JP2022190330A - Cyclic olefin-based polymer for fiber, and fiber - Google Patents

Abstract

To provide a cyclic olefin-based polymer for a fiber, in which deterioration is suppressed, and fibers can be continuously spun.SOLUTION: A cyclic olefin-based polymer for fibers of the present invention satisfies the following conditions: a ratio of complex viscosity when a shear is continuously applied at 260°C, a frequency of 1 Hz, and in the atmosphere is 1≤η*2/η*1≤5, in which η*1 is a complex viscosity (Pa sec) immediately after a shear is applied, and η*2 is a complex viscosity (Pa sec) after 3600 sec from application of a shear.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a cyclic olefin polymer for fibers and a fiber comprising the polymer.

Cyclic olefin polymers have excellent transparency, high heat resistance, and chemical resistance, so they are used for medical applications such as drug packaging materials and inspection containers, optical applications such as lenses and optical films, and electronic device applications. , used in textiles and non-woven fabrics.

For example, Patent Document 1 discloses a fiber made of a copolymer of ethylene and a given cyclic olefin or a ring-opening polymer of a given cyclic olefin.
Patent Document 2 discloses a meltblown nonwoven fabric composed of fibers containing a cyclic olefin polymer.

Patent Document 3 discloses a fiber containing a cyclic polyolefin resin having a glass transition temperature of 70°C or more and less than 150°C.
Patent Document 4 discloses a fiber obtained by spinning pellets obtained from a resin powder of a cyclic olefin polymer having a predetermined bulk density and then heat-treating the pellets under predetermined conditions.

Patent Document 5 discloses a structural unit derived from an α-olefin having 2 to 20 carbon atoms, a structural unit derived from a cyclic olefin having no aromatic ring, and a structural unit derived from a cyclic olefin having an aromatic ring. is disclosed.

JP-A-6-158420 WO2019/049706 JP 2017-222934 A WO2015/060242 WO2019/107363

However, in the conventional technology, when the pellets containing the cyclic olefin polymer are melt-spun, if the spinning is continued, shear is applied between the nozzle and the resin, which deteriorates the resin, and when the spinning is continued, the resin deteriorates. Fibers were sometimes broken.

As a result of intensive studies by the present inventors, when a cyclic olefin polymer is sheared under predetermined conditions, if the ratio of the complex viscosities before and after shearing is within a specific range, the cyclic olefin polymer The inventors have found that the fibers made of the polymer can be continuously spun because deterioration is suppressed, and have completed the present invention.
That is, the present invention can be shown below.

（前記式［Ｂ－１］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原子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。ただし、芳香環を含まない。）
［８］ 前記芳香環を有する環状オレフィンが、下記式（Ｃ－１）で示される化合物、下記式（Ｃ－２）で示される化合物、および下記式（Ｃ－３）で示される化合物からなる群から選択される一種または二種以上を含む、［３］～［７］のいずれかに記載の繊維用環状オレフィン系重合体。

（上記式（Ｃ－１）中、ｎおよびｑはそれぞれ独立に０、１または２であり、Ｒ^１～Ｒ^１７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、Ｒ^１０～Ｒ^１７のうち一つは結合手であり、またｑ＝０のときＲ^１０とＲ^１１、Ｒ^１１とＲ^１２、Ｒ^１２とＲ^１３、Ｒ^１３とＲ^１４、Ｒ^１４とＲ^１５、Ｒ^１５とＲ^１０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＝１または２のときＲ^１０とＲ^１１、Ｒ^１１とＲ^１７、Ｒ^１７とＲ^１７、Ｒ^１７とＲ^１２、Ｒ^１２とＲ^１３、Ｒ^１３とＲ^１４、Ｒ^１４とＲ^１５、Ｒ^１５とＲ^１６、Ｒ^１６とＲ^１６、Ｒ^１６とＲ^１０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、また前記単環または前記多環が二重結合を有していてもよく、前記単環または前記多環が芳香族環であってもよい。）

（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、前記単環または前記多環が二重結合を有していてもよく、また前記単環または前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、前記単環または前記多環が二重結合を有していてもよく、また前記単環または前記多環が芳香族環であってもよい。）
［９］ ［１］～［８］のいずれかに記載の繊維用環状オレフィン系重合体からなる繊維。 [1] A cyclic olefin polymer for fiber that satisfies the following conditions.
(conditions)
The complex viscosity ratio is 1 ≤ η*2/η*1 ≤ 5 when shear is applied continuously at 260°C, frequency 1 Hz, and in the atmosphere.
η*1: complex viscosity immediately after shearing (Pa・sec)
η*2: Complex viscosity after 3600 sec from application of shear (Pa·sec)
[2] The cyclic olefin polymer for fibers according to [1], which contains at least one selected from the cyclic olefin copolymer (I-1) and the ring-opened cyclic olefin polymer (I-2).
[3] The cyclic olefin copolymer (I-1) is
a structural unit (A) derived from an α-olefin having 2 to 20 carbon atoms;
a structural unit (B) derived from a cyclic olefin having no aromatic ring;
a structural unit (C) derived from a cyclic olefin having an aromatic ring;
The cyclic olefin polymer for fibers according to [1] or [2], having
[4] When the total content of the structural unit (A), the structural unit (B) and the structural unit (C) in the cyclic olefin copolymer (I-1) is 100 mol%, the cyclic olefin copolymer The cyclic olefin polymer for fibers according to [3], wherein the content of the structural unit (A) in the coalescence (I-1) is 10 mol% or more and 80 mol% or less.
[5] When the total content of the structural unit (A), the structural unit (B) and the structural unit (C) in the cyclic olefin copolymer (I-1) is 100 mol%, the cyclic olefin copolymer The cyclic olefin polymer for fibers according to any one of [3] to [4], wherein the content of the structural unit (C) in the coalescence (I-1) is 0.1 mol% or more and 50 mol% or less. .
[6] Cyclic olefin copolymer (I-1) when the total content of structural units (B) and structural units (C) in cyclic olefin copolymer (I-1) is 100 mol% The cyclic olefin polymer for fibers according to any one of [3] to [5], wherein the content of the structural unit (C) therein is 5 mol% or more and 95 mol% or less.
[7] The cyclic olefin polymer for fiber according to any one of [3] to [6], wherein the aromatic ring-free cyclic olefin contains a compound represented by the following formula (B-1).

(In the above formula [B-1], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, 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 a halogen atom; The monocyclic or polycyclic ring may have a double bond, and R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group, provided that aromatic rings are included. No.)
[8] The cyclic olefin having an aromatic ring consists of a compound represented by the following formula (C-1), a compound represented by the following formula (C-2), and a compound represented by the following formula (C-3). The cyclic olefin polymer for fiber according to any one of [3] to [7], which contains one or more selected from the group.

(In formula (C-1) above, n and q are each independently 0, 1 or 2, and R ¹ to R ¹⁷ are each independently a hydrogen atom, a halogen atom other than a fluorine atom, or a fluorine atom a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom, one of R ¹⁰ to R ¹⁷ is a bond, and when q=0, R ¹⁰ and R ¹¹ , R ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁵ and R ¹⁰ may be bonded together to form a monocyclic or polycyclic ring, and q=1 or when ² , R10 and R11, ^R11 and ^R17 , ^R17 and ^R17 , ^R17 and ^R12 , ^R12 and ^R13 , ^R13 and ^R14 , ^R14 and ^R15 , ^R15 and ^{R 16} , R ¹⁶ and R ¹⁶ , R ¹⁶ and R ¹⁰ may combine with each other to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring may have a double bond. , said monocyclic ring or said polycyclic ring may be an aromatic ring.)

(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. )
[9] A fiber made of the cyclic olefin polymer for fiber according to any one of [1] to [8].

The cyclic olefin polymer for fibers of the present invention is suppressed in deterioration, and can provide fibers that can be continuously spun.

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.

[Fiber cyclic olefin polymer (I)]
In this embodiment, the fiber cyclic olefin polymer (I) satisfies the following conditions. In addition, in this embodiment, it is simply referred to as a cyclic olefin polymer (I).
(conditions)
The ratio of the complex viscosity when continuously sheared at 260° C., frequency of 1 Hz, and atmospheric air is 1≦η*2/η*1≦5, preferably 1≦η*2/η*1≦4. 5
η*1: complex viscosity immediately after shearing (Pa・sec)
η*2: Complex viscosity after 3600 sec from application of shear (Pa·sec)

The cyclic olefin polymer (I) for fibers of the present embodiment has a complex viscosity ratio within a predetermined range, and an increase in viscosity is suppressed. That is, the ratio of the complex viscosities can be used as an indicator of the deterioration of the cyclic olefin polymer for fibers (I), and by using the cyclic olefin polymer for fibers (I) in which the ratio is within a predetermined range, , it is possible to provide a fiber that is suppressed from breaking and can be continuously spun. Further, by setting the complex viscosity ratio of the cyclic olefin polymer (I) for fibers within a predetermined range, it is possible to provide fibers having excellent resistance to electron beam or gamma ray irradiation.

The cyclic olefin-based polymer (I) for fibers of the present embodiment is selected from cyclic olefin-based copolymers (I-1) and ring-opening polymers of cyclic olefins (I-2) from the viewpoint of the effects of the present invention. It is preferable to contain at least one kind of cyclic olefin-based copolymer (I-1).

(Cyclic olefin copolymer (I-1))
The cyclic olefin copolymer (I-1) comprises a structural unit (A) derived from an α-olefin having 2 to 20 carbon atoms and a structural unit (B) derived from a cyclic olefin having no aromatic ring. and at least one of structural units (C) derived from a cyclic olefin having an aromatic ring. That is, the cyclic olefin copolymer (I-1) has the structural unit (A) and the structural unit (B), or has the structural unit (A) and the structural unit (C), or , the structural unit (A), the structural unit (B) and the structural unit (C).
Preferably, it has the structural unit (A) and the structural unit (C), or it has the structural unit (A) and the structural unit (B) and the structural unit (C).

By having these constitutional units, the cyclic olefin copolymer (I-1) can be spun continuously due to its further suppressed deterioration, and furthermore has excellent resistance to electron beam or gamma ray irradiation. You can get fiber.
When the cyclic olefin copolymer (I-1) has the structural unit (A), the structural unit (B), and the structural unit (C), generation of radicals is suppressed even by electron beam or gamma ray irradiation. , a fiber excellent in resistance to electron beams or gamma rays can be obtained. Fibers and non-woven fabrics made from cyclic olefin polymers can be applied to medical applications due to their excellent properties such as high heat resistance and chemical resistance. It was difficult to apply because it occurred. However, the use of the above-mentioned structural units provides fibers with excellent resistance to electron beams or gamma rays.

(Constituent unit (A))
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), the structural unit (B) and the structural unit (C) in the cyclic olefin copolymer (I-1) according to the present embodiment is 100 mol%, The content of the structural unit (A) in the cyclic olefin copolymer (I-1) according to the present embodiment is preferably 10 mol% or more and 80 mol% or less, more preferably 30 mol% or more and 75 mol%. Below, it is more preferably 40 mol % or more and 70 mol % or less.

When the content of the structural unit (A) is at least the lower limit, the heat resistance of the cyclic olefin copolymer (I-1) can be improved and deterioration can be suppressed. Further, when the content of the structural unit (A) is equal to or less than the above upper limit, the electron beam or gamma ray resistance of the resulting fiber can be improved. That is, when the content of the structural unit (A) is within the above range, these properties are excellent.
In this embodiment, the content of the structural unit (A) can be measured, for example, by ¹ H-NMR or ¹³ C-NMR.

(Constituent unit (B))
The structural unit (B) according to this embodiment is a structural unit derived from a cyclic olefin having no aromatic ring. The structural unit (B) according to the present embodiment preferably contains a structural unit derived from a compound represented by the following formula (B-1) from the viewpoint of further improving the refractive index of the resulting molded product.

In the above formula [B-1], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, R ¹ to R ¹⁸ and R ^a and R ^b are each independently , is a hydrogen atom, a halogen atom, or a hydrocarbon group optionally substituted with a ^{halogen atom} ; The ring or polycyclic ring may have a double bond and R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group. However, it does not contain an aromatic ring.
As a structural unit (B), it can be used individually by 1 type or in combination of 2 or more types.

Among these, structural units derived from bicyclo[2.2.1]-2-heptene, tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene-derived structural units and hexacyclo[6,6,1,1 ^3,6 ,1 ^10,13 ,0 ^2,7 ,0 ^9,14 ]heptadecene-4-derived structural units, etc. It preferably contains at least one structural unit selected from a structural unit derived from bicyclo[2.2.1]-2-heptene and tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3- ^dodecene -derived structural units. 1 ^7,10 ]-3-dodecene-derived structural units are particularly preferred.

When the total content of the structural unit (A), the structural unit (B) and the structural unit (C) in the cyclic olefin copolymer (I-1) according to the present embodiment is 100 mol%, The content of the structural unit (B) in the cyclic olefin copolymer (I-1) according to the present embodiment is preferably from the viewpoint of the effect of the present invention when the structural unit (C) is not included. is 20 mol % or more and 90 mol % or less, more preferably 25 mol % or more and 70 mol % or less, and still more preferably 30 mol % or more and 60 mol % or less.
When the above structural unit (C) is included, from the viewpoint of the effect of the present invention, it is preferably 5 mol% or more and 60 mol% or less, more preferably 10 mol% or more and 55 mol% or less, still more preferably 14 mol% or more and 45 mol% or less. mol% or less.

(Constituent unit (C))
The structural unit (C) according to this embodiment is a structural unit derived from a cyclic olefin having an aromatic ring. Viscosity when the cyclic olefin copolymer (I-1) contains the structural unit (C) derived from the cyclic olefin having an aromatic ring and is continuously spun (when continuously sheared) It can suppress the rise. Furthermore, generation of radicals is also suppressed by electron beam or gamma ray irradiation, and a fiber excellent in resistance to electron beams or gamma rays can be obtained.

Examples of the cyclic olefin having an aromatic ring according to the present embodiment include a compound (C-1) represented by the following formula (C-1), a compound (C-2) represented by the following formula (C-2), A compound (C-3) represented by the following formula (C-3) and the like are included. These aromatic ring-containing cyclic olefins may be used singly or in combination of two or more.

That is, the cyclic olefin-based copolymer (I-1) according to the present embodiment includes, as the structural unit (C), a structural unit (C ¹ ) derived from the compound (C-1) and a compound (C-2) It contains at least one selected from a structural unit (C ² ) derived from a compound (C-3) and a structural unit (C ³ ) derived from a compound (C-3).

In formula (C-1) above, n and q are each independently 0, 1 or 2. n is preferably 0 or 1, more preferably 0. q is preferably 0 or 1, more preferably 0.

R ¹ to R ¹⁷ are each independently a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms optionally substituted with a halogen atom other than a fluorine atom, and R ¹⁰ to It is preferred that one of R ¹⁷ is a bond and R ¹⁵ is a bond.
Each of R ¹ to R ¹⁷ is preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrogen atom.

When q=0, R ¹⁰ and R ¹¹ , R ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁵ and R ¹⁰ are bonded to each other to form a monocyclic or polycyclic ring. may form a ring, and when q=1 or 2, R ¹⁰ and R ¹¹ , R ¹¹ and R ¹⁷ , R ¹⁷ and R ¹⁷ , R ¹⁷ and R ¹² , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁵ and R ¹⁶ , R ¹⁶ and R ¹⁶ , R ¹⁶ and R ¹⁰ may be bonded together to form a monocyclic or polycyclic ring, and the monocyclic or The polycycle may have a double bond and the monocycle or the polycycle may be an aromatic ring.
Among the above formula (C-1), compounds represented by the following formula (C-1A) are preferable.

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.

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 the aromatic hydrocarbon group include aryl groups such as phenyl group, tolyl group, naphthyl group, benzyl group and phenylethyl group, and aralkyl groups. These hydrocarbon groups may be substituted with halogen atoms other than fluorine atoms.

Among these, the cyclic olefin having an aromatic ring according to the present embodiment is preferably one having one aromatic ring. 1,4,4a,9a-tetrahydro-1,4-methanofluorene (hereinafter also referred to as indenenorbornene) and methylphenylnorbornene are preferred.

Further, as the cyclic olefin having an aromatic ring according to the present embodiment, for example, a compound represented by the following formula (C-1′), a compound represented by the following formula (C-2′), a compound represented by the following formula (C-3 ') are also included. These aromatic ring-containing cyclic olefins may be used singly or in combination of two or more.

In formula (C-1′), formula (C-2′) and formula (C-3′) above, m and n are 0, 1 or 2, R ¹ to R ³⁶ are each independently a hydrogen atom , a halogen atom excluding a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms optionally substituted with a halogen atom excluding a fluorine atom, wherein R ¹⁰ and R ¹¹ , R ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ²⁵ and R ²⁶ , R ²⁶ and R ²⁷ , R ²⁷ and R ²⁸ , R ³³ and R ³⁴ , R ³⁴ and R ³⁵ , R ³⁵ and R ³⁶ are bonded to each other to form a single A ring may be formed, and the single ring may have a double bond.

In the above formulas (C-1′), (C-2′) and (C-3′), m is preferably 0 or 1, more preferably 1. n is preferably 0 or 1, more preferably 0. R ¹ to R ³⁶ are preferably hydrogen atoms or hydrocarbon groups having 1 to 20 carbon atoms, more preferably hydrogen atoms.

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 the aromatic hydrocarbon group include aryl groups such as phenyl group, tolyl group, naphthyl group, benzyl group and phenylethyl group, and aralkyl groups. These hydrocarbon groups may be substituted with halogen atoms other than fluorine atoms.

Among these, the cyclic olefin having an aromatic ring according to the present embodiment preferably has one aromatic ring, and for example, at least one selected from benzonorbornadiene, indenenorbornene and methylphenylnorbornene is preferred. .

When the total content of the structural unit (A), the structural unit (B) and the structural unit (C) in the cyclic olefin copolymer (I-1) according to the present embodiment is 100 mol%, The content of the structural unit (C) in the cyclic olefin copolymer (I-1) according to the present embodiment is preferably from the viewpoint of the effect of the present invention when the structural unit (B) is not included. is 20 mol % or more and 90 mol % or less, more preferably 25 mol % or more and 70 mol % or less, and still more preferably 30 mol % or more and 60 mol % or less.

When the total content of the structural unit (B) and the structural unit (C) in the cyclic olefin copolymer (I-1) according to the present embodiment is 100 mol%, the cyclic olefin according to the present embodiment The content of the structural unit (C) in the system copolymer (I-1) is preferably 5 mol% or more and 95 mol% or less, more preferably 10 mol% or more and 90 mol, from the viewpoint of the effect of the present invention. %, more preferably 20 mol % or more and 80 mol % or less, even more preferably 30 mol % or more and 80 mol % or less, still more preferably 40 mol % or more and 78 mol % or less.

When the total content of the structural unit (A), the structural unit (B) and the structural unit (C) in the cyclic olefin copolymer (I-1) according to the present embodiment is 100 mol%, From the viewpoint of the effects of the present invention, the content of the structural unit (C) in the cyclic olefin copolymer (I-1) is preferably 0.1 mol% or more and 50 mol% or less, more preferably 1 It is mol % or more, more preferably 3 mol % or more, more preferably 40 mol % or less, still more preferably 30 mol % or less, still more preferably 25 mol % or less, and particularly preferably 20 mol % or less.

In the present embodiment, the content of structural unit (A), structural unit (B) and structural unit (C) can be measured by ¹ H-NMR or ¹³ C-NMR, for example.

Although the copolymerization type of the cyclic olefin copolymer (I-1) 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 (I-1) according to the present embodiment is used from the viewpoint that a molded article having excellent optical properties such as transparency, Abbe number, refractive index and birefringence can be obtained. is preferably a random copolymer.

The cyclic olefin copolymer (I-1) according to the present embodiment is, for example, JP-A-60-168708, JP-A-61-120816, JP-A-61-115912, JP-A-61 61-115916, JP-A-61-271308, JP-A-61-272216, JP-A-62-252406, JP-A-62-252407, JP-A-2007-314806, It can be produced by appropriately selecting conditions according to the method disclosed in Japanese Patent Application Laid-Open No. 2010-241932.

(Ring-opening polymer of cyclic olefin (I-2))
In this embodiment, the cyclic olefin polymer (I) for fiber can be a ring-opened cyclic olefin polymer (I-2).

Examples of the ring-opening polymer (I-2) of a cyclic olefin include ring-opening polymers of norbornene-based monomers and ring-opening polymers of norbornene-based monomers and other monomers capable of ring-opening copolymerization thereof. Ring polymers, hydrides thereof, and the like are included.

Examples of norbornene-based monomers include, for example, bicyclo[2.2.1]hept-2-ene (common name: norbornene) and derivatives thereof (having a substituent on the ring), tricyclo[ ^{4.3.01 , 6} . 1 ^2,5 ]deca-3,7-diene (common name dicyclopentadiene) and its derivatives, 7,8-benzotricyclo[4.3.0.1 ^2,5 ]dec-3-ene (common name methanotetrahydrofluorene: 1,4-methano-1,4,4a,9a-tetrahydrofluorene) and its derivatives, tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene (common name: tetracyclododecene) and derivatives thereof, and the like.

Examples of substituents on the ring of these derivatives include an alkyl group, an alkylene group, a vinyl group, an alkoxycarbonyl group, and an alkylidene group. In addition, the substituent can have 1 or 2 or more. Derivatives having a substituent on such a ring include, for example, 8-methoxycarbonyl-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodeca-3-ene, 8-methyl-8-methoxycarbonyl-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodeca-3-ene, 8-ethylidene-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodeca-3-ene and the like.
These norbornene-based monomers may be used alone or in combination of two or more.

A ring-opening polymer of a norbornene-based monomer, or a ring-opening polymer of a norbornene-based monomer and other monomers capable of ring-opening copolymerization with the monomer component is prepared by a known ring-opening polymerization. It can be obtained by polymerization in the presence of a catalyst.

The ring-opening polymerization catalyst includes, for example, a metal halide such as ruthenium and osmium, a nitrate or an acetylacetone compound, and a reducing agent; , an organoaluminum compound; and the like.

Other monomers capable of ring-opening copolymerization with norbornene monomers include, for example, monocyclic cyclic olefin monomers such as cyclohexene, cycloheptene, and cyclooctene.

A hydride of a ring-opening polymer of a norbornene-based monomer, or a hydride of a ring-opening polymer of a norbornene-based monomer and another monomer capable of ring-opening copolymerization thereof is usually the above ring-opening It can be obtained by adding a known hydrogenation catalyst containing a transition metal such as nickel or palladium to a polymerization solution of the polymer to hydrogenate the carbon-carbon unsaturated bond.

The ring-opening polymer (I-2) of a cyclic olefin according to the present embodiment is, for example, JP-A-60-26024, JP-A-9-268250, JP-A-63-145324, JP-A-2001. It can be produced by appropriately selecting conditions according to the method disclosed in JP-A-72839 or the like.
The cyclic olefin ring-opening polymer (I-2) according to the present embodiment may be used alone or in combination of two or more.

The glass transition temperature (Tg) of the cyclic olefin polymer (I) for fiber according to the present embodiment, measured by a differential scanning calorimeter (DSC), is heat resistant while maintaining good transparency of the resulting fiber. is preferably 120° C. or higher and 180° C. or lower, more preferably 125° C. or higher and 170° C. or lower, and still more preferably 130° C. or higher and 165° C. or lower.

According to ASTM D1238, the melt flow rate (MFR) of the cyclic olefin polymer for fibers (I) measured at 260° C. and a load of 2.16 kg is 3 to 100 g/10 minutes from the viewpoint of spinning processability in the spinning process. , preferably 5 to 50 g/10 min.

[Cyclic olefin polymer composition]
Since the cyclic olefin polymer (I) for fibers according to the present embodiment forms fibers, it can contain other components other than the cyclic olefin polymer (I) as necessary. It can be a combined composition. In this embodiment, the cyclic olefin polymer composition containing only the fiber cyclic olefin polymer (I) is also referred to as a cyclic olefin polymer composition.

In addition, the content of the fiber cyclic olefin polymer (I) in the cyclic olefin polymer composition according to the present embodiment is such that deterioration suppression of the cyclic olefin polymer and resistance to electron rays or gamma rays From the viewpoint of further improving the balance, it is preferably 50% by mass or more and 100% by mass or less, more preferably 70% by mass or more and 100% by mass or less when the entire cyclic olefin polymer composition is 100% by mass. , 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 polymer composition according to the present embodiment contains the cyclic olefin polymer (I) for fibers in the above ratio, so that the deterioration of the cyclic olefin polymer for fibers is suppressed, and the composition is resistant to electrons. Ray or gamma ray resistance performance can be further improved.

(other ingredients)
The cyclic olefin polymer 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. agents, anti-blocking agents, anti-fogging agents, lubricants, natural oils, synthetic oils, waxes, organic or inorganic fillers, resins other than the cyclic olefin copolymer (I), etc., to the extent that they do not impair the object of the present invention. It can be blended, and the blending ratio is an appropriate amount.
The cyclic olefin-based polymer composition according to this embodiment may contain a hindered amine-based compound [D], if necessary.

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.

In addition, 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 (above UV-Cyasorb) ADEKA STAB LA-52, ADEKA STAB LA-57, ADEKA STAB LA-63P, ADEKA STAB LA-68, ADEKA STAB LA-72, ADEKA STAB LA-77Y, ADEKA STAB LA-81, ADEKA STAB LA-82, ADEKA STAB LA-87 (above, A commercially available product such as ADEKA Corporation) can be used.

The cyclic olefin polymer composition according to the present embodiment may contain a phosphorus compound [E], if necessary.

There are no particular restrictions on the usable phosphorus-based 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- 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 cyclic olefin-based polymer composition according to the present embodiment is a method of melt-kneading the cyclic olefin-based polymer (I) for fibers and other components using a known kneading device such as an extruder and a Banbury mixer; A method of dissolving the cyclic olefin polymer (I) for fibers and other components in a common solvent and then evaporating the solvent; It can be obtained by a method such as a method of precipitating with

<Fiber>
The fiber of the present embodiment can be obtained by a conventionally known fiberization method, using a composition in which the cyclic olefin polymer (I) described above and, if necessary, other components are added.

Spinning methods for fiberization include a dry spinning method, a wet spinning method, a melt spinning method, an emulsion spinning method, and the like. Among these spinning methods, the melt spinning method is particularly preferred.

In this melt spinning method, the cyclic olefin polymer (I) (or composition) for fiber is heated to a temperature above the melting point (or softening point) and below the decomposition temperature, preferably at a temperature of 120 to 300 ° C. to melt it. After that, it is extruded from a nozzle, and the extruded resin is cooled and wound up. Although various types of nozzles can be used in this method, nozzles with an L/D value of about 10/0.5 to 60/3 mm are suitable. The extrusion speed of the resin from the nozzle is usually about 0.01-100 m/min, preferably about 0.05-10 m/min. The winding speed of the monofilament extruded at the above speed is usually 10-10,000 m/min, preferably 100-5,000 m/min. Therefore, the monofilament extruded from the nozzle is normally stretched during winding. The draw ratio at this time is usually 10 to 10,000, preferably 100 to 5,000.

The raw yarn obtained by spinning in this way can be subjected to post-treatment processes for the purpose of removal of impurities, strain drawing, heat treatment, refining, dyeing, and the like.
The fibers thus obtained can be used for applications such as clothes, ropes, fishing lines, non-woven fabrics, and reinforcing agents for various resin compounds.

In addition, the fiber composed of the cyclic olefin polymer (I) for fibers of the present embodiment is irradiated with gamma rays or electron beams to obtain gamma-ray or electron beam-irradiated fibers (fibers irradiated with gamma rays or electron beams). be able to. This fiber 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.
Thus, the fiber of the present embodiment has excellent resistance to electron beam or gamma ray irradiation, and can be applied to medical uses and the like.

Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various configurations other than those described above can be employed within the scope that does not impair the effects 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 to these.

<Production of cyclic olefin copolymer>
[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, tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene (24 mmol, hereinafter also referred to as tetracyclododecene) and benzonorbornadiene (40 mmol, hereinafter also referred to as BNBD) were added. 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 reaches a predetermined temperature, the flow gas is switched from nitrogen to ethylene, and 50 Nl/hr of ethylene and 0.5 Nl/hr of hydrogen are flowed into the reaction vessel. Methylaluminoxane (PMAO) (1.8 mmol) and a catalyst of the following formula (A-1) (0.0030 mmol) 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, tetracyclododecene and BNBD. Thereafter, the polymerization solution was transferred to a separately prepared 2 L beaker, 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 for 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 obtained solvent-containing polymer was dried under reduced pressure at 130° C. for 10 hours to obtain 1.83 g of white powdery ethylene/tetracyclododecene/BNBD copolymer.
Thus, a cyclic olefin copolymer (P-1) was obtained.

[Production Examples 2 to 8]
The same operation as in Production Example 1 was carried out, except that the structural units constituting the cyclic olefin copolymer and the content thereof were adjusted to the types and values shown in Table 1. cyclic olefin copolymers (P-2) to (P-8) were obtained.

Here, BNBD in Table 1 means benzonorbornadiene represented by the following formula (1), and IndNB means indene norbornene represented by the following formula (2). MePhNB means methylphenylnorbornene represented by the following formula (3).

[Production Example 9]
7 parts of a monomer mixture (40 mol% of structural units derived from dicyclopentadiene, 40 mol% of structural units derived from indenenorbornene, 20 mol% of structural units derived from methanotetrahydrofluorene) and 1,600 parts of dehydrated cyclohexane were placed in a polymerization reactor whose interior was replaced with nitrogen. 0.6 parts of 1-hexene, 1.3 parts of diisopropyl ether, 0.33 parts of isobutyl alcohol, 0.84 parts of triisobutylaluminum, and 30 parts of a cyclohexane solution of tungsten hexachloride (concentration: 0.66%) were added. , and the whole volume was stirred at 55° C. for 10 minutes.
Then, while continuing to stir, 693 parts of the above monomer mixture and 72 parts of a cyclohexane solution of tungsten hexachloride (concentration: 0.77%) were continuously added dropwise at 55° C. over 150 minutes. After the dropwise addition was completed, stirring was continued for an additional 30 minutes, and then 1.0 part of isopropyl alcohol was added to terminate the polymerization reaction. When the polymerization reaction solution was measured by gas chromatography, the conversion rate of monomer to polymer was 100%.

Next, 300 parts of the polymerization reaction solution containing the above polymer was transferred to an autoclave equipped with a stirrer, and 100 parts of cyclohexane and 2.0 parts of diatomaceous earth-supported nickel catalyst (nickel support rate: 58%) were added. After purging the inside of the autoclave with hydrogen, a hydrogenation reaction was carried out at 180° C. under a hydrogen pressure of 4.5 MPa for 6 hours.
After completion of the hydrogenation reaction, pressure filtration was carried out at a pressure of 0.25 MPa using a pressure filter with diatomaceous earth as a filter bed to obtain a colorless and transparent solution. The resulting solution was added to a beaker containing acetone three times as much as the solution while stirring to precipitate a ring-opening polymer, and P-9 was obtained in the same manner as in Production Example 1.

[Method for Measuring Content of Each Structural Unit Constituting Cyclic Olefin Copolymer]
The contents of ethylene and cyclic olefin were 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
The compositions of ethylene and cyclic olefins were quantified by the ¹³ C-NMR spectrum measured under the above conditions.

[Glass transition temperature Tg (°C)]
Using DSC-6220 manufactured by Shimadzu Science Co., Ltd., the glass transition temperature Tg of the cyclic olefin polymer was measured under an N ₂ (nitrogen) atmosphere. The cyclic olefin polymer was heated from room temperature to 200°C at a rate of 10°C/min, held for 5 minutes, then cooled to -20°C at a rate of 10°C/min, and held for 5 minutes. Then, the glass transition point (Tg) of the cyclic olefin polymer was obtained from the endothermic curve when the temperature was raised to 200°C at a temperature elevation rate of 10°C/min. Table 1 shows the results.

[Melt flow rate (MFR)]
The melt flow rate (MFR) of the cyclic olefin-based polymer was measured at 260° C. under a load of 2.16 kg according to ASTM D1238. Table 1 shows the results.

[Examples 1 to 4, Comparative Examples 1 to 5]
The obtained cyclic olefin polymer was melted at 230°C in a cylindrical barrel with a diameter of 10 mm and then extruded through a nozzle of L/D = 20/1 mm at a speed of 0.1 m/min to give the extruded resin was taken up at a take-up speed of 300 m/min and stretched while air cooling, to obtain a monofilament of a cyclic olefin polymer.
Using the obtained monofilaments, physical properties were measured and evaluated according to the following methods. Table 1 shows the results.

[Ratio of complex viscosity]
Using ARES-G2 manufactured by TA Instruments, a measurement sample is sandwiched between cones and parallel plates with a diameter of 25 mm (cone angle: 0.1 rad) in the atmosphere, a frequency of 1 Hz, a temperature of 260 ° C., The complex viscosity η* was measured under the condition that the measurement time was 1 hour. Of the obtained η*, the complex viscosity immediately after the start of measurement was defined as η*1 (Pa·sec), and the complex viscosity at the measurement time of 3600 sec was defined as η*2 (Pa·sec). Table 1 shows the obtained complex viscosity ratio η*2/η*1.

[Spinnability]
Spinnability after spinning for 1 hour by the above melt spinning was visually evaluated according to the following criteria. Table 1 shows the results.
○: Continuous spinning for 1 hour is possible without yarn breakage △: Molding is defective, but continuous spinning for 1 hour is possible ×: Molding is very defective, continuous spinning is impossible

[Gamma resistance]
(Evaluation: Radical generation amount)
The amount of radicals in the sample after gamma ray irradiation was measured by electron spin resonance (ESR).
Specifically, about 6 mg of the test piece was cut out immediately after the gamma ray irradiation, put in a sample 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: Mn2+ 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 Mn2+ (second signal).
Usually, in the relative comparison of the amount of radicals, Mn2+ (third signal) is used as the reference area of the Mn2+-derived signal. However, since the spectrum of organic radical-derived radicals overlaps with Mn2+ (third signal), Mn2+ (second signal) was used for all measurements (external standard memory=700).
When the organic radical-derived signal overlapped with Mn2+ (third signal), the ESR spectrum with external standard memory=0 was used for calculation.

The amount of radicals generated five days after the gamma ray irradiation obtained in the above measurement was compared in terms of relative values, with the standard value of Comparative Example 2 being 100. Table 1 shows the results.
○: Less than 70 △: 70 or more and less than 100 ×: 100 or more

Claims (9)

A cyclic olefin polymer for fiber that satisfies the following conditions.
(conditions)
The complex viscosity ratio is 1 ≤ η*2/η*1 ≤ 5 when shear is applied continuously at 260°C, frequency 1 Hz, and in the atmosphere.
η*1: complex viscosity immediately after shearing (Pa・sec)
η*2: Complex viscosity after 3600 sec from application of shear (Pa·sec) 2. The cyclic olefin polymer for fibers according to claim 1, comprising at least one selected from the cyclic olefin copolymer (I-1) and the cyclic olefin ring-opening polymer (I-2). The cyclic olefin copolymer (I-1) is
a structural unit (A) derived from an α-olefin having 2 to 20 carbon atoms;
a structural unit (B) derived from a cyclic olefin having no aromatic ring;
a structural unit (C) derived from a cyclic olefin having an aromatic ring;
The cyclic olefin polymer for fibers according to claim 1 or 2, having When the total content of the structural unit (A), the structural unit (B) and the structural unit (C) in the cyclic olefin copolymer (I-1) is 100 mol%, the cyclic olefin copolymer (I 4. The cyclic olefin polymer for fibers according to claim 3, wherein the content of the structural unit (A) in -1) is 10 mol % or more and 80 mol % or less. When the total content of the structural unit (A), the structural unit (B) and the structural unit (C) in the cyclic olefin copolymer (I-1) is 100 mol%, the cyclic olefin copolymer (I The cyclic olefin polymer for fiber according to any one of claims 3 and 4, wherein the content of the structural unit (C) in -1) is 0.1 mol% or more and 50 mol% or less. When the total content of the structural unit (B) and the structural unit (C) in the cyclic olefin copolymer (I-1) is 100 mol%, the structure in the cyclic olefin copolymer (I-1) The cyclic olefin polymer for fibers according to any one of claims 3 to 5, wherein the content of the units (C) is 5 mol% or more and 95 mol% or less. The cyclic olefin polymer for fiber according to any one of claims 3 to 6, wherein the cyclic olefin having no aromatic ring contains a compound represented by the following formula (B-1).

(In the above formula [B-1], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, 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 a halogen atom; The monocyclic or polycyclic ring may have a double bond, and R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group, provided that aromatic rings are included. No.) The cyclic olefin having an aromatic ring is selected from the group consisting of a compound represented by the following formula (C-1), a compound represented by the following formula (C-2), and a compound represented by the following formula (C-3). The cyclic olefin polymer for fiber according to any one of claims 3 to 7, which contains one or more of the above.

(In formula (C-1) above, n and q are each independently 0, 1 or 2, and R ¹ to R ¹⁷ are each independently a hydrogen atom, a halogen atom other than a fluorine atom, or a fluorine atom a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom, one of R ¹⁰ to R ¹⁷ is a bond, and when q=0, R ¹⁰ and R ¹¹ , R ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁵ and R ¹⁰ may be bonded together to form a monocyclic or polycyclic ring, and q=1 or when ² , R10 and R11, ^R11 and ^R17 , ^R17 and ^R17 , ^R17 and ^R12 , ^R12 and ^R13 , ^R13 and ^R14 , ^R14 and ^R15 , ^R15 and ^{R 16} , R ¹⁶ and R ¹⁶ , R ¹⁶ and R ¹⁰ may combine with each other to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring may have a double bond. , said monocyclic ring or said polycyclic ring may be an aromatic ring.)

(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. ) A fiber comprising the cyclic olefin polymer for fiber according to any one of claims 1 to 8.