (A) in the cyclic olefin copolymer (P) is 40 mol% or more and 99.5 mol% or less, and the content of the structural unit (C) is 0.5 mol%. 60 mol% or less,
A molded article having a radical amount of 5.0×10 ¹² spins/mg or less after 5 days of irradiation with 50 kGy of gamma rays . In the molded article according to claim 1 or 2 ,
A molded product in which the aromatic ring-containing cyclic olefin is one or more selected from the group consisting of compounds represented by the following formula (C-2) and compounds represented by the following formula (C-3).

(In formula (C-2) above, n and m are each independently 0, 1 or 2, q is 1, 2 or 3, R ¹⁸ to R ³¹ are each independently a hydrogen atom, a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms optionally 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 combine with each other to form a monocyclic or polycyclic ring, and when q=2 or 3, R ²⁸ and R ²⁸ , R ²⁸ and R ²⁹ , R ²⁹ and R ³⁰ , R ³⁰ and R ³¹ , R ³¹ and R ³¹ may be bonded to each other to form a monocyclic or polycyclic ring, the monocyclic or polycyclic ring may have a double bond, or the monocyclic The ring or said polycycle may be an aromatic ring.)

(In formula (C-3) above, q is 1, 2 or 3, and R ³² to R ³⁹ are each independently substituted with a hydrogen atom, a halogen atom excluding a fluorine atom, or a halogen atom excluding a fluorine atom. a hydrocarbon group having 1 to 20 carbon atoms which may be substituted, and when q=1, R ³⁶ and R ³⁷ , R ³⁷ and R ³⁸ , R ³⁸ and R ³⁹ are bonded to each other to form a monocyclic or polycyclic 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 are} bonded to each other It may form a monocyclic ring or a polycyclic ring, the monocyclic ring or the polycyclic ring may have a double bond, and the monocyclic ring or the polycyclic ring may be an aromatic ring. ) In the molded article according to any one of claims 1 to 3 ,
A molded article, wherein the cyclic olefin copolymer composition (Q) has a glass transition temperature (Tg) of 0° C. or higher and 180° C. or lower as measured by a differential scanning calorimeter (DSC). In the molded article according to any one of claims 1 to 4 ,
A molded product, wherein the intrinsic viscosity [η] of the cyclic olefin copolymer composition (Q) measured in decalin at 135°C is 0.05 dl/g or more and 6.0 dl/g or less. In the molded article according to any one of claims 1 to 5 ,
A molded article in which the cyclic olefin having an aromatic ring contains at least one selected from benzonorbornadiene and indenenorbornene. A medical container comprising the molded article according to any one of claims 1 to 6 . In the medical container according to claim 7 ,
A medical container that is a syringe or a drug storage container.