JP7133997B2 - Medical container and cyclic olefin resin composition for medical container - Google Patents

Description

The present invention relates to medical containers and cyclic olefin resin compositions for 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 the studies of the present inventors, it has become clear that in medical containers using conventional cyclic olefin resins, discoloration may occur 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 medical container that is less discolored by electron beam or gamma ray irradiation and has excellent transparency.

The present inventors have diligently studied to solve the above problems. As a result, the inventors have found that the above problems can be solved by blending an oligomer having an aromatic cyclic structure with a specific molecular weight and solubility parameter in a specific ratio to a cyclic olefin resin. And the present invention shown below was completed.

That is, according to the present invention, the following medical containers and cyclic olefin resin compositions for medical containers are provided.

（上記式［Ｉ］中、ｎは０または１であり、ｍは０または正の整数であり、ｑは０または１であり、Ｒ^１～Ｒ^１８ならびにＲ^ａおよびＲ^ｂは、それぞれ独立に、水素原子、ハロゲン原子またはハロゲンで置換されていてもよい炭化水素基であり、Ｒ^１５～Ｒ^１８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、かつ、該単環または多環は二重結合を有していてもよく、またＲ^１５とＲ^１６とで、またはＲ^１７とＲ^１８とで、アルキリデン基を形成していてもよい。）、

（上記式［ＩＩ］中、ｐおよびｑは０または正の整数であり、ｍおよびｎは０、１または２であり、Ｒ^１～Ｒ^１９はそれぞれ独立に水素原子、ハロゲン原子、ハロゲン原子で置換されていてもよい炭化水素基またはアルコキシ基であり、Ｒ^９およびＲ^１０が結合している炭素原子と、Ｒ^１３が結合している炭素原子またはＲ^１１が結合している炭素原子とは直接あるいは炭素数１～３のアルキレン基を介して結合していてもよく、またｎ＝ｍ＝０のときＲ^１５とＲ^１２またはＲ^１５とＲ^１９とは互いに結合して単環または多環の芳香族環を形成していてもよい。）、
［Ａ－２］上記式［Ｉ］または［ＩＩ］で示される環状オレフィンの開環重合体または共重合体、
［Ａ－３］上記開環重合体または共重合体［Ａ－２］の水素化物、
［Ａ－４］上記［Ａ－１］、［Ａ－２］または［Ａ－３］のグラフト変性物。
［３］
上記［１］または［２］に記載の医療用容器において、
上記環状オレフィン系樹脂（Ａ）中の環状オレフィンが、ビシクロ［２．２．１］－２－ヘプテンおよびテトラシクロ［４．４．０．１^２，５．１^７，１０］－３－ドデセンから選ばれる少なくとも一種の化合物に由来する繰り返し単位である医療用容器。
［４］
上記［１］乃至［３］のいずれか一つに記載の医療用容器において、
上記芳香族環状構造を有するオリゴマー（Ｂ）がスチレン系化合物およびインデン系化合物から選ばれる少なくとも１種のモノマー由来の繰り返し単位を有する医療用容器。
［５］
上記［１］乃至［４］のいずれか一つ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。
［６］
医療用容器を形成するための環状オレフィン系樹脂組成物であって、
環状オレフィン系樹脂（Ａ）と、芳香族環状構造を有するオリゴマー（Ｂ）と、を含み、
上記芳香族環状構造を有するオリゴマー（Ｂ）の重量平均分子量（Ｍｗ）が５００以上５０００以下であり、
上記芳香族環状構造を有するオリゴマー（Ｂ）の溶解度パラメータが１８．０ＭＰａ^１／２以上２１．０ＭＰａ^１／２以下であり、
上記環状オレフィン系樹脂組成物に含まれる上記環状オレフィン系樹脂（Ａ）および上記芳香族環状構造を有するオリゴマー（Ｂ）の合計を１００質量部としたとき、上記環状オレフィン系樹脂（Ａ）の含有量が７０質量部以上９９質量部以下であり、上記芳香族環状構造を有するオリゴマー（Ｂ）の含有量が１質量部以上３０質量部以下である医療用容器用環状オレフィン系樹脂組成物。
［７］
上記［６］に記載の医療用容器用環状オレフィン系樹脂組成物において、
上記環状オレフィン系樹脂（Ａ）が、
下記の［Ａ－１］、［Ａ－２］、［Ａ－３］および［Ａ－４］から選択される少なくとも一種を含む医療用容器用環状オレフィン系樹脂組成物。
［Ａ－１］炭素原子数が２～２０のα－オレフィンと下記式［Ｉ］または［ＩＩ］で示される環状オレフィンとのランダム共重合体；

（上記式［Ｉ］中、ｎは０または１であり、ｍは０または正の整数であり、ｑは０または１であり、Ｒ^１～Ｒ^１８ならびにＲ^ａおよびＲ^ｂは、それぞれ独立に、水素原子、ハロゲン原子またはハロゲンで置換されていてもよい炭化水素基であり、Ｒ^１５～Ｒ^１８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、かつ、該単環または多環は二重結合を有していてもよく、またＲ^１５とＲ^１６とで、またはＲ^１７とＲ^１８とで、アルキリデン基を形成していてもよい。）、

（上記式［ＩＩ］中、ｐおよびｑは０または正の整数であり、ｍおよびｎは０、１または２であり、Ｒ^１～Ｒ^１９はそれぞれ独立に水素原子、ハロゲン原子、ハロゲン原子で置換されていてもよい炭化水素基またはアルコキシ基であり、Ｒ^９およびＲ^１０が結合している炭素原子と、Ｒ^１３が結合している炭素原子またはＲ^１１が結合している炭素原子とは直接あるいは炭素数１～３のアルキレン基を介して結合していてもよく、またｎ＝ｍ＝０のときＲ^１５とＲ^１２またはＲ^１５とＲ^１９とは互いに結合して単環または多環の芳香族環を形成していてもよい。）、
［Ａ－２］上記式［Ｉ］または［ＩＩ］で示される環状オレフィンの開環重合体または共重合体、
［Ａ－３］上記開環重合体または共重合体［Ａ－２］の水素化物、
［Ａ－４］上記［Ａ－１］、［Ａ－２］または［Ａ－３］のグラフト変性物。
［８］
上記［６］または［７］に記載の医療用容器用環状オレフィン系樹脂組成物において、
上記環状オレフィン系樹脂（Ａ）中の環状オレフィンが、ビシクロ［２．２．１］－２－ヘプテンおよびテトラシクロ［４．４．０．１^２，５．１^７，１０］－３－ドデセンから選ばれる少なくとも一種の化合物に由来する繰り返し単位である医療用容器用環状オレフィン系樹脂組成物。
［９］
上記［６］乃至［８］のいずれか一つに記載の医療用容器用環状オレフィン系樹脂組成物において、
上記芳香族環状構造を有するオリゴマー（Ｂ）がスチレン系化合物およびインデン系化合物から選ばれる少なくとも１種のモノマー由来の繰り返し単位を有する医療用容器用環状オレフィン系樹脂組成物。
［１０］
上記［６］乃至［９］のいずれか一つに記載の医療用容器用環状オレフィン系樹脂組成物において、
上記医療用容器がシリンジまたは薬液保存容器である医療用容器用環状オレフィン系樹脂組成物。 [1]
A medical container containing a cyclic olefin resin composition containing a cyclic olefin resin (A) and an oligomer (B) having an aromatic cyclic structure,
The weight average molecular weight (Mw) of the oligomer (B) having an aromatic cyclic structure is 500 or more and 5000 or less,
The solubility parameter of the oligomer (B) having an aromatic cyclic structure is 18.0 MPa ^1/2 or more and 21.0 MPa ^1/2 or less,
When the total of the cyclic olefin resin (A) and the oligomer (B) having an aromatic cyclic structure contained in the cyclic olefin resin composition is 100 parts by mass, the content of the cyclic olefin resin (A) A medical container in which the amount is 70 parts by mass or more and 99 parts by mass or less, and the content of the oligomer (B) having the aromatic ring structure is 1 part by mass or more and 30 parts by mass or less.
[2]
In the medical container according to [1] above,
The cyclic olefin resin (A) is
A medical container containing at least one selected from the following [A-1], [A-2], [A-3] and [A-4].
[A-1] A random copolymer of an α-olefin having 2 to 20 carbon atoms and a cyclic olefin represented by the following formula [I] or [II];

(In the above formula [I], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, R ¹ to R ¹⁸ and R ^a and R ^b are each independently , a hydrogen atom, a halogen atom, or a hydrocarbon group optionally substituted with halogen, and R ¹⁵ to R ¹⁸ may be bonded together to form a monocyclic or polycyclic ring, and the monocyclic or The polycyclic ring may have a double bond, and R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group.),

(In formula [II] above, p and q are 0 or positive integers, m and n are 0, 1 or 2, and R ¹ to R ¹⁹ are each independently a hydrogen atom, a halogen atom, or a halogen atom. An optionally substituted hydrocarbon group or alkoxy group, the carbon atom to which R ⁹ and R ¹⁰ are bonded and the carbon atom to which R ¹³ is bonded or the carbon atom to which R ¹¹ is bonded They may be bonded directly or through an alkylene group having 1 to 3 carbon atoms, and when n=m=0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ are bonded to each other to form a monocyclic or polycyclic may form an aromatic ring of.),
[A-2] A ring-opening polymer or copolymer of a cyclic olefin represented by the above formula [I] or [II],
[A-3] hydride of the above ring-opening polymer or copolymer [A-2],
[A-4] A graft modified product of [A-1], [A-2] or [A-3] above.
[3]
In the medical container according to [1] or [2] above,
The cyclic olefins in the cyclic olefin resin (A) are bicyclo[2.2.1]-2-heptene and tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene, a repeating unit derived from at least one compound selected from medical containers.
[4]
In the medical container according to any one of [1] to [3] above,
A medical container, wherein the oligomer (B) having an aromatic ring structure has repeating units derived from at least one monomer selected from styrene compounds and indene compounds.
[5]
In the medical container according to any one of [1] to [4] above,
A medical container, which is a syringe or a drug storage container.
[6]
A cyclic olefin resin composition for forming a medical container,
including a cyclic olefin resin (A) and an oligomer (B) having an aromatic cyclic structure,
The weight average molecular weight (Mw) of the oligomer (B) having an aromatic cyclic structure is 500 or more and 5000 or less,
The solubility parameter of the oligomer (B) having an aromatic cyclic structure is 18.0 MPa ^1/2 or more and 21.0 MPa ^1/2 or less,
When the total of the cyclic olefin resin (A) and the oligomer (B) having an aromatic cyclic structure contained in the cyclic olefin resin composition is 100 parts by mass, the content of the cyclic olefin resin (A) A cyclic olefin resin composition for medical containers, wherein the amount is 70 parts by mass or more and 99 parts by mass or less, and the content of the oligomer (B) having an aromatic cyclic structure is 1 part by mass or more and 30 parts by mass or less.
[7]
In the cyclic olefin resin composition for medical containers according to [6] above,
The cyclic olefin resin (A) is
A cyclic olefin resin composition for medical containers, comprising at least one selected from the following [A-1], [A-2], [A-3] and [A-4].
[A-1] A random copolymer of an α-olefin having 2 to 20 carbon atoms and a cyclic olefin represented by the following formula [I] or [II];

(In the above formula [I], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, R ¹ to R ¹⁸ and R ^a and R ^b are each independently , a hydrogen atom, a halogen atom, or a hydrocarbon group optionally substituted with halogen, and R ¹⁵ to R ¹⁸ may be bonded together to form a monocyclic or polycyclic ring, and the monocyclic or The polycyclic ring may have a double bond, and R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group.),

(In formula [II] above, p and q are 0 or positive integers, m and n are 0, 1 or 2, and R ¹ to R ¹⁹ are each independently a hydrogen atom, a halogen atom, or a halogen atom. An optionally substituted hydrocarbon group or alkoxy group, the carbon atom to which R ⁹ and R ¹⁰ are bonded and the carbon atom to which R ¹³ is bonded or the carbon atom to which R ¹¹ is bonded They may be bonded directly or through an alkylene group having 1 to 3 carbon atoms, and when n=m=0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ are bonded to each other to form a monocyclic or polycyclic may form an aromatic ring of.),
[A-2] A ring-opening polymer or copolymer of a cyclic olefin represented by the above formula [I] or [II],
[A-3] hydride of the above ring-opening polymer or copolymer [A-2],
[A-4] A graft modified product of [A-1], [A-2] or [A-3] above.
[8]
In the cyclic olefin resin composition for medical containers according to [6] or [7] above,
The cyclic olefins in the cyclic olefin resin (A) are bicyclo[2.2.1]-2-heptene and tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene.
[9]
In the cyclic olefin resin composition for medical containers according to any one of [6] to [8] above,
A cyclic olefin resin composition for medical containers, wherein the oligomer (B) having an aromatic cyclic structure has a repeating unit derived from at least one monomer selected from styrene compounds and indene compounds.
[10]
In the cyclic olefin resin composition for medical containers according to any one of [6] to [9] above,
A cyclic olefin resin composition for a medical container, wherein the medical container is a syringe or a drug storage container.

According to the present invention, it is possible to provide a medical container that is less discolored by electron beam or gamma ray irradiation and has excellent transparency.

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 resin composition]
First, a cyclic olefin-based resin composition according to an embodiment of the present invention will be described.
The cyclic olefin-based resin composition according to this embodiment includes a cyclic olefin-based resin (A) and an oligomer (B) having an aromatic cyclic structure. The weight average molecular weight (Mw) of the oligomer (B) having an aromatic cyclic structure is 500 or more and 5000 or less, and the solubility parameter of the oligomer (B) having an aromatic cyclic structure is 18.0 MPa ^1/2 or more21. It is 0 MPa ^1/2 or less. Furthermore, when the total of the cyclic olefin resin (A) and the oligomer (B) having an aromatic cyclic structure contained in the cyclic olefin resin composition is 100 parts by mass, the content of the cyclic olefin resin (A) is It is 70 parts by mass or more and 99 parts by mass or less, and the content of the oligomer (B) having an aromatic ring structure is 1 part by mass or more and 30 parts by mass or less.

By highly controlling the content of the oligomer (B) having an aromatic cyclic structure, the weight average molecular weight (Mw) and the solubility parameter within the above ranges, the cyclic olefin resin (A) and the oligomer having an aromatic cyclic structure The compatibility with (B) is improved, and as a result, a medical container that is less discolored by electron beam or gamma ray irradiation and has excellent transparency can be obtained.

The content of the cyclic olefin resin (A) is 70 parts by mass or more and 99 parts by mass or less. 75 parts by mass or more and 95 parts by mass or less is preferable, and 80 parts by mass or more and 90 parts by mass or less is more preferable.
In addition, although the content of the oligomer (B) having an aromatic cyclic structure is 1 part by mass or more and 30 parts by mass or less, the transparency of the obtained medical container and the performance balance of gamma ray resistance or electron ray resistance performance can be improved. From the viewpoint of improvement, it is preferably 5 parts by mass or more and 25 parts by mass or less, more preferably 10 parts by mass or more and 20 parts by mass or less.

In addition, the total content of the cyclic olefin resin (A) and the oligomer (B) having an aromatic cyclic structure in the cyclic olefin resin composition according to the present embodiment should be From the viewpoint of further improving the performance balance of gamma ray or electron ray resistance performance, when the entire cyclic olefin resin composition is 100% by mass, it is preferably 50% by mass or more and 100% by mass or less, more preferably 70% by mass. % 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 resin composition according to the present embodiment contains the cyclic olefin-based resin (A) and the oligomer (B) having an aromatic cyclic structure in the above ratio. It is possible to further improve gamma ray resistance or electron ray resistance performance while satisfying the good transparency required for .

Each component will be specifically described below.

(Cyclic olefin resin (A))
The cyclic olefin-based resin (A) according to the present embodiment is a resin having a repeating unit derived from a cyclic olefin as an essential structural unit.
The cyclic olefin compound that constitutes the cyclic olefin-based resin (A) according to the present embodiment is not particularly limited. .

（上記式［Ｉ］中、ｎは０または１であり、ｍは０または正の整数であり、ｑは０または１であり、Ｒ^１～Ｒ^１８ならびにＲ^ａおよびＲ^ｂは、それぞれ独立に、水素原子、ハロゲン原子またはハロゲンで置換されていてもよい炭化水素基であり、Ｒ^１５～Ｒ^１８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、かつ、該単環または多環は二重結合を有していてもよく、またＲ^１５とＲ^１６とで、またはＲ^１７とＲ^１８とで、アルキリデン基を形成していてもよい。） The cyclic olefin resin (A) according to this embodiment contains at least one selected from the following [A-1], [A-2], [A-3] and [A-4].
[A-1] A random copolymer of an α-olefin having 2 to 20 carbon atoms and a cyclic olefin represented by the following formula [I] or [II];

(In the above formula [I], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, R ¹ to R ¹⁸ and R ^a and R ^b are each independently , a hydrogen atom, a halogen atom, or a hydrocarbon group optionally substituted with halogen, and R ¹⁵ to R ¹⁸ may be bonded together to form a monocyclic or polycyclic ring, and the monocyclic or The polycyclic ring may have a double bond, and R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group.)

（上記式［ＩＩ］中、ｐおよびｑは０または正の整数であり、ｍおよびｎは０、１または２であり、Ｒ^１～Ｒ^１９はそれぞれ独立に水素原子、ハロゲン原子、ハロゲン原子で置換されていてもよい炭化水素基またはアルコキシ基であり、Ｒ^９およびＲ^１０が結合している炭素原子と、Ｒ^１３が結合している炭素原子またはＲ^１１が結合している炭素原子とは直接あるいは炭素数１～３のアルキレン基を介して結合していてもよく、またｎ＝ｍ＝０のときＲ^１５とＲ^１２またはＲ^１５とＲ^１９とは互いに結合して単環または多環の芳香族環を形成していてもよい。）

(In formula [II] above, p and q are 0 or positive integers, m and n are 0, 1 or 2, and R ¹ to R ¹⁹ are each independently a hydrogen atom, a halogen atom, or a halogen atom. An optionally substituted hydrocarbon group or alkoxy group, the carbon atom to which R ⁹ and R ¹⁰ are bonded and the carbon atom to which R ¹³ is bonded or the carbon atom to which R ¹¹ is bonded They may be bonded directly or through an alkylene group having 1 to 3 carbon atoms, and when n=m=0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ are bonded to each other to form a monocyclic or polycyclic may form an aromatic ring of

[A-2] A ring-opening polymer or copolymer of a cyclic olefin represented by the above formula [I] or [II] [A-3] A hydride of the above ring-opening polymer or copolymer [A-2] [A-4] Graft modified product of [A-1], [A-2] or [A-3] above

α-Olefins having 2 to 20 carbon atoms may be linear or branched. Specifically, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc. Linear α-olefins having 2 to 20 carbon atoms; 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl -1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, etc., having 4 to 20 carbon atoms and branched α-olefins.
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.

Cyclic olefins represented by formulas [I] or [II] forming such cyclic olefin resins [A-1], [A-2], [A-3] and [A-4] are described below. .

上記式［Ｉ］中、ｎは０または１であり、ｍは０または正の整数であり、ｑは０または１である。なお、ｑが１の場合には、Ｒ^ａおよびＲ^ｂは、それぞれ独立に、下記の原子または炭化水素基であり、ｑが０の場合には、それぞれの結合手が結合して５員環を形成する。

In formula [I] above, n is 0 or 1, m is 0 or a positive integer, and q is 0 or 1. When q is 1, R ^a and R ^b are each independently the following atoms or hydrocarbon groups; to form

R ¹ to R ¹⁸ and R ^a and R ^b are each independently a hydrogen atom, a halogen atom or a hydrocarbon group. A halogen atom here is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

The hydrocarbon groups each independently include, for example, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, an aromatic hydrocarbon group, and the like. 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 and the like, and the aromatic hydrocarbon group includes a phenyl group, a naphthyl group, and the like. These hydrocarbon groups may be substituted with halogen atoms.

Furthermore, in the above formula [I], each of R ¹⁵ to R ¹⁸ may be bonded (together with each other) to form a monocyclic or polycyclic ring, and the thus formed monocyclic or polycyclic ring may have a double bond. Specific examples of the monocyclic or polycyclic ring formed here are shown below.

In the above examples, the carbon atoms numbered 1 or 2 indicate the carbon atoms to which R ¹⁵ (R ¹⁶ ) or R ¹⁷ (R ¹⁸ ) is bonded in the above formula [I]. . In addition, R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group. Such an alkylidene group is, for example, an alkylidene group having 2 to 20 carbon atoms, and specific examples of such an alkylidene group include an ethylidene group, a propylidene group and an isopropylidene group.

上記式［ＩＩ］中、ｐおよびｑは０または正の整数であり、ｍおよびｎは０、１または２である。またＲ^１～Ｒ^１９はそれぞれ独立に水素原子、ハロゲン原子、炭化水素基またはアルコキシ基である。

In formula [II] above, p and q are 0 or positive integers, and m and n are 0, 1 or 2. R ¹ to R ¹⁹ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group or an alkoxy group.

A halogen atom has the same meaning as the halogen atom in the above formula [I]. In addition, as the hydrocarbon group, each independently, for example, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, and an aromatic hydrocarbon and the like. 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 and aralkyl groups, specifically phenyl, tolyl, naphthyl, benzyl and phenylethyl groups. Examples of alkoxy groups include methoxy, ethoxy and propoxy groups. These hydrocarbon groups and alkoxy groups may be substituted with fluorine, chlorine, bromine or iodine atoms.

Here, the carbon atom to which R ⁹ and R ¹⁰ are bonded and the carbon atom to which R ¹³ is bonded or the carbon atom to which R ¹¹ is bonded are directly or an alkylene group having 1 to 3 carbon atoms may be connected via That is, when the above two carbon atoms are bonded through an alkylene group, the groups represented by R ⁹ and R ¹³ or the groups represented by R ¹⁰ and R ¹¹ jointly form a methylene group (- CH ₂ —), an ethylene group (—CH ₂ CH ₂ —) or a propylene group (—CH ₂ CH ₂ CH ₂ —). Furthermore, when n=m=0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ may combine with each other to form a monocyclic or polycyclic aromatic ring. Examples of monocyclic or polycyclic aromatic rings in this case include groups in which R ¹⁵ and R ¹² further form an aromatic ring when n=m=0 as shown below.

Here, q has the same meaning as q in the above formula [II].

（上記式中、１～７の数字は炭素の位置番号を示す。）およびこのビシクロ［２．２．１］－２－ヘプテンに炭化水素基が置換した誘導体等が挙げられる。この炭化水素基としては、例えば、５－メチル、５，６－ジメチル、１－メチル、５－エチル、５－ｎ－ブチル、５－イソブチル、７－メチル、５－フェニル、５－メチル－５－フェニル、５－ベンジル、５－トリル、５－（エチルフェニル）、５－（イソプロピルフェニル）、５－（ビフェニル）、５－（β－ナフチル）、５－（α－ナフチル）、５－（アントラセニル）、５，６－ジフェニル等が挙げられる。 Examples of the cyclic olefin represented by the above formula [I] or [II] include:

(In the above formula, the numbers 1 to 7 indicate the positions of carbon atoms.) and derivatives in which this bicyclo[2.2.1]-2-heptene is substituted with a hydrocarbon group. Examples of the hydrocarbon group include 5-methyl, 5,6-dimethyl, 1-methyl, 5-ethyl, 5-n-butyl, 5-isobutyl, 7-methyl, 5-phenyl, 5-methyl-5 -phenyl, 5-benzyl, 5-tolyl, 5-(ethylphenyl), 5-(isopropylphenyl), 5-(biphenyl), 5-(β-naphthyl), 5-(α-naphthyl), 5-( anthracenyl), 5,6-diphenyl and the like.

Further, the cyclic olefin represented by the formula [I] or [II] includes, for example, cyclopentadiene-acenaphthylene adduct, 1,4-methano-1,4,4a,9a-tetrahydrofluorene, 1,4-methano bicyclo[2.2.1]-2-heptene derivatives such as -1,4,4a,5,10,10a-hexahydroanthracene;

Furthermore, the cyclic olefins represented by the formula [I] or [II] include, for example, tricyclo[4.3.0.1 ^2,5 ]-3-decene, 2-methyltricyclo[4.3.0 .1 ^2,5 ]-3-decene, 5-methyltricyclo[4.3.0.1 ^2,5 ]-3-decene, and other tricyclo[4.3.0.1 ^2,5 ]-3- Decene derivatives, tricyclo[4.4.0.1 ^2,5 ]-3-undecene, 10-methyltricyclo[4.4.0.1 ^2,5 ]-3-undecene, etc. 0.1 ^2,5 ]-3-undecene derivative,

(In the above formula, the numbers 1 to 12 indicate the carbon position numbers.) and tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene substituted with a hydrocarbon group. Examples of the hydrocarbon group include 8-methyl, 8-ethyl, 8-propyl, 8-butyl, 8-isobutyl, 8-hexyl, 8-cyclohexyl, 8-stearyl, 5,10-dimethyl, 2,10 -dimethyl, 8,9-dimethyl, 8-ethyl-9-methyl, 11,12-dimethyl, 2,7,9-trimethyl, 2,7-dimethyl-9-ethyl, 9-isobutyl-2,7-dimethyl , 9,11,12-trimethyl, 9-ethyl-11,12-dimethyl, 9-isobutyl-11,12-dimethyl, 5,8,9,10-tetramethyl, 8-ethylidene, 8-ethylidene-9- methyl, 8-ethylidene-9-ethyl, 8-ethylidene-9-isopropyl, 8-ethylidene-9-butyl, 8-n-propylidene, 8-n-propylidene-9-methyl, 8-n-propylidene-9- ethyl, 8-n-propylidene-9-isopropyl, 8-n-propylidene-9-butyl, 8-isopropylidene, 8-isopropylidene-9-methyl, 8-isopropylidene-9-ethyl, 8-isopropylidene- 9-isopropyl, 8-isopropylidene-9-butyl, 8-chloro, 8-bromo, 8-fluoro, 8,9-dichloro, 8-phenyl, 8-methyl-8-phenyl, 8-benzyl, 8-tolyl , 8-(ethylphenyl), 8-(isopropylphenyl), 8,9-diphenyl, 8-(biphenyl), 8-(β-naphthyl), 8-(α-naphthyl), 8-(anthracenyl), 5 , 6-diphenyl and the like.

Further, the cyclic olefin represented by the above formula [I] or [II] includes, for example, an adduct of (cyclopentadiene-acenaphthylene adduct) and cyclopentadiene, pentacyclo[6.5.1.1 ^3,6 . 0 ^{2, 7} . 0 ^9,13 ]-4-pentadecene and its derivatives, pentacyclo[7.4.0.1 ^2,5 . ^{19, 12} . 0 ^8,13 ]-3-pentadecene and its derivatives, pentacyclo[6.5.1.1 ^3,6 . 0 ^{2, 7} . 0 ^9,13 ]-4,10-pentadecadiene and other pentacyclopentadecadiene compounds, pentacyclo[8.4.0.1 ^2,5 . ^{19, 12} . 0 ^8,13 ]-3-hexadecene and its derivatives, pentacyclo[6.6.1.1 ^3,6 . 0 ^{2, 7} . 0 ^9,14 ]-4-hexadecene and its derivatives, hexacyclo[6.6.1.1 ^3,6 . 1 ^{10, 13} . 0 ^{2, 7} . 0 ^9,14 ]-4-heptadecene and its derivatives, heptacyclo[8.7.0.1 ^2,9 . 1 ^{4, 7} . 1 ^{11, 17} . 0 ^{3, 8} . 0 ^12,16 ]-5-eicosene and its derivatives, heptacyclo[8.8.0.1 ^2,9 . 1 ^{4, 7} . 1 ^{11, 18} . 0 ^{3, 8} . 0 ^12,17 ]-5-heneicosene and its derivatives, octacyclo[8.8.0.1 ^2,9 . 1 ^{4, 7} . 1 ^{11, 18} . 1 ^{13, 16} . 0 ^{3, 8} . 0 ^12,17 ]-5-docosene and its derivatives, nonacyclo[10.9.1.1 ^4,7 . 1 ^{13, 20} . 1 ^{15, 18} . 0 ^{2, 10} . 0 ^{3, 8} . 0 ^{12, 21} . 0 ^14,19 ]-5-pentacosene and its derivatives, nonacyclo[10.10.1.1 ^5,8 . 1 14 ^{, 21} . 1 ^{16, 19} . 0 ^{2, 11} . 0 ^{4, 9} . 0 ^{13, 22} . 0 ^15,20 ]-6-hexacosene and its derivatives.
Cyclic olefins represented by the above formula [I] or [II] include bicyclo[2.2.1]-2-heptene and tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene is preferred.
That is, the cyclic olefins in the cyclic olefin resin (A) are bicyclo[2.2.1]-2-heptene and tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene is preferably a repeating unit derived from at least one compound selected from.

Specific examples of the cyclic olefins represented by the above formula [I] or [II] are shown above. ] to [0054]. The cyclic olefin-based resin (A) according to the present embodiment may contain two or more units derived from the cyclic olefin.

The cyclic olefin represented by the above formula [I] or [II] can be produced, for example, by subjecting cyclopentadiene and olefins having a corresponding structure to Diels-Alder reaction.

The cyclic olefin-based resin (A) according to the present embodiment is prepared by using the cyclic olefin represented by the above formula [I] or [II], for example, in 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 and international publications It can be produced by appropriately selecting conditions according to the method described in publications such as 2008/068897.

([A-1] random copolymer of α-olefin having 2 to 20 carbon atoms and cyclic olefin)
[A-1] A random copolymer of an α-olefin having 2 to 20 carbon atoms and a cyclic olefin represented by the above formula [I] or [II] (hereinafter referred to as α- Also referred to as an olefin/cyclic olefin random copolymer [A-1].) is derived from an α-olefin having 2 to 20 carbon atoms when the total structural units constituting the copolymer are taken as 100 mol%. The content of units derived from a cyclic olefin is, for example, 5 mol% or more and 95 mol% or less, preferably 20 mol% or more and 80 mol% or less, and the content of units derived from a cyclic olefin is, for example, 5 mol% or more and 95 mol% or less. , preferably 20 mol % or more and 80 mol % or less.
The composition of α-olefins having 2 to 20 carbon atoms and the composition of cyclic olefins can be measured by ¹³ C-NMR.

In the α-olefin/cyclic olefin random copolymer [A-1] having 2 to 20 carbon atoms, units derived from an α-olefin having 2 to 20 carbon atoms and units derived from a cyclic olefin are random. are preferably aligned and bonded to each other and have a substantially linear structure. The fact that this copolymer is substantially linear and does not substantially have a gel-like crosslinked structure means that when this copolymer is dissolved in an organic solvent, the solution contains insoluble matter. It can be confirmed by not For example, when measuring the intrinsic viscosity [η], it can be confirmed by completely dissolving this copolymer in decalin at 135°C.

In the α-olefin/cyclic olefin random copolymer [A-1] having 2 to 20 carbon atoms, at least part of the cyclic olefin represented by the above formula [I] or [II] is represented by the following formula [III] or It is thought to constitute a repeating unit represented by [IV].

上記式［ＩＩＩ］において、ｎ、ｍ、ｑ、Ｒ^１～Ｒ^１８、Ｒ^ａおよびＲ^ｂは上記式［Ｉ］と同じ意味である。

In formula [III] above, n, m, q, R ¹ to R ¹⁸ , R ^a and R ^b have the same meanings as in formula [I] above.

上記式［IＶ］において、ｎ、ｍ、ｐ、ｑおよびＲ^１～Ｒ^１９は上記式［ＩＩ］と同じ意味である。

In formula [IV] above, n, m, p, q and R ¹ to R ¹⁹ have the same meanings as in formula [II] above.

In addition, the α-olefin/cyclic olefin random copolymer [A-1] having 2 to 20 carbon atoms may optionally be mixed with other copolymerizable monomers as long as the object of the present invention is not impaired. It may contain derived units, and specifically, units derived from other monomers may be contained in an amount of usually 20 mol % or less, preferably 10 mol % or less.

Examples of such other monomers include olefins other than α-olefins or cyclic olefins having 2 to 20 carbon atoms as described above, specifically cyclobutene, cyclopentene, cyclohexene, -cycloolefins such as dimethylcyclopentene, 3-methylcyclohexene, 2-(2-methylbutyl)-1-cyclohexene, cyclooctene, and 3a,5,6,7a-tetrahydro-4,7-methano-1H-indene, 1 ,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene, dicyclopentadiene and non-conjugated dienes such as 5-vinyl-2-norbornene. be able to.
The α-olefin/cyclic olefin random copolymer [A-1] having 2 to 20 carbon atoms may contain two or more units derived from the above other monomers.

The α-olefin/cyclic olefin random copolymer [A-1] having 2 to 20 carbon atoms is an α-olefin having 2 to 20 carbon atoms and a cyclic compound represented by the above formula [I] or [II] It can be produced by the production method disclosed in the above publication using an olefin. Among these, the copolymerization reaction is carried out in a hydrocarbon solvent, and a catalyst formed from a vanadium compound and an organoaluminum compound soluble in the hydrocarbon solvent is used as a catalyst to obtain an α-olefin having 2 to 20 carbon atoms. - It is preferable to produce a cyclic olefin random copolymer [A-1].

Also, an α-olefin/cyclic olefin random copolymer [A-1] having 2 to 20 carbon atoms can be produced using a solid Group IVA metallocene catalyst. The solid Group IVA metallocene catalyst comprises a transition metal compound (metallocene compound) containing a ligand having at least one cyclopentadienyl skeleton, an organoaluminum oxy compound, and optionally an organoaluminum compound. It is formed. Here, the group IVA transition metal is zirconium, titanium or hafnium. Examples of the ligand containing a cyclopentadienyl skeleton include a cyclopentadienyl group optionally substituted with an alkyl group, an indenyl group, a tetrahydroindenyl group, a fluorenyl group, and the like. These groups may be bonded via another group such as an alkylene group. Ligands other than ligands containing a cyclopentadienyl skeleton are, for example, alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and the like.

As the organoaluminum oxy compound and the organoaluminum compound, for example, those used in the production of olefinic polymers can be used. Such solid Group IVA metallocene catalysts are described in detail, for example, in JP-A-61-221206, JP-A-64-106 and JP-A-2-173112.

Alternatively, an α-olefin/cyclic olefin random copolymer [A-1] having 2 to 20 carbon atoms may be produced using a phenoxyimine-based catalyst (FI catalyst) or a pyrrole imine-based catalyst (PI catalyst). can. These catalysts, as described in JP-A-2001-72706, JP-A-2002-332312, JP-A-2003-313247, JP-A-2004-107486, JP-A-2004-107563, (a) phenoxyimine or a transition metal compound having pyrrole imine as a ligand, reacting with (b) (b-1) organometallic compound, (b-2) organoaluminum oxy compound, and (b-3) transition metal compound (a) and at least one compound selected from compounds that form an ion pair with each other. As the transition metal contained in the transition metal compound, transition metals of Groups 3 to 11 of the periodic table can be used.

([A-2] Ring-opening polymer or copolymer of cyclic olefin)
[A-2] A ring-opening polymer or copolymer of a cyclic olefin represented by the above formula [I] or [II] (hereinafter also referred to as a ring-opening (co)polymer of a cyclic olefin [A-2].) At least part of the units derived from the cyclic olefin represented by the above formula [I] or [II] are represented by the following formula [V] or [VI].

上記式［Ｖ］において、ｎ、ｍ、ｑ、Ｒ^１～Ｒ^１８、Ｒ^ａおよびＲ^ｂは上記式［Ｉ］と同じ意味である。

In formula [V] above, n, m, q, R ¹ to R ¹⁸ , R ^a and R ^b have the same meanings as in formula [I] above.

上記式［ＶI］において、ｎ、ｍ、ｐ、ｑおよびＲ^１～Ｒ^１９は上記式［ＩＩ］と同じ意味である。

In formula [VI] above, n, m, p, q and R ¹ to R ¹⁹ have the same meanings as in formula [II] above.

The ring-opening (co)polymer of cyclic olefin [A-2] can be produced by the production method disclosed in the above publication. It can be produced by polymerizing or copolymerizing in the presence.

Examples of such ring-opening polymerization catalysts include catalysts composed of metal halides, nitrates or acetylacetone compounds selected from ruthenium, rhodium, palladium, osmium, indium and platinum, and reducing agents, or titanium, palladium and zirconium. A catalyst comprising a metal halide or an acetylacetone compound selected from molybdenum and the like, and an organoaluminum compound can be used.
The ring-opened (co)polymer of cyclic olefin [A-2] can also be obtained, for example, by the method described in JP-A-7-324108.

([A-3] Hydride of Ring-Opening (Co)polymer of Cyclic Olefin [A-2])
A hydride of a ring-opened (co)polymer of a cyclic olefin [A-2] (hereinafter also referred to as a hydride of a ring-opened (co)polymer [A-3]) is a ring-opened (co)polymer of a cyclic olefin. Polymer [A-2] can be obtained by a conventionally known method, for example, hydrogenation in the presence of a hydrogenation catalyst disclosed in JP-A-7-324108.

In the ring-opening (co)polymer hydride [A-3], at least some of the units derived from the above formula [I] or [II] are considered to be represented by the following formula [VII] or [VIII]. be done.

上記式［ＶII］において、ｎ、ｍ、ｑ、Ｒ^１～Ｒ^１８、Ｒ^ａおよびＲ^ｂは上記式［Ｉ］と同じ意味である。

In the above formula [VII], n, m, q, R ¹ to R ¹⁸ , R ^a and R ^b have the same meanings as in the above formula [I].

上記式［ＶIII］において、ｎ、ｍ、ｐ、ｑおよびＲ^１～Ｒ^１９は上記式［ＩＩ］と同じ意味である。

In formula [VIII] above, n, m, p, q and R ¹ to R ¹⁹ have the same meanings as in formula [II] above.

As the hydrogenated ring-opening (co)polymer [A-3], for example, Zeonex 1020R, 690R, 790R manufactured by Nippon Zeon Co., Ltd. can be used.

([A-4] graft modified product)
[A-4] The graft-modified product of [A-1], [A-2] or [A-3] (also referred to as graft-modified product [A-4]) has 2 to 20 carbon atoms. Graft modification of α-olefin/cyclic olefin random copolymer [A-1], ring-opening (co)polymer of cyclic olefin [A-2] or hydride of ring-opening (co)polymer [A-3] It is a thing.

As a modifier for obtaining the graft-modified product [A-4], for example, unsaturated carboxylic acids are used, and specific examples include (meth)acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, Unsaturated carboxylic acids such as citraconic acid, crotonic acid, isocrotonic acid, endocis-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid (nadic acid ^TM ); derivatives of the above unsaturated carboxylic acids , for example, unsaturated carboxylic acid anhydrides, unsaturated carboxylic acid halides, unsaturated carboxylic acid amides, unsaturated carboxylic acid imides, ester compounds of unsaturated carboxylic acids, and the like. Derivatives of unsaturated carboxylic acids more specifically include maleic anhydride, citraconic anhydride, malenyl chloride, maleimide, monomethyl maleate, dimethyl maleate, glycidyl maleate and the like.

Among these modifiers, α,β-unsaturated dicarboxylic acids and α,β-unsaturated dicarboxylic acid anhydrides such as maleic acid, nadic acid and anhydrides of these acids are preferably used. These modifiers may be used alone or in combination of two or more.
The modification ratio of the graft-modified product [A-4] is generally desirably 10 mol % or less.

α-olefin/cyclic olefin random copolymer having 2 to 20 carbon atoms [A-1], ring-opening (co)polymer of cyclic olefin [A-2] or hydride of ring-opening (co)polymer In order to obtain the graft-modified product [A-4] using [A-3] and a modifier, conventionally known polymer modification methods can be widely applied. For example, a cyclic olefin random copolymer [A-1] in a molten state, a ring-opening (co)polymer of a cyclic olefin [A-2], or a hydride of a ring-opening (co)polymer [A-3] A method of graft polymerization (reaction) by adding a modifier; Alternatively, a cyclic olefin random copolymer [A-1], a ring-opening (co)polymer of a cyclic olefin [A-2], or a ring-opening (co)polymer A graft-modified product [A-4] can be obtained by a method such as adding a modifier to a solution of the combined hydride [A-3] and causing a graft reaction. Such grafting reactions are carried out at temperatures of, for example, 60-350.degree. Also, the graft reaction can be carried out in the presence of a radical initiator such as an organic peroxide and an azo compound.

In addition, the graft modified product [A-4] having the modification rate as described above is an unmodified α-olefin/cyclic olefin random copolymer [A-1] having 2 to 20 carbon atoms, a modified cyclic olefin It can be directly obtained by a graft reaction between the ring (co)polymer [A-2] or the hydrogenated ring-opening (co)polymer [A-3] and a modifier. In addition, an α-olefin/cyclic olefin random copolymer [A-1] having 2 to 20 carbon atoms, a ring-opening (co)polymer of a cyclic olefin [A-2] or a ring-opening (co)polymer A modified product with a high modification rate is prepared in advance by a graft reaction between the hydride [A-3] and a modifier, and then this modified product is mixed with an unmodified α-olefin having 2 to 20 carbon atoms and a cyclic olefin randomly. Dilute with the polymer [A-1], the ring-opening (co)polymer of cyclic olefin [A-2], or the hydride of the ring-opening (co)polymer [A-3] so as to obtain the desired modification rate. can also be obtained by doing

In the present embodiment, as the cyclic olefin resin (A), the α-olefin/cyclic olefin random copolymer [A-1] having 2 to 20 carbon atoms as described above, a ring-opening (co) cyclic olefin Any of the polymer [A-2], the hydrogenated ring-opening (co)polymer [A-3] and the graft-modified product [A-4] may be used alone, or two or more of the same type may be used. may be used, or they may be used in combination. Among these, the α-olefin/cyclic olefin random copolymer [A-1] having 2 to 20 carbon atoms is preferable as the cyclic olefin resin (A).

The molecular weight of the cyclic olefin resin (A) according to the present embodiment is not particularly limited, but the intrinsic viscosity [η] measured in decalin at 135° C. is preferably 0.03 dl/g to 10 dl/g, more preferably is a molecular weight exhibiting 0.05 dl/g to 5 dl/g, more preferably 0.10 dl/g to 2 dl/g.
When the molecular weight is at least the above lower limit, the mechanical strength of the medical container can be improved. Moreover, moldability can be improved as molecular weight is below the said upper limit.

(Oligomer (B) having an aromatic cyclic structure)
Although the weight average molecular weight (Mw) of the oligomer (B) having an aromatic cyclic structure is 500 or more and 5000 or less, it further improves the transparency of the obtained medical container and the performance balance of gamma ray resistance or electron ray resistance performance. From the viewpoint, it is preferably 800 or more and 4000 or less, more preferably 1000 or more and 3500 or less, and particularly preferably 1500 or more and 3000 or less.
Here, the weight average molecular weight (Mw) of the oligomer (B) having an aromatic ring structure is a polystyrene-equivalent value measured by gel permeation chromatography (GPC).

The solubility parameter of the oligomer (B) having an aromatic cyclic structure is 18.0 MPa ^1/2 or more and 21.0 MPa ^1/2 or less. From the viewpoint of further improving the performance balance, 18.5 MPa ^1/2 or more and 20.5 MPa ^1/2 or less is preferable, and 19.0 MPa ^1/2 or more and 20.0 MPa ^1/2 or less is more preferable.
In this embodiment, the solubility parameter is the Fedors parameter calculated using the Synthia module of Materials Studio.

The oligomer (B) having an aromatic cyclic structure according to the present embodiment preferably has repeating units derived from at least one monomer selected from styrene-based compounds and indene-based compounds.
Examples of such styrenic compounds include styrene, α-methylstyrene, α-ethylstyrene, α-propylstyrene, α-isopropylstyrene, α-t-butylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-diisopropylstyrene, 2,4-dimethylstyrene, 4-t-butylstyrene, 5-t-butyl-2-methylstyrene, 4-isopropenyltoluene, monochlorostyrene, dichlorostyrene, mono fluorostyrene, 4-phenylstyrene, and the like.
Examples of such indene compounds include indene, methylindene, ethylindene, propylindene, and butylindene.
The oligomer (B) having an aromatic cyclic structure according to this embodiment may further have repeating units derived from other monomers copolymerizable with the styrene-based compound or indene-based compound.

In the oligomer (B) having an aromatic cyclic structure according to the present embodiment, at least one monomer selected from styrene-based compounds and indene-based compounds from the viewpoint of further improving transparency and resistance to gamma rays or electron rays. The content of the derived repeating unit is preferably 50% by mass or more and 100% by mass or less, more preferably 70% by mass or more and 100% by mass, when the whole oligomer (B) having an aromatic cyclic structure is taken as 100% by mass. Below, more preferably 80% by mass or more and 100% by mass or less.
The method for polymerizing the aromatic vinyl compound is not particularly limited, and can be carried out according to known methods.

The softening point of the oligomer (B) having an aromatic cyclic structure according to the present embodiment is preferably 80°C or higher, more preferably 95°C or higher, from the viewpoint of improving the heat resistance of the resulting medical container. more preferred.

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

The cyclic olefin-based resin composition according to the present embodiment may contain a hindered amine-based compound [C], if necessary.
As the hindered amine compound [C] (hereinafter simply referred to as compound [C] or [C]), 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.

Specific examples of the compound [C] include compounds known as Hindered Amine Light Stabilizers (abbreviated as HALS).

Examples of the compound [C] 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 [C] 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 [C], which is a polymer or oligomer such as this compound, it is believed that compatibility with the cyclic olefin resin (A) 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 the 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 [C], only 1 type may be used and 2 or more types may be used.
The content of the compound [C] in the composition is, for example, 0.01 to 2.0 parts by mass, preferably 0.05 to 1.0 part by mass when the content of the cyclic olefin resin (A) is 100 parts by mass. 5 parts by mass, more preferably 0.10 to 1.0 parts by mass. Within this range, it is possible to effectively reduce discoloration and generation of radicals due to electron beam or gamma ray irradiation while maintaining other properties (for example, moldability and mechanical strength).

The cyclic olefin-based resin composition according to the present embodiment may contain a phosphorus-based compound [D], if necessary.
There are no particular restrictions on the usable phosphorus-based compound [D] (hereinafter sometimes simply referred to as compound [D] or [D]). 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- 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 neopentanetetrayl bis (isodecyl phosphite), cyclic neopentane tetrayl bis (nonylphenyl phosphite), cyclic neopentane tetrayl bis (2 ,4-di-t-butylphenylphosphite), cyclic neopentanetetraylbis(2,4-dimethylphenylphosphite), cyclic neopentanetetraylbis(2,6-di-t-butylphenylphosphite) phyto) and other diphosphite compounds.

The compound [D] preferably used is a trivalent organophosphorus compound. More specifically, compound [D] 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 [D] 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 groups in which these are substituted 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.

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 1.5 parts by mass, preferably 0.02 to 1.0 parts by mass when the amount of the cyclic olefin resin (A) is 100 parts by mass. parts by mass, more preferably 0.05 to 0.5 parts by mass. Within this range, it is possible to effectively reduce discoloration and generation of radicals due to electron beam or gamma ray irradiation while maintaining other properties (for example, moldability and mechanical strength).

On the other hand, from another point of view, when the amount of the cyclic olefin resin (A) is 100 parts by mass, the content of the phosphorus compound [D] is preferably less than 0.05 parts by mass, more preferably 0.03 parts by mass. parts or less, more preferably 0.02 parts by mass or less.

The cyclic olefin-based resin composition according to the present embodiment is produced by melt-kneading the cyclic olefin-based resin (A) and the oligomer (B) having an aromatic cyclic structure using a known kneading device such as an extruder and a Banbury mixer. Method; A method of dissolving the cyclic olefin resin (A) and the oligomer (B) having an aromatic cyclic structure in a common solvent and then evaporating the solvent; A method of adding a solution of the oligomer (B) having a structure to precipitate it;

[Medical containers]
Next, a medical container according to an embodiment of the present invention will be described.
The medical container according to this embodiment contains the cyclic olefin resin composition according to this embodiment.
Since the medical container according to the present embodiment contains the cyclic olefin-based resin composition according to the present embodiment, it has an excellent performance balance between transparency and resistance to gamma rays or electron rays. This medical container is less discolored by electron beam or gamma ray irradiation.
Here, according to another study by the present inventors, it has become clear that conventional medical containers may generate radicals 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 medical container with the content.
In contrast, 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 this embodiment, it is possible to reduce the risk of deterioration of the contents.

The method for molding the cyclic olefin-based resin composition according to the present embodiment to obtain a medical container is not particularly limited, and 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, for example, by irradiating the medical container manufactured as described above with gamma rays or electron beams, it is possible to obtain a gamma-ray or electron beam-irradiated medical container (a medical container irradiated with gamma rays or electron beams). can. This medical container is clean because it is sterilized or sterilized by irradiation, and discoloration and generation of radicals are suppressed. Although the irradiation dose is not particularly limited, it is usually 5 to 100 kiloGrays, preferably 10 to 80 kiloGrays.

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, hooks, gauze, and contact lenses; such as laboratory instruments; artificial organ housings, and the like.

The medical container 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. and a method of measuring the total light transmittance of a sheet obtained by molding the cyclic olefin resin composition 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 described in more detail below with reference to examples, but the present invention is not limited by these examples.

<Examples 1 to 6 and Comparative Examples 1 to 3>
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.

(Evaluation of cyclic olefin resin composition)
[Pelletization]
With respect to 100 parts by mass of a resin composition obtained by mixing the cyclic olefin resin (A) and the oligomer (B) having an aromatic cyclic structure in the amounts shown in Table 2, Tri 0.2 parts by mass of (2,4-di-t-butylphenyl) phosphate, dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2, 0.5 part by mass of a polycondensate of 6,6-tetramethyl-4-piperidine (TINUVIN622LD manufactured by BASF) was blended. Next, using a twin-screw extruder BT-30 (screw diameter 30 mmφ, L/D = 46) manufactured by Plastic Engineering Laboratory, granulation was performed under the conditions of a set temperature of 270°C, a resin throughput of 80 g/min, and a screw rotation speed of 200 rpm. Then, pellets for various measurements were obtained.

[injection molding]
Using an injection molding machine IS-55 manufactured by Toshiba Machine Co., Ltd., the pellets obtained above are processed at a cylinder temperature of 270 to 290 ° C., an injection speed of 70 to 90%, a screw rotation speed of 70 to 100 rpm, and a mold temperature of 120. °C to prepare an injection square plate test piece with a thickness of 2 mm and an HDT injection test piece (1/4 inch).

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

[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 Industries Co., Ltd.).
○: Internal haze is less than 6.0% ×: The test piece is visually cloudy, or the internal haze is 6.0% or more

[Load Deflection Temperature (HDT)]
Using an ASTM HDT test piece (1/4 inch) molded by injection molding, the bending stress was measured at a bending stress of 0.45 MPa and a heating rate of 2° C./min according to ASTM D648.

[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 10GY. 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 generated]
The amount of radicals in the sample after gamma ray irradiation was measured by electron spin resonance (ESR).
Specifically, about 6 mg of a test piece was cut out immediately after gamma ray irradiation, 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: 1mW
・Central magnetic field: 326.5mT
・Sweep width: ±15mT
・Modulation frequency: 100 kHz
- Sweep time: 8min.
・Time constant: 0.1sec
・Amplification: 25
・Sample tube: sample tube with quartz tip corresponding to X band ・External sight: Mn ²⁺ standard sample supported on magnesium oxide ・External standard memory: 0,700
・Measurement temperature: Room temperature ・Measurement atmosphere: Atmosphere

A normalized value represented by the following formula was used for the relative comparison of the amount of generated radicals.

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 reference area of the Mn ²⁺ -derived signal. However, since the spectrum of organic radical-derived radicals overlaps with Mn ²⁺ (third signal), Mn ²⁺ (second signal) was used for all measurements this time (external standard memory=700).
When the organic radical-derived signal overlapped with Mn ²⁺ (third signal), the ESR spectrum with external standard memory=0 was used for calculation.

The components used in Examples and Comparative Examples are shown below.

[Cyclic olefin resin (A)]
A-1: Random copolymer of ethylene and cyclic olefin (ethylene content: 66 mol%, glass transition temperature: 145°C, intrinsic viscosity [η]: 0.60 dl/g)
A-2: Random copolymer of ethylene and cyclic olefin (ethylene content: 44 mol%, glass transition temperature: 135°C, intrinsic viscosity [η]: 0.60 dl/g)
Here, the above cyclic olefin resin (A) was synthesized by a method according to the synthesis examples described in the examples of International Publication No. 2008/068897. Table 1 shows the type, content and physical properties of the comonomer (cyclic olefin monomer) of each cyclic olefin resin (A). In Table 1, TD is tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene and NB is bicyclo[2.2.1]-2-heptene.
TD is n=0, m=1, and R ¹ to R ¹⁸ are hydrogen atoms in the above formula [I], and NB is n=0, m=0, R ¹ to R ¹⁸ in the above formula [I]. is a hydrogen atom.

[Components other than cyclic olefin polymer]
B-1: Aromatic cyclic structure-containing oligomer (weight average molecular weight: 2000, solubility parameter: 19.3 MPa ^1/2 )
B-2: Aromatic cyclic structure-containing oligomer (weight average molecular weight: 2105, solubility parameter: 19.6 MPa ^1/2 )
B-3: Aromatic cyclic structure-containing oligomer (weight average molecular weight: 2590, solubility parameter: 19.7 MPa ^1/2 )
B-4: Polystyrene (weight average molecular weight: 35000, solubility parameter: 20.1 MPa ^1/2 )

[Synthesis Example 1: Synthesis of aromatic cyclic structure-containing oligomer (B-1)]
A mixture of α-methylstyrene and dehydrated toluene (volume ratio: sum of monomers/toluene = 1/1) and a boron triad diluted 10-fold with dehydrated toluene were placed in an autoclave with an actual capacity of 1270 ml equipped with a stirring blade. A fluoride phenolate complex (1.7 equivalents of phenol) was continuously supplied, and the polymerization reaction was carried out at a reaction temperature of 5°C. At this time, the amount of the catalyst was set to 0.20 wt % with respect to the total amount of the monomers, and the raw materials were supplied so that the amount of the monomers supplied was 1.0 liter/hour. Subsequently, the reaction mixture was transferred to the second-stage autoclave and allowed to continue the polymerization reaction at 5° C. When the total residence time in the first-stage and second-stage autoclaves reached 2 hours, The reaction mixture was continuously discharged, and 1 liter of the reaction mixture was collected when the residence time was tripled to terminate the polymerization reaction. After completion of the polymerization, a 1 N NaOH aqueous solution was added to the sampled reaction mixture to deash the catalyst residue. Further, the obtained reaction mixture was washed with a large amount of water five times, and then the solvent and unreacted monomers were distilled off under reduced pressure using an evaporator to obtain an aromatic ring structure-containing oligomer (B-1). The obtained aromatic ring structure-containing oligomer (B-1) had a weight average molecular weight Mw of 2,000.

[Synthesis Example 2: Synthesis of aromatic ring structure-containing oligomer (B-2)]
A mixture of isopropenyl toluene, indene and dehydrated toluene (volume ratio: total monomer/toluene = 1/1) and boron diluted 10-fold with dehydrated toluene were placed in an autoclave with an actual capacity of 1270 ml equipped with a stirring blade. A trifluoride phenolate complex (1.7 equivalents of phenol) was continuously supplied, and the polymerization reaction was carried out at a reaction temperature of 5°C. At this time, the weight ratio of isopropenyltoluene and indene was 50/50, the amount of catalyst was 0.20 wt% with respect to the total monomers, and the raw materials were supplied so that the monomer supply amount was 1.0 liter/hour. . Subsequently, the reaction mixture was transferred to the second-stage autoclave and allowed to continue the polymerization reaction at 5° C. When the total residence time in the first-stage and second-stage autoclaves reached 2 hours, The reaction mixture was continuously discharged, and 1 liter of the reaction mixture was collected when the residence time was tripled to terminate the polymerization reaction. After completion of the polymerization, a 1 N NaOH aqueous solution was added to the sampled reaction mixture to deash the catalyst residue. Further, the obtained reaction mixture was washed with a large amount of water five times, and then the solvent and unreacted monomers were distilled off under reduced pressure using an evaporator to obtain an aromatic ring structure-containing oligomer (B-2). The obtained aromatic ring structure-containing oligomer (B-2) had a weight average molecular weight Mw of 2,105.

[Synthesis Example 3: Synthesis of aromatic cyclic structure-containing oligomer (B-3)]
A mixture of α-methylstyrene, styrene and dehydrated toluene (volume ratio: sum of monomers/toluene = 1/1) and dehydrated toluene were diluted 10 times in an autoclave with an actual capacity of 1270 ml equipped with a stirring blade. A boron trifluoride phenolate complex (1.7 equivalents of phenol) was continuously supplied, and the polymerization reaction was carried out at a reaction temperature of 5°C. At this time, the weight ratio of α-methylstyrene and styrene was 63/37, the amount of catalyst was 0.11 wt% with respect to the total monomers, and the raw materials were supplied so that the monomer supply amount was 1.0 liter/hour. did. Subsequently, the reaction mixture was transferred to the second-stage autoclave and allowed to continue the polymerization reaction at 5° C. When the total residence time in the first-stage and second-stage autoclaves reached 2 hours, The reaction mixture was continuously discharged, and 1 liter of the reaction mixture was collected when the residence time was tripled to terminate the polymerization reaction. After completion of the polymerization, a 1 N NaOH aqueous solution was added to the sampled reaction mixture to deash the catalyst residue. Further, the obtained reaction mixture was washed with a large amount of water five times, and then the solvent and unreacted monomers were distilled off under reduced pressure using an evaporator to obtain an aromatic ring structure-containing oligomer (B-3). The obtained aromatic ring structure-containing oligomer (B-3) had a weight average molecular weight Mw of 2,590.

[Weight average molecular weight]
Here, the weight-average molecular weights of the components other than the cyclic olefin polymer were measured by GPC measurement and calculated as standard polystyrene conversion values. GPC measurement was performed under the following conditions.
Apparatus: GPC HLC-8320 (manufactured by Tosoh Corporation)
Solvent: Tetrahydrofuran Column: TSKgel G7000×1, TSKgel G4000×2, TSKgel G2000×1 (both manufactured by Tosoh Corporation)
Flow rate: 1.0 ml/min Sample: 20 mg/mL tetrahydrofuran solution Temperature: Room temperature Standard polystyrene: Tosoh standard polystyrene [solubility parameter]
For the solubility parameters of the components other than the cyclic olefin polymer, the Fedors parameters calculated using the Synthia module of Materials Studio were employed.

[Limiting viscosity]
Intrinsic viscosity ([η]) was measured in decalin at 135°C.
Specifically, the resin (about 20 mg) was dissolved in decalin solvent (15 mL), and the specific viscosity η _sp was measured in an oil bath at 135°C. The decalin solution was diluted with additional decalin solvent (5 mL), after which the specific viscosity η _sp was measured in the same manner as previously described. This dilution operation was repeated twice, and the value of η _sp /C when the concentration (C) of the sample was extrapolated to 0 was defined as the intrinsic viscosity [η].
Intrinsic viscosity [η] = lim (η _sp /C) (C→0)

[Glass transition temperature Tg (°C)]
DSC measurement was performed under the following conditions.
・ Apparatus: DSC7000 manufactured by SII Nano Technology Co., Ltd.
Measurement conditions: Under a nitrogen atmosphere, the temperature was raised from room temperature to 260°C at a temperature elevation rate of 10°C/min, and then held for 5 minutes. Then, the temperature was lowered to 30°C at a temperature lowering rate of 10°C/min and held for 5 minutes. After that, a DSC curve in the process of increasing the temperature up to 260° C. at a rate of temperature increase of 10° C./min was obtained.

In the obtained DSC curve, the temperature at the point where a straight line equidistant from the extended straight line of each base line in the direction of the vertical axis intersects with the curve of the stepwise change portion of the glass transition was defined as the glass transition temperature.

As described above, the molded articles (sheets) composed of the cyclic olefin-based resin compositions obtained in Examples 1 to 6 had an excellent balance of transparency and gamma ray resistance. On the other hand, the molded articles of Comparative Example 1, in which the content of the oligomer (B) having an aromatic cyclic structure is large, and Comparative Example 2, which contains polystyrene instead of the oligomer (B) having an aromatic cyclic structure, are inferior in transparency. rice field. Comparative Example 3, which does not contain the oligomer (B) having an aromatic ring structure, was inferior to the Examples in terms of radical generation amount and discoloration.

Claims (7)

A medical container containing a cyclic olefin resin composition containing a cyclic olefin resin (A) and an oligomer (B) having an aromatic cyclic structure,
The weight average molecular weight (Mw) of the oligomer (B) having an aromatic ring structure is 500 or more and 5000 or less,
The solubility parameter of the oligomer (B) having an aromatic cyclic structure is 18.0 MPa ^1/2 or more and 21.0 MPa ^1/2 or less,
When the total of the cyclic olefin resin (A) and the oligomer (B) having an aromatic cyclic structure contained in the cyclic olefin resin composition is 100 parts by mass, the content of the cyclic olefin resin (A) the amount is 70 parts by mass or more and 99 parts by mass or less, and the content of the oligomer (B) having an aromatic ring structure is 1 part by mass or more and 30 parts by mass or less ;
A medical container , wherein the oligomer (B) having an aromatic ring structure has a repeating unit derived from at least one monomer selected from styrene-based compounds and indene-based compounds . The medical container according to claim 1,
The cyclic olefin resin (A) is
A medical container containing at least one selected from the following [A-1], [A-2], [A-3] and [A-4].
[A-1] A random copolymer of an α-olefin having 2 to 20 carbon atoms and a cyclic olefin represented by the following formula [I] or [II];

(In the above formula [I], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, R ¹ to R ¹⁸ and R ^a and R ^b are each independently , a hydrogen atom, a halogen atom, or a hydrocarbon group optionally substituted with halogen, and R ¹⁵ to R ¹⁸ may be bonded together to form a monocyclic or polycyclic ring, and the monocyclic or The polycyclic ring may have a double bond, and R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group.),

(In formula [II] above, p and q are 0 or positive integers, m and n are 0, 1 or 2, and R ¹ to R ¹⁹ are each independently a hydrogen atom, a halogen atom, or a halogen atom. An optionally substituted hydrocarbon group or alkoxy group, the carbon atom to which R ⁹ and R ¹⁰ are bonded and the carbon atom to which R ¹³ is bonded or the carbon atom to which R ¹¹ is bonded They may be bonded directly or through an alkylene group having 1 to 3 carbon atoms, and when n=m=0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ are bonded to each other to form a monocyclic or polycyclic may form an aromatic ring of.),
[A-2] A ring-opening polymer or copolymer of a cyclic olefin represented by the formula [I] or [II],
[A-3] hydride of the ring-opening polymer or copolymer [A-2],
[A-4] A graft modified product of the above [A-1], [A-2] or [A-3]. In the medical container according to claim 1 or 2,
The cyclic olefins in the cyclic olefin resin (A) are bicyclo[2.2.1]-2-heptene and tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene, a repeating unit derived from at least one compound selected from medical containers. In the medical container according to any one of claims 1 to 3 ,
A medical container, which is a syringe or a drug storage container. A cyclic olefin resin composition for forming a medical container,
including a cyclic olefin resin (A) and an oligomer (B) having an aromatic cyclic structure,
The weight average molecular weight (Mw) of the oligomer (B) having an aromatic ring structure is 500 or more and 5000 or less,
The solubility parameter of the oligomer (B) having an aromatic cyclic structure is 18.0 MPa ^1/2 or more and 21.0 MPa ^1/2 or less,
When the total of the cyclic olefin resin (A) and the oligomer (B) having an aromatic cyclic structure contained in the cyclic olefin resin composition is 100 parts by mass, the content of the cyclic olefin resin (A) the amount is 70 parts by mass or more and 99 parts by mass or less, and the content of the oligomer (B) having an aromatic ring structure is 1 part by mass or more and 30 parts by mass or less;
The medical container is a syringe or a drug solution storage container ,
A cyclic olefin resin composition for medical containers, wherein the oligomer (B) having an aromatic cyclic structure has a repeating unit derived from at least one monomer selected from styrene compounds and indene compounds . In the cyclic olefin resin composition for medical containers according to claim 5 ,
The cyclic olefin resin (A) is
A cyclic olefin resin composition for medical containers, comprising at least one selected from the following [A-1], [A-2], [A-3] and [A-4].
[A-1] A random copolymer of an α-olefin having 2 to 20 carbon atoms and a cyclic olefin represented by the following formula [I] or [II];

(In the above formula [I], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, R ¹ to R ¹⁸ and R ^a and R ^b are each independently , a hydrogen atom, a halogen atom, or a hydrocarbon group optionally substituted with halogen, and R ¹⁵ to R ¹⁸ may be bonded together to form a monocyclic or polycyclic ring, and the monocyclic or The polycyclic ring may have a double bond, and R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group.),

(In formula [II] above, p and q are 0 or positive integers, m and n are 0, 1 or 2, and R ¹ to R ¹⁹ are each independently a hydrogen atom, a halogen atom, or a halogen atom. An optionally substituted hydrocarbon group or alkoxy group, the carbon atom to which R ⁹ and R ¹⁰ are bonded and the carbon atom to which R ¹³ is bonded or the carbon atom to which R ¹¹ is bonded They may be bonded directly or through an alkylene group having 1 to 3 carbon atoms, and when n=m=0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ are bonded to each other to form a monocyclic or polycyclic may form an aromatic ring of.),
[A-2] A ring-opening polymer or copolymer of a cyclic olefin represented by the formula [I] or [II],
[A-3] hydride of the ring-opening polymer or copolymer [A-2],
[A-4] A graft modified product of the above [A-1], [A-2] or [A-3]. In the cyclic olefin resin composition for medical containers according to claim 5 or 6 ,
The cyclic olefins in the cyclic olefin resin (A) are bicyclo[2.2.1]-2-heptene and tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene.