JP2023005379A - Method for producing cyclic olefin-based copolymer composition, cyclic olefin-based copolymer composition, molded body, method for producing molded body, and optical lens - Google Patents

Abstract

To provide a method for producing a cyclic olefin-based copolymer composition, in which lowering of polymerization activity is suppressed, and which can provide a molded body and an optical lens which are suppressed from deterioration of optical characteristics such as haze, light transmission, and the like.SOLUTION: Provided is a method for producing a cyclic olefin-based copolymer composition, comprising: step a of purifying a composition containing a cyclic olefin (d) having an aromatic ring and an oxidant (B) of the cyclic olefin (d) having an aromatic ring to reduce the amount of the oxidant (B); and step b where, after the step a, an α-olefin (a) having a carbon atom number of 2 to 20, tetracyclo[4.4.0.12,5.17,10]-3-dodecene (b) and/or norbornene (c), and the cyclic olefin (d) having an aromatic ring, contained in the composition, to produce a cyclic olefin-based copolymer (A). The oxidant (B) is contained in an amount of 0.01 to 2.2 ppm relative to the cyclic olefin-based copolymer (A).SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a method for producing a cyclic olefin copolymer composition, a cyclic olefin copolymer composition, a molded article, a method for producing a molded article, and an optical lens.

Cyclic olefin polymers are used for optical lenses such as imaging lenses, fθ lenses, and pickup lenses. Cyclic olefin polymers used for molded articles such as optical lenses are required to have characteristics such as low haze and high light transmittance.
Techniques relating to cyclic olefin polymers used in such optical lenses include, for example, Patent Documents 1 to 3.

Patent Document 1 discloses a cyclic olefin composition comprising a purified cyclic olefin obtained by contacting a cyclic olefin with an alkali and an antioxidant. This document describes further removal of low-boiling and/or high-boiling components from the purified cyclic olefin.

In Patent Document 2, a step of obtaining a purified norbornene-based compound by contacting a crude norbornene-based compound containing the epoxide impurity with a predetermined adsorbent; and polymerizing in the presence of a metal complex catalyst.
Patent Document 3 discloses a method for purifying a monomer composition, including a sulfur removal step of removing sulfur from a monomer composition containing a predetermined polycyclic aromatic vinyl compound.

JP 2005-145855 A WO2020-071494 JP 2020-050743 A

However, the cyclic olefin polymers described in Patent Documents 1 to 3 have room for improvement in haze and light transmittance.

As a result of intensive studies by the present inventors, when a polymer is prepared using a cyclic olefin having an aromatic ring, the cyclic olefin having an aromatic ring contains an oxidized product obtained by oxidizing the compound. It was found that the optical properties are lowered, and furthermore, it becomes a catalyst poison (substance that reacts with the catalyst and inhibits the catalytic action), thereby lowering the catalytic activity.

In terms of production, it is difficult to prevent the formation of the oxidant when synthesizing an aromatic ring-containing cyclic olefin, and it is very difficult to completely remove the oxidant that is formed. In view of such circumstances, the present inventors have found that if the amount of the oxidant contained together with the cyclic olefin-based copolymer is a predetermined value or less, the polymerization activity is lowered and the optical properties such as haze and light transmittance are deteriorated. The inventors have completed the present invention by discovering that the decrease can be suppressed. That is, the present invention is characterized in that the permissible value of the impurity oxidant is found from the standpoint of the productivity and production cost of the cyclic olefin copolymer.
That is, the present invention can be shown below.

（上記式（Ｄ－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、また上記単環または上記多環が二重結合を有していてもよく、上記単環または上記多環が芳香族環であってもよい。）

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

（上記式（Ｄ－３）中、ｑは１、２または３であり、Ｒ^３２～Ｒ^３９はそれぞれ独立に、水素原子、フッ素原子を除くハロゲン原子、またはフッ素原子を除くハロゲン原子で置換されていてもよい炭素原子数１～２０の炭化水素基であり、またｑ＝１のときＲ^３６とＲ^３７、Ｒ^３７とＲ^３８、Ｒ^３８とＲ^３９は互いに結合して単環または多環を形成していてもよく、またｑ＝２または３のときＲ^３６とＲ^３６、Ｒ^３６とＲ^３７、Ｒ^３７とＲ^３８、Ｒ^３８とＲ^３９、Ｒ^３９とＲ^３９は互いに結合して単環または多環を形成していてもよく、上記単環または上記多環が二重結合を有していてもよく、また上記単環または上記多環が芳香族環であってもよい。）
［９］ 酸化体（Ｂ）が、下記式（Ｂ－１）で示される化合物、下記式（Ｂ－２）で示される化合物、および下記式（Ｂ－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含む、［８］に記載の環状オレフィン系共重合体組成物の製造方法。

（上記式（Ｂ－１）中、ｎ、ｑ、Ｒ^１～Ｒ^１７は一般式（Ｄ－１）と同義である。）

（上記式（Ｂ－２）中、ｎ、ｍ、ｑ、Ｒ^１８～Ｒ^３１は一般式（Ｄ－２）と同義である。）

（上記式（Ｂ－３）中、ｑ、Ｒ^３２～Ｒ^３９は一般式（Ｄ－３）と同義である。）
［１０］ 芳香環を含有する環状オレフィン（ｄ）が、１，４－ジヒドロ－１，４－メタノナフタレンまたは１，４，４ａ，９ａ－テトラヒドロ－１，４－メタノフルオレンである、［１］～［９］のいずれかに記載の環状オレフィン系共重合体組成物の製造方法。
［１１］ 下記の構成単位（ａ１）と、構成単位（ｂ１）および構成単位（ｃ１）から選択される少なくとも１種を含む構成単位（ｂｃ１）と、構成単位（ｄ１）と、を含む環状オレフィン系共重合体（Ａ）と、
下記の芳香環を含有する環状オレフィン（ｄ）の酸化体（Ｂ）と、を含み、
環状オレフィン系共重合体（Ａ）に対して、酸化体（Ｂ）を０．０１ｐｐｍ～２．２ｐｐｍ含む、環状オレフィン系共重合体組成物。
構成単位（ａ１）：炭素原子数が２～２０のα－オレフィン（ａ）由来の構成単位
構成単位（ｂ１）：テトラシクロ［４．４．０．１^２，５．１^７，１０］－３－ドデセン（ｂ）由来の構成単位
構成単位（ｃ１）：ノルボルネン（ｃ）由来の構成単位
構成単位（ｄ１）：芳香環を含有する環状オレフィン（ｄ）由来の構成単位
［１２］ 前記芳香環を有する環状オレフィン（ｄ）は、ノルボルネン構造を有する、［１１］に記載の環状オレフィン系共重合体組成物。
［１３］ 酸化体（Ｂ）は、エポキシノルボルネン構造を含む、［１２］に記載の環状オレフィン系共重合体組成物。
［１４］ 構成単位（ａ１）、構成単位（ｂｃ１）、および構成単位（ｄ１）の合計１００モル％における、構成単位（ａ１）の含有量が４０～８０モル％の範囲にある、［１１］～［１３］のいずれかに記載の環状オレフィン系共重合体組成物。
［１５］ 芳香環を含有する環状オレフィン（ｄ）が、下記式（Ｄ－１）で示される化合物、下記式（Ｄ－２）で示される化合物、および下記式（Ｄ－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含む、［１１］～［１４］のいずれかに記載の環状オレフィン系共重合体組成物。

（上記式（Ｄ－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、また上記単環または上記多環が二重結合を有していてもよく、上記単環または上記多環が芳香族環であってもよい。）

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

（上記式（Ｄ－３）中、ｑは１、２または３であり、Ｒ^３２～Ｒ^３９はそれぞれ独立に、水素原子、フッ素原子を除くハロゲン原子、またはフッ素原子を除くハロゲン原子で置換されていてもよい炭素原子数１～２０の炭化水素基であり、またｑ＝１のときＲ^３６とＲ^３７、Ｒ^３７とＲ^３８、Ｒ^３８とＲ^３９は互いに結合して単環または多環を形成していてもよく、またｑ＝２または３のときＲ^３６とＲ^３６、Ｒ^３６とＲ^３７、Ｒ^３７とＲ^３８、Ｒ^３８とＲ^３９、Ｒ^３９とＲ^３９は互いに結合して単環または多環を形成していてもよく、上記単環または上記多環が二重結合を有していてもよく、また上記単環または上記多環が芳香族環であってもよい。）
［１６］ 酸化体（Ｂ）が、下記式（Ｂ－１）で示される化合物、下記式（Ｂ－２）で示される化合物、および下記式（Ｂ－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含む、［１５］に記載の環状オレフィン系共重合体組成物。

（上記式（Ｂ－１）中、ｎ、ｑ、Ｒ^１～Ｒ^１７は一般式（Ｄ－１）と同義である。）

（上記式（Ｂ－２）中、ｎ、ｍ、ｑ、Ｒ^１８～Ｒ^３１は一般式（Ｄ－２）と同義である。）

（上記式（Ｂ－３）中、ｑ、Ｒ^３２～Ｒ^３９は一般式（Ｄ－３）と同義である。）
［１７］ 前記環状オレフィン系共重合体組成物からなる厚さ１．０ｍｍの射出成形シートを作製したとき、当該射出成形シートのアッベ数νが３５～５５の範囲にある、［１１］～［１６］のいずれかに記載の環状オレフィン系共重合体組成物。
［１８］ 前記環状オレフィン系共重合体組成物からなる厚さ１．０ｍｍの射出成形シートを作製したとき、当該射出成形シートの複屈折が４０ｎｍ未満である、［１１］～［１７］のいずれかに記載の環状オレフィン系共重合体組成物。
［１９］ 前記環状オレフィン系共重合体組成物からなる厚さ１．０ｍｍの射出成形シートを作製したとき、当該射出成形シートの波長４５０ｎｍの平行光線透過率が８５％以上である、［１１］～［１８］のいずれかに記載の環状オレフィン系共重合体組成物。
［２０］ 芳香環を含有する環状オレフィン（ｄ）が、１，４－ジヒドロ－１，４－メタノナフタレンまたは１，４，４ａ，９ａ－テトラヒドロ－１，４－メタノフルオレンである、［１１］～［１９］のいずれかに記載の環状オレフィン系共重合体組成物。
［２１］ ［１１］～［２０］のいずれかに記載の環状オレフィン系共重合体組成物を含んでなる成形体。
［２２］ 下記の構成単位（ａ１）と、構成単位（ｂ１）および構成単位（ｃ１）から選択される少なくとも１種を含む構成単位（ｂｃ１）と、構成単位（ｄ１）と、を含む環状オレフィン系共重合体（Ａ）と、
下記の芳香環を含有する環状オレフィン（ｄ）の酸化体（Ｂ）と、を含み、
環状オレフィン系共重合体（Ａ）に対して、酸化体（Ｂ）を０．０１ｐｐｍ～２．２ｐｐｍ含む環状オレフィン系共重合体組成物を、金型内で成形する工程を含む、成形体の製造方法。
構成単位（ａ１）：炭素原子数が２～２０のα－オレフィン（ａ）由来の構成単位
構成単位（ｂ１）：テトラシクロ［４．４．０．１^２，５．１^７，１０］－３－ドデセン（ｂ）由来の構成単位
構成単位（ｃ１）：ノルボルネン（ｃ）由来の構成単位
構成単位（ｄ１）：芳香環を含有する環状オレフィン（ｄ）由来の構成単位
［２３］ ［２１］に記載の成形体からなる光学レンズ。 [1] Purifying a composition containing a cyclic olefin (d) having an aromatic ring and an oxidant (B) of the cyclic olefin (d) containing an aromatic ring to reduce the amount of the oxidant (B) a step of
After step a, α-olefin (a) having 2 to 20 carbon atoms and tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene (b) and/or norbornene (c) and the aromatic ring-containing cyclic olefin (d) contained in the composition are copolymerized to obtain a cyclic olefin copolymer. and a step b of manufacturing (A);
A method for producing a cyclic olefin copolymer composition comprising 0.01 ppm to 2.2 ppm of the oxidant (B) relative to the cyclic olefin copolymer (A).
[2] The method for producing a cyclic olefin copolymer composition according to [1], wherein the aromatic ring-containing cyclic olefin (d) has a norbornene structure.
[3] The method for producing a cyclic olefin copolymer composition according to [2], wherein the oxidant (B) contains an epoxynorbornene structure.
[4] In the step a, the amount of the oxidant (B) in the composition containing the aromatic ring-containing cyclic olefin (d) and the oxidant (B) is 150 ppm with respect to the composition. The method for producing a cyclic olefin-based copolymer composition according to any one of [1] to [3], which is reduced to the following.
[5] The content of the structural unit (a1) is in the range of 40 to 80 mol% in the total 100 mol% of the structural unit (a1), the structural unit (bc1), and the structural unit (d1), [1] A method for producing a cyclic olefin copolymer composition according to any one of to [4].
[6] Any one of [1] to [5], wherein the content of the structural unit (d1) is in the range of 5 to 95 mol% based on the total 100 mol% of the structural unit (bc1) and the structural unit (d1) A method for producing the cyclic olefin copolymer composition according to .
[7] The method for producing a cyclic olefin copolymer composition according to any one of [1] to [6], wherein the structural unit (bc1) contains the structural unit (b1).
[8] The cyclic olefin (d) containing an aromatic ring is a compound represented by the following formula (D-1), a compound represented by the following formula (D-2), and a compound represented by the following formula (D-3). The method for producing a cyclic olefin copolymer composition according to any one of [1] to [7], containing one or more selected from the group consisting of compounds.

(In the above formula (D-1), n and q are each independently 0, 1 or 2, and R ¹ to R ¹⁷ are each independently a hydrogen atom, a halogen atom other than a fluorine atom, or 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. , the monocyclic ring or the polycyclic ring may be an aromatic ring.)

(In formula (D-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 (D-3) above, q is 1, 2 or 3, and each of R ³² to R ³⁹ is 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] The oxidant (B) is selected from the group consisting of a compound represented by the following formula (B-1), a compound represented by the following formula (B-2), and a compound represented by the following formula (B-3) The method for producing a cyclic olefin copolymer composition according to [8], which contains one or more selected types.

(In formula (B-1) above, n, q, and R ¹ to R ¹⁷ have the same meanings as in general formula (D-1).)

(In formula (B-2) above, n, m, q, and R ¹⁸ to R ³¹ have the same meanings as in general formula (D-2).)

(In formula (B-3) above, q and R ³² to R ³⁹ have the same meanings as in general formula (D-3).)
[10] The cyclic olefin (d) containing an aromatic ring is 1,4-dihydro-1,4-methanonaphthalene or 1,4,4a,9a-tetrahydro-1,4-methanofluorene, [1] A method for producing a cyclic olefin copolymer composition according to any one of [9].
[11] A cyclic olefin comprising the following structural unit (a1), a structural unit (bc1) containing at least one selected from structural units (b1) and structural units (c1), and a structural unit (d1) System copolymer (A),
and an oxidized product (B) of a cyclic olefin (d) containing the following aromatic ring,
A cyclic olefin copolymer composition containing 0.01 ppm to 2.2 ppm of an oxidant (B) relative to the cyclic olefin copolymer (A).
Structural unit (a1): structural unit derived from α-olefin (a) having 2 to 20 carbon atoms Structural unit (b1): tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene (b)-derived structural unit Structural unit (c1): Norbornene (c)-derived structural unit Structural unit (d1): Aromatic ring-containing cyclic olefin (d)-derived structural unit [12] The cyclic olefin copolymer composition according to [11], wherein the aromatic ring-containing cyclic olefin (d) has a norbornene structure.
[13] The cyclic olefin copolymer composition according to [12], wherein the oxidant (B) contains an epoxynorbornene structure.
[14] The content of the structural unit (a1) is in the range of 40 to 80 mol% in the total 100 mol% of the structural unit (a1), the structural unit (bc1), and the structural unit (d1), [11] The cyclic olefin copolymer composition according to any one of [13].
[15] The cyclic olefin (d) containing an aromatic ring is a compound represented by the following formula (D-1), a compound represented by the following formula (D-2), and a compound represented by the following formula (D-3). The cyclic olefin copolymer composition according to any one of [11] to [14], containing one or more selected from the group consisting of compounds.

(In the above formula (D-1), n and q are each independently 0, 1 or 2, and R ¹ to R ¹⁷ are each independently a hydrogen atom, a halogen atom other than a fluorine atom, or 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. , the monocyclic ring or the polycyclic ring may be an aromatic ring.)

(In formula (D-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 (D-3) above, q is 1, 2 or 3, and each of R ³² to R ³⁹ is 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. )
[16] The oxidant (B) is from the group consisting of a compound represented by the following formula (B-1), a compound represented by the following formula (B-2), and a compound represented by the following formula (B-3) The cyclic olefin copolymer composition according to [15], containing one or more selected types.

(In formula (B-1) above, n, q, and R ¹ to R ¹⁷ have the same meanings as in general formula (D-1).)

(In formula (B-2) above, n, m, q, and R ¹⁸ to R ³¹ have the same meanings as in general formula (D-2).)

(In formula (B-3) above, q and R ³² to R ³⁹ have the same meanings as in general formula (D-3).)
[17] When an injection-molded sheet having a thickness of 1.0 mm is produced from the cyclic olefin copolymer composition, the Abbe number ν of the injection-molded sheet is in the range of 35 to 55, [11] to [ 16], the cyclic olefin copolymer composition according to any one of the above.
[18] Any one of [11] to [17], wherein when an injection-molded sheet having a thickness of 1.0 mm is produced from the cyclic olefin copolymer composition, the birefringence of the injection-molded sheet is less than 40 nm. The cyclic olefin copolymer composition according to 1.
[19] When an injection-molded sheet having a thickness of 1.0 mm is produced from the cyclic olefin copolymer composition, the parallel light transmittance of the injection-molded sheet at a wavelength of 450 nm is 85% or more. The cyclic olefin copolymer composition according to any one of [18].
[20] The cyclic olefin (d) containing an aromatic ring is 1,4-dihydro-1,4-methanonaphthalene or 1,4,4a,9a-tetrahydro-1,4-methanofluorene, [11] The cyclic olefin copolymer composition according to any one of [19].
[21] A molded article comprising the cyclic olefin copolymer composition according to any one of [11] to [20].
[22] A cyclic olefin comprising the following structural unit (a1), a structural unit (bc1) containing at least one selected from structural units (b1) and structural units (c1), and a structural unit (d1) System copolymer (A),
and an oxidized product (B) of a cyclic olefin (d) containing the following aromatic ring,
A molded body, comprising a step of molding a cyclic olefin copolymer composition containing 0.01 ppm to 2.2 ppm of the oxidized product (B) in a mold with respect to the cyclic olefin copolymer (A). Production method.
Structural unit (a1): structural unit derived from α-olefin (a) having 2 to 20 carbon atoms Structural unit (b1): tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene (b)-derived structural unit Structural unit (c1): Norbornene (c)-derived structural unit Structural unit (d1): Aromatic ring-containing cyclic olefin (d)-derived structural unit [23] An optical lens comprising the molded article according to [21].

According to the present invention, it is possible to provide a method for producing a cyclic olefin copolymer composition in which a cyclic olefin copolymer composition in which a decrease in polymerization activity is suppressed is obtained. Also, it is possible to provide a molded article, an optical lens, and a method for producing a molded article in which deterioration of optical properties such as light transmittance is suppressed.

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described below based on embodiments. In addition, "~" represents "more than" to "less than" unless otherwise specified.

The cyclic olefin copolymer composition of the present embodiment is
A cyclic olefin-based copolymer comprising the following structural unit (a1), a structural unit (bc1) containing at least one selected from structural units (b1) and structural units (c1), and a structural unit (d1) Union (A);
and an oxidized product (B) of a cyclic olefin (d) containing the following aromatic ring,
The oxidant (B) is contained in an amount of 0.01 ppm to 2.2 ppm with respect to the cyclic olefin copolymer (A).
Structural unit (a1): structural unit derived from α-olefin (a) having 2 to 20 carbon atoms Structural unit (b1): tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene (b)-derived structural unit Structural unit (c1): Norbornene (c)-derived structural unit Structural unit (d1): Aromatic ring-containing cyclic olefin (d)-derived structural unit

According to the present embodiment, it is possible to provide a cyclic olefin-based copolymer composition in which a decrease in polymerization activity is suppressed, and the composition suppresses a decrease in optical properties such as haze and light transmittance. It is possible to provide a molded article and an optical lens. That is, the present invention is characterized in that the permissible value of the impurity oxidant is found from the standpoint of the productivity and production cost of the cyclic olefin copolymer.

[Cyclic olefin copolymer (A)]
The cyclic olefin copolymer (A) of the present embodiment comprises a structural unit (a1), a structural unit (bc1) containing at least one selected from the structural unit (b1) and the structural unit (c1), and a structural and the unit (d1).

(Constituent unit (a1))
The structural unit (a1) according to the present embodiment is a structural unit derived from an α-olefin (a) having 2 to 20 carbon atoms.

The α-olefin (a) 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 (a1), the structural unit (bc1) and the structural unit (d1) in the cyclic olefin-based copolymer according to the present embodiment is 100 mol%, the cyclic olefin-based copolymer according to the present embodiment The content of the structural unit (a1) in the copolymer is preferably 40 mol% or more and 80 mol% or less, more preferably 45 mol% or more and 75 mol% or less, still more preferably 50 mol% or more and 70 mol% or less. is.

When the content of the structural unit (a1) is at least the above lower limit, the heat resistance and dimensional stability of the resulting molded article can be improved. Further, when the content of the structural unit (a1) is equal to or less than the upper limit, the obtained molded article can be improved in transparency and the like.

That is, when the content of the structural unit (a1) is within the above numerical range, excellent heat resistance, dimensional stability and transparency are achieved in a well-balanced manner.
In this embodiment, the content of the structural unit (a1) can be measured, for example, by ¹ H-NMR or ¹³ C-NMR.

(Constituent unit (bc1))
The structural unit (bc1) according to this embodiment is tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene (b)-derived structural unit (b1) and norbornene (bicyclo[2.2.1]-2-heptene) (c)-derived structural unit (c1) at least Includes 1 species. In the present embodiment, the structural unit (bc1) preferably contains the structural unit (b1).

From the viewpoint of the effect of the present invention, when the total content of the structural unit (a1), the structural unit (bc1) and the structural unit (d1) in the cyclic olefin copolymer according to the present embodiment is 100 mol%, The content of the structural unit (bc1) in the cyclic olefin copolymer according to the present embodiment is preferably 5 mol% or more and 50 mol% or less, more preferably 10 mol% or more and 40 mol% or less, still more preferably It is 15 mol % or more and 30 mol % or less.

In this embodiment, the content of the structural unit (bc1) can be measured by, for example, ¹ H-NMR or ¹³ C-NMR.

(Constituent unit (d1))
The structural unit (d1) according to this embodiment is a structural unit derived from a cyclic olefin (d) containing an aromatic ring.
The aromatic ring-containing cyclic olefin (d) can be selected from conventionally known compounds and used as long as the effects of the present invention are achieved.

In the present embodiment, the aromatic ring-containing cyclic olefin (d) preferably has a norbornene structure. For example, a compound represented by the following formula (D-1), a compound represented by the following formula (D-2), and a compound represented by the following formula (D-3) are more preferable. These aromatic ring-containing cyclic olefins may be used singly or in combination of two or more.

In formula (D-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 (D-1), compounds represented by the following formula (D-1A) are preferable.

In formula (D-2) above, n and m are each independently 0, 1 or 2, and q is 1, 2 or 3. m is preferably 0 or 1, more preferably 1. n is preferably 0 or 1, more preferably 0. q is preferably 1 or 2, more preferably 1.

Each of R ¹⁸ to R ³¹ is independently a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom other than a fluorine atom.
Each of R ¹⁸ to R ³¹ is preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrogen atom.

When q=1, R ²⁸ and R ²⁹ , R ²⁹ and R ³⁰ , R ³⁰ and R ³¹ may be bonded together to form a monocyclic or polycyclic ring, and when q=2 or 3, R ²⁸ and R ²⁸ , R ²⁸ and R ²⁹ , R ²⁹ and R ³⁰ , R ³⁰ and R ³¹ , R ³¹ and R ³¹ may be bonded together to form a monocyclic or polycyclic ring, and the monocyclic or The polycyclic ring may have a double bond, and the monocyclic or polycyclic ring may be an aromatic ring.

上記式（Ｄ－３）中、ｑは１、２または３であり、１または２であることが好ましく、１であることがより好ましい。

In formula (D-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 (d) having an aromatic ring according to the present embodiment is preferably one having one aromatic ring. For example, 1,4-dihydro-1,4-methanonaphthalene (hereinafter , benzonorbornadiene or BNBD), 1,4,4a,9a-tetrahydro-1,4-methanofluorene (hereinafter also referred to as indenenorbornene) and at least one selected from methylphenylnorbornene preferable.

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

In formula (D-1′), formula (D-2′) and formula (D-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 (D-1′), (D-2′) and (D-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 (d) having an aromatic ring according to the present embodiment preferably has one aromatic ring, such as 1,4-dihydro-1,4-methanonaphthalene and 1 ,4,4a,9a-tetrahydro-1,4-methanofluorene is preferred.

When the total content of the structural unit (bc1) and the structural unit (d1) in the cyclic olefin copolymer according to the present embodiment is 100 mol%, the cyclic olefin copolymer according to the present embodiment The content of the above structural unit (d1) is preferably 5 mol% or more and 95 mol% or less, more preferably 10 mol% or more and 90 mol% or less, still more preferably 20 mol% or more and 80 mol% or less, still more preferably 30 mol % or more and 80 mol % or less, more preferably 40 mol % or more and 78 mol % or less.

When the content of the structural unit (d1) is equal to or higher than the lower limit, the resulting molded article can have a high refractive index and an even lower Abbe number. Further, when the content of the structural unit (d1) is equal to or less than the upper limit, the obtained molded article can have a better balance of refractive index and Abbe number.

From the viewpoint of the effect of the present invention, when the total content of the structural unit (a1), the structural unit (bc1) and the structural unit (d1) in the cyclic olefin copolymer according to the present embodiment is 100 mol%, The content of the structural unit (d1) in the cyclic olefin copolymer according to the present embodiment is preferably 5 mol% or more and 45 mol% or less, more preferably 8 mol% or more and 30 mol% or less, still more preferably It is 10 mol % or more and 25 mol % or less.

In this embodiment, the content of the structural unit (d1) can be measured, for example, by ¹ H-NMR or ¹³ C-NMR.

[Oxidant (B)]
The oxidant (B) is a by-product of the oxidation of the cyclic olefin (d) containing an aromatic ring, and is used during synthesis of the cyclic olefin (d), storage of the cyclic olefin (d), etc. generated.

When synthesizing the cyclic olefin (d) having an aromatic ring, when storing the cyclic olefin (d), it is difficult from a production standpoint to prevent the generation of the oxidized product (B). Since it is very difficult to completely remove the oxidant (B), a cyclic olefin contained in the cyclic olefin (d) containing an aromatic ring and synthesized using the cyclic olefin (d) Included with the copolymer.

The oxidant (B) has a structure in which the carbon-carbon double bond of the norbornene structure in the aromatic ring-containing cyclic olefin (d) is oxidized. Structures in which carbon-carbon double bonds are oxidized include epoxy rings (epoxynorbornene structures), ketones, hydroxyl groups, and the like. In this embodiment, the oxidant (B) can contain an epoxynorbornene structure.

The oxidant (B) of the present embodiment is a group consisting of a compound represented by the following formula (B-1), a compound represented by the following formula (B-2), and a compound represented by the following formula (B-3). It can contain one or more selected from.

In formula (B-1) above, n, q, and R ¹ to R ¹⁷ have the same meanings as in general formula (D-1).

In formula (B-2) above, n, m, q, and R ¹⁸ to R ³¹ have the same meanings as in general formula (D-2).

In formula (B-3) above, q and R ³² to R ³⁹ have the same meanings as in general formula (D-3).

Oxidant (B) may comprise an oxidant of a dimer of cyclic olefin (d) containing an aromatic ring.
For example, when 1,4-dihydro-1,4-methanonaphthalene (BNBD) is used as the cyclic olefin (d) having an aromatic ring, the oxidized dimer includes a compound represented by the following formula. be

From the viewpoint of the effect of the present invention, the oxidant (B) has a mass of 0.01 ppm to 2.2 ppm, preferably 0.05 ppm to 2.2 ppm, more preferably 0.05 ppm to 2.2 ppm, more preferably It can contain from 0.1 ppm to 2.2 ppm.
The content of the oxidant (B) can be determined from the area ratio of GC-MS (internal standard method).

The content of the oxidant (B) in the cyclic olefin-based copolymer composition is determined by purifying the raw material, the cyclic olefin (d) composition containing an aromatic ring containing the oxidant (B). The amount of (B) can be reduced.
A purification method can be carried out by a conventionally known method. For example, there is a method of immersing in alumina and drying.
In the purification step, it is preferable that the mass of the oxidant (B) is reduced to 150 ppm or less with respect to the aromatic ring-containing cyclic olefin (d) composition. More preferably 100 ppm or less, more preferably 80 ppm or less.
When polymerizing a cyclic olefin copolymer containing many structural units (d1), for example, the total content of the structural unit (a1), the structural unit (bc1) and the structural unit (d1) in the cyclic olefin copolymer is When the content of the structural unit (d1) in the cyclic olefin copolymer is 20 mol% or more and 25 mol% or less when 100 mol%, the structural unit (d1) is replaced with an aromatic ring in the purification step. It is preferable that the oxidant (B) is reduced to 100 ppm or less by mass with respect to the cyclic olefin (d) composition containing In the production process, the charged amount of the cyclic olefin (d) having an aromatic ring and the content of the oxidant (B) in the resulting cyclic olefin copolymer composition are not necessarily in a proportional relationship. However, since the oxidant (B) affects the polymerization activity in the polymerization step, when the charged amount of the cyclic olefin (d) having an aromatic ring is large, the content of the oxidant (B) is increased in the purification step. preferably reduced.

The cyclic olefin copolymer (A) contained in the cyclic olefin copolymer composition according to the present embodiment is, for example, JP-A-60-168708, JP-A-61-120816, 61-115912, JP-A-61-115916, JP-A-61-271308, JP-A-61-272216, JP-A-62-252406, JP-A-62-252407 , JP-A-2007-314806, JP-A-2010-241932, etc. Select appropriate conditions according to the method, and the cyclic olefin (d) composition containing an aromatic ring in which the oxidant (B) is reduced by the above method The cyclic olefin copolymer (A) and the oxidized product (B) of the cyclic olefin (d) containing an aromatic ring are also included. That is, by the synthesis method, a cyclic olefin copolymer composition containing the cyclic olefin copolymer (A) and the oxidant (B) is obtained.

Specifically, the method for producing a cyclic olefin copolymer composition according to the present embodiment includes:
a step a of purifying a composition containing an aromatic ring-containing cyclic olefin (d) and an oxidant (B) of the aromatic ring-containing cyclic olefin (d) to reduce the amount of the oxidant (B); ,
After step a, the compound (a), the compound (b) and/or the compound (c), and the compound (d) contained in the composition are copolymerized to obtain a cyclic olefin copolymer (A) a step b of producing
including.

After step a, the amount of the oxidant (B) contained in the composition comprising the aromatic ring-containing cyclic olefin (d) and the oxidant (B) of the aromatic ring-containing cyclic olefin (d) is It can be confirmed by a method such as gas chromatography. The amount of the oxidant (B) contained in the composition containing the aromatic ring-containing cyclic olefin (d) and the oxidant (B) of the aromatic ring-containing cyclic olefin (d) is If not reduced to preferably 150 ppm or less by mass relative to the cyclic olefin (d) composition, step a can be repeated.

The cyclic olefin copolymer composition according to the present embodiment contains the cyclic olefin copolymer (A) and the oxidant (B), and if necessary, may further contain other components.
Other components include a hydrophilic stabilizer and the like. It is more preferable to contain a hydrophilic stabilizer because deterioration of optical performance under high temperature and high humidity conditions can be suppressed.

The hydrophilic stabilizer is preferably a fatty acid ester of fatty acid and polyhydric alcohol. Fatty acid esters of fatty acids and polyhydric alcohols having one or more ether groups are more preferred.

Examples of fatty acid esters include monoglycerin fatty acid ester, diglycerin fatty acid ester, triglycerin fatty acid ester, pentaerythritol monostearate, pentaerythritol distearate, and pentaerythritol tristearate.

Fatty acid esters of fatty acids and polyhydric alcohols having one or more ether groups are esters of fatty acids and polyhydric alcohols having one or more ether groups. Note that the ether group of the polyhydric alcohol does not include the ether group in the ester group.

Examples of polyhydric alcohols having one or more ether groups include monoglycerin, diglycerin, triglycerin, tetraglycerin, and sorbitan.

In this embodiment, the fatty acid ester preferably includes monoglycerin fatty acid ester, diglycerin fatty acid ester, and triglycerin fatty acid ester. A diglycerin fatty acid ester is obtained by esterifying at least one of the four hydroxy groups contained in diglycerin with a fatty acid.

Fatty acids include saturated fatty acids such as butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, capric acid, lauric acid, myristic acid, palmitic acid, and stearic acid; crotonic acid, myristoleic acid, palmitoleic acid; , sapienic acid, oleic acid, elaidic acid, gadoleic acid, eicosenoic acid, and other monounsaturated fatty acids; linoleic acid, eicosadienoic acid, docosadienoic acid, and other diunsaturated fatty acids; triunsaturated fatty acids such as enoic acid; tetraunsaturated fatty acids such as stearidonic acid, arachidonic acid and eicosatetraenoic acid; and the like.

Diglycerin fatty acid esters include diglycerin monocaprylate, diglycerin dicaprylate, diglycerin monocaprate, diglycerin dicaprate, diglycerin monolaurate, diglycerin dilaurate, diglycerin monomyristate, and diglycerin dimyristate. , diglycerin monopalmitate, diglycerin dipalmitate, diglycerin monostearate, diglycerin distearate, diglycerin monobehenate, diglycerin dibehenate; diglycerin unsaturated fatty acid esters such as glycerin dioleate; and the like, and one or more selected from these can be used in combination.

In this embodiment, the diglycerin fatty acid ester is preferably an ester of diglycerin and a saturated or unsaturated fatty acid having 12 to 18 carbon atoms selected from the above.

From the viewpoint of the effects of the present embodiment, it is preferable to contain a diglycerin unsaturated fatty acid ester as a main component, and among these, it is more preferable to contain a diglycerin monooleate as a main component. Since the diglycerin skeleton is hydrophilic and the fatty acid improves the compatibility with the resin, the transparency is maintained and the moisture and heat resistance is excellent.

The cyclic olefin copolymer composition according to the present embodiment may contain at least one diglycerin fatty acid ester. Preferred embodiments of the at least one diglycerol fatty acid ester include a monoester alone or a combination of a monoester and a diester.
Triglycerin fatty acid esters are esters of fatty acids and triglycerin.
The triglycerin fatty acid ester according to this embodiment is obtained by esterifying at least one of the five hydroxy groups contained in triglycerin with a fatty acid.

Triglycerin fatty acid esters include triglycerin monocaprylate, triglycerin dicaprylate, triglycerin tricaprylate, triglycerin monocaprate, triglycerin dicaprate, triglycerin tricaprate, triglycerin monolaurate, triglycerin dilaurate, Triglycerin Trilaurate, Triglycerin Monomyristate, Triglycerin Dimyristate, Triglycerin Trimyristate, Triglycerin Monopalmitate, Triglycerin Dipalmitate, Triglycerin Tripalmyrate, Triglycerin Monostearate, Triglycerin Triglycerin saturated fatty acid esters such as distearate, triglycerin tristearate, triglycerin monobehenate, triglycerin dibehenate, triglycerin tribehenate; triglycerin monooleate, triglycerin dioleate, triglycerin trioleate Triglycerin unsaturated fatty acid esters such as;

The triglycerin fatty acid ester according to the present embodiment preferably contains an ester of triglycerin and a saturated or unsaturated fatty acid having 8 to 24 carbon atoms, and triglycerin and a saturated or unsaturated fatty acid having 12 to 18 carbon atoms. More preferably, it contains an ester with

Examples of the triglycerin fatty acid ester according to the present embodiment include a monoester alone, a mixture of a monoester and a diester, a mixture of a monoester, a diester and a triester, and the like.

As such a triglycerol fatty acid ester, for example, compounds described in JP-A-2006-232714, JP-A-2002-275308, JP-A-10-165152, etc. can be used.

Commercially available hydrophilic stabilizers according to the present embodiment include, for example, Rikemal DO-100 (manufactured by Riken Vitamin Co., Ltd.) and Excepar PE-MS (manufactured by Kao Corporation).

In the cyclic olefin copolymer composition according to the present embodiment, the lower limit of the content of the hydrophilic stabilizer is 0.05 parts by mass or more with respect to 100 parts by mass of the cyclic olefin copolymer (A). is preferred, and 0.4 parts by mass or more is more preferred. The upper limit of the content of the hydrophilic stabilizer is preferably 3.0 parts by mass or less, more preferably 2.5 parts by mass or less, relative to 100 parts by mass of the cyclic olefin copolymer (A). , 1.2 parts by mass or less.

<Cyclic olefin copolymer composition>
In the cyclic olefin-based copolymer composition according to the present embodiment, when an injection-molded sheet having a thickness of 1.0 mm made of the cyclic olefin-based copolymer composition is produced, the above injection molding measured according to ASTM D542 The refractive index (nd) of the sheet at a wavelength of 589 nm is preferably 1.545 or higher, preferably 1.550 or higher, and more preferably 1.555 or higher. Although the upper limit of the refractive index (nd) is not particularly limited, it is, for example, 1.580 or less.

When the refractive index is within the above range, the thickness of the molded article obtained by using the cyclic olefin copolymer composition according to the present embodiment can be kept excellent while maintaining good optical properties.

In addition, in the cyclic olefin copolymer composition according to the present embodiment, from the viewpoint of further improving the transparency of the molded product obtained, an injection-molded sheet having a thickness of 1.0 mm made of the cyclic olefin copolymer composition is used. , the haze of the injection-molded sheet measured according to JIS K7136 is preferably less than 5%.

In addition, in the cyclic olefin copolymer composition according to the present embodiment, from the viewpoint of adjusting the Abbe number (ν) of the obtained molded body to a more suitable range, the thickness of the cyclic olefin copolymer composition When a 1.0 mm injection-molded sheet is produced, the Abbe number (ν) of the injection-molded sheet is preferably 35 or more and 55 or less, more preferably 40 or more and 50 or less, and still more preferably 43 or more and 47 or less.

The Abbe number (ν) of the injection-molded sheet can be calculated from the refractive index of the injection-molded sheet at wavelengths of 486 nm, 589 nm and 656 nm at 23° C. using the following formula.
ν=(nD−1)/(nF−nC)
nD: refractive index at a wavelength of 589 nm nC: refractive index at a wavelength of 656 nm nF: refractive index at a wavelength of 486 nm

In addition, in the cyclic olefin copolymer composition according to the present embodiment, from the viewpoint of adjusting the birefringence of the obtained molded body to a more suitable range, the thickness of the cyclic olefin copolymer composition is 1.0 mm. When the injection-molded sheet of is produced, the birefringence of the injection-molded sheet is preferably less than 40 nm.

In the present embodiment, the birefringence of the injection-molded sheet is the average value of phase differences of 20 to 35 mm from the gate direction measured at a measurement wavelength of 650 nm using a KOBRA CCD manufactured by Oji Scientific Instruments.

In the cyclic olefin copolymer composition according to the present embodiment, from the viewpoint of adjusting the parallel light transmittance of the resulting molded article to a more suitable range, the thickness of the cyclic olefin copolymer composition is 1.0 mm. When the injection-molded sheet of (1) is produced, it is preferable that the parallel light transmittance of the injection-molded sheet at a wavelength of 450 nm is 85% or more. In this embodiment, the decrease in light transmittance is suppressed, and the parallel light transmittance can be maintained within the above range.

The glass transition temperature (Tg) of the cyclic olefin copolymer composition according to the present embodiment, measured by a differential scanning calorimeter (DSC), is determined by the transparency, haze, Abbe number, birefringence and From the viewpoint of further improving heat resistance while maintaining a good refractive index, the temperature is preferably 120° C. or higher and 180° C. or lower, more preferably 130° C. or higher and 170° C. or lower, and still more preferably 140° C. or higher and 160° C. or lower. .

The intrinsic viscosity [η] (in decalin at 135° C.) of the cyclic olefin copolymer composition according to the present embodiment is, for example, 0.05 to 5.0 dl/g, preferably 0.2 to 4.0 dl/g. g, more preferably 0.3 to 2.0 dl/g, particularly preferably 0.4 to 1.0 dl/g.

[Molded body]
The molded article according to this embodiment is a molded article made of the cyclic olefin copolymer composition according to this embodiment.

Since the molded article according to the present embodiment contains the cyclic olefin copolymer (A) according to the present embodiment, it has an excellent balance of heat resistance, transparency, haze, birefringence, chemical resistance, low hygroscopicity, etc. In addition, it exhibits a lower Abbe number than conventional resin materials while having a higher refractive index. Therefore, it is suitable for use as an optical lens.

Since the molded article according to the present embodiment has excellent optical properties, it can be suitably used as an optical lens such as a spectacle lens, an fθ lens, a pickup lens, an imaging lens, a sensor lens, a prism, a light guide plate, and an in-vehicle camera lens. Since it exhibits a lower Abbe number than conventional resin materials while having a high refractive index, it can be particularly suitably used as an imaging lens.

The imaging lens unit is composed of a plurality of lenses having different Abbe numbers and refractive indices, and generally, a plurality of lenses having a large Abbe number and a plurality of lenses having a small Abbe number are combined. The molded article according to the present embodiment can be suitably used as a lens corresponding to an intermediate region between a high Abbe number and a low Abbe number, and can improve the degree of freedom in designing the lens unit.

In addition, the content of the cyclic olefin copolymer (A) in the molded article according to the present embodiment is, from the viewpoint of further improving the performance balance of transparency, haze, birefringence, Abbe number and refractive index, the molding When the entire body is 100% by mass, it is preferably 50% by mass or more and 100% by mass or less, more preferably 70% by mass or more and 100% by mass or less, and still 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 molded article according to this embodiment can be obtained by molding a resin composition containing the cyclic olefin copolymer (A) into a predetermined shape in a mold. The method for obtaining a molded article by molding the resin composition containing the cyclic olefin copolymer (A) is not particularly limited, and known methods can be used. Depending on the application and shape, for example, extrusion molding, injection molding, compression molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, vacuum molding, powder slush molding, calendar molding, foam molding, etc. is applicable. 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.

The molded article according to this embodiment can be used in various forms such as lens-shaped, spherical, rod-shaped, plate-shaped, cylindrical, cylindrical, tube-shaped, fibrous, film- or sheet-shaped.

The molded article or cyclic olefin copolymer composition according to the present embodiment may optionally contain known additives as optional components within a range that does not impair the good physical properties of the molded article according to the present embodiment. can be made Additives include, for example, phenol stabilizers, higher fatty acid metal salts, antioxidants, ultraviolet absorbers, hindered amine light stabilizers, hydrochloric acid absorbers, metal deactivators, antistatic agents, antifog agents, and lubricants. , a slip agent, a nucleating agent, a plasticizer, a flame retardant, a phosphorus stabilizer, and the like 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 optical lens according to this embodiment may be combined with an optical lens different from the optical lens described above to form an optical lens system.
That is, the optical lens system according to the present embodiment is different from the first optical lens constituted by the molded body containing the cyclic olefin copolymer (A) according to the present embodiment and the first optical lens. a second optical lens;

Although the second optical lens is not particularly limited, for example, an optical lens made of at least one kind of resin selected from polycarbonate resin and polyester resin can be used.
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.
In each Production Example, Example and Comparative Example, various physical properties were measured or evaluated by the following methods.

[Method for measuring oxidant content in benzonorbornadiene (BNBD)]
The oxide compound content in BNBD was measured using GC2014 SHIMADZU GASCHROMATOGRAPH under the following conditions.
Injection volume: 2 μL
Injection Mode: Split Spirit Ratio: 30
Vaporization chamber temperature: 280°C
Carrier gas: He
Control mode: linear velocity Total flow rate: 119 mL/min
Column flow rate: 3.75 mL/min
Linear velocity: 28.9 cm/sec
Pressure: 21.2kPa
Column name: DB1
Column size: length 30.0m, inner diameter 0.53mm ID
Detector temperature: 320°C
Measurement limit: 1.0 ppm
Quantification was performed by the internal standard method (cumene).

[Method for measuring BNBD-derived oxidant content in polymer]
Soxhlet extraction (acetone/hexane=1/1 (v/v)) was performed for 7 hours, and the constant volume was analyzed by the same method as the method for measuring the content of oxidized compounds in BNBD.

[Method for Measuring Content of Each Structural Unit Constituting Cyclic Olefin Copolymer]
ethylene, tetracyclo[4.4.0.1 ^2,5 . The contents of 1 ^7,10 ]-3-dodecene and aromatic ring-containing cyclic olefins 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
Accumulated times: 6000 to 16000 times
Measurement temperature: 120°C
Compositions of ethylene, tetracyclododecene, and aromatic ring-containing cyclic olefins were quantified by ¹³ C-NMR spectra 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 copolymer was measured under an N2 (nitrogen) atmosphere. The cyclic olefin copolymer 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 copolymer was obtained from the endothermic curve when the temperature was raised to 200°C at a temperature elevation rate of 10°C/min.

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

[Micro compounder molding]
The cyclic olefin copolymer composition was kneaded at a kneading temperature of 280° C. and 50 rpm for 5 minutes using a small kneader manufactured by Xplore Instruments, and then kneaded at a cylinder temperature of 280 using an injection molding machine manufactured by Xplore Instruments. °C, an injection pressure of 12 to 15 bar, and a mold temperature of 135°C to prepare an injection-molded sheet having a thickness of 1.0 mm.

[Internal haze]
Using an injection-molded sheet of 30 mm×30 mm×1.0 mm in thickness molded by a microcompounder, benzyl alcohol was used and measurement was performed according to JIS K7136. Then, internal haze was evaluated according to the following criteria.
○: less than 5%
×: 5% or more

[Birefringence]
For an injection molded sheet of 30 mm × 30 mm × thickness 1.0 mm molded with a microcompounder, using KOBRA-CCD manufactured by Oji Scientific Instruments Co., Ltd., at a measurement wavelength of 650 nm, the average value of the phase difference of 20 to 35 mm from the gate direction. asked for
Then, each birefringence was evaluated according to the following criteria.
◎: the average value of the retardation is less than 30 nm
○: the average value of the retardation is 30 nm or more and less than 40 nm
×: the average value of the retardation is 40 nm or more

[Refractive index]
Using a refractometer (manufactured by Shimadzu Science, KPR200), the refractive index (nd) at a wavelength of 589 nm of an injection molded sheet of 30 mm × 30 mm × thickness 1.0 mm molded with a microcompounder according to ASTM D542. It was measured.

[Abbe number (ν)]
For an injection molded sheet of 30 mm × 30 mm × thickness 1.0 mm molded with a microcompounder, an Abbe refractometer was used to measure the refractive index at wavelengths of 486 nm, 589 nm and 656 nm at 23 ° C., and further using the following formula The Abbe number (ν) was calculated.
ν=(nD−1)/(nF−nC)
nD: refractive index at a wavelength of 589 nm
nC: refractive index at a wavelength of 656 nm
nF: refractive index at a wavelength of 486 nm

[Parallel light transmittance measurement]
Using an injection molded sheet of 30 mm × 30 mm × thickness 1.0 mm molded with a microcompounder, measure the parallel light transmittance at a wavelength of 450 nm using a UV-visible near-infrared spectrophotometer (Hitachi High-Tech Science UH4150). bottom.

<Preparation of cyclic olefin (d) containing aromatic ring>
[Production Example 1]
Alumina (Sumitomo Activated Alumina NKHD-24) was dried at 150° C. for 24 hours. 40% by mass of the dried alumina was immersed in 60% by mass of benzonorbornadiene (hereinafter also referred to as BNBD) at room temperature in a nitrogen atmosphere for 24 hours. The amount of oxidized compounds in BNBD was measured with GC2014 SHIMADZU GASCHROMATOGRAPH. Table 1 shows the results.

[Production Example 2]
Alumina (Sumitomo Activated Alumina NKHD-24) was dried at 150° C. for 24 hours. 20% by mass of the dried alumina was immersed in 80% by mass of BNBD at room temperature in a nitrogen atmosphere for 24 hours. Table 1 shows the results.

[Production Example 3]
Alumina (Sumitomo Activated Alumina NKHD-24) was dried at 150° C. for 24 hours. 10% by mass of the dried alumina was immersed in 90% by mass of BNBD at room temperature in a nitrogen atmosphere for 24 hours. Table 1 shows the results.

[Production Example 4]
Alumina (Sumitomo Activated Alumina NKHD-24) was dried at 150° C. for 24 hours. 5% by mass of the dried alumina was immersed in 95% by mass of BNBD at room temperature in a nitrogen atmosphere for 24 hours. Table 1 shows the results.

[Production Example 5]
Alumina (Sumitomo Activated Alumina NKHD-24) was dried at 150° C. for 24 hours. 2% by mass of the dried alumina was immersed in 98% by mass of BNBD at room temperature in a nitrogen atmosphere for 24 hours. Table 1 shows the results.

[Production Example 6]
Air was blown into 100 mL of BNBD at 100 mL/min for 168 hours. Table 1 shows the results.
Analysis of the produced BNBD oxidized compound by ¹ H-NMR (ECX-400P manufactured by JEOL Ltd.) revealed that the double bond portion of BNBD was 1a,2,7,7a-tetrahydro-2,7- It was methanonaphtho[2,3-b]oxirene.

[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 (40 mmol, hereinafter also referred to as tetracyclododecene) and BNBD prepared in Production Example 1 (88 mmol) 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 reached a predetermined temperature, the flow gas was switched from nitrogen to ethylene, and 50 NL/hr of ethylene and 2.0 NL/hr of hydrogen were passed through the reaction vessel. Methylaluminoxane (PMAO) (1.8 mmol) and the complex compound (A1) (0.0030 mmol) described in Example 1 of JP-A-2010-241932 were added to a glass reactor to initiate polymerization.
After 10 minutes had passed, 5 ml of isobutyl alcohol was added to terminate the polymerization to obtain a polymerization solution containing a copolymer of ethylene, tetracyclododecene and BNBD and an oxidized BNBD. After that, the polymerization solution was transferred to a 1 L separating funnel, and 0.1 mol/L hydrochloric acid was further added so that the oil layer/aqueous layer=1/1 vol %, and shaken to perform deashing operation. Furthermore, it was washed twice with pure water. After the oil layer was transferred to a Teflon bat and the solvent was volatilized at room temperature in a nitrogen atmosphere, it was dried under reduced pressure at 130° C. for 10 hours. 5.01 g of a white powdery ethylene/tetracyclododecene/BNBD copolymer composition containing a BNBD oxidized compound was obtained. The polymerization activity per 1 mmol of Ti atoms in the catalyst was 1.67 kg/mmol-Ti.
Thus, a cyclic olefin copolymer composition (P-1) was obtained. Table 2 shows the results.
The activity ratio was based on the polymerization activity of Example 1, and the ratio with the polymerization activity of Example 1 was calculated.

[Example 2]
A cyclic olefin copolymer composition (P-2) was obtained in the same manner as in Example 1 except that the BNBD prepared in Production Example 2 was used as BNBD. Table 2 shows the results.

[Example 3]
A cyclic olefin copolymer composition (P-3) was obtained in the same manner as in Example 1 except that the BNBD prepared in Production Example 3 was used as BNBD. Table 2 shows the results.

[Comparative Example 1]
A cyclic olefin copolymer composition (P-4) was obtained in the same manner as in Example 1 except that the BNBD prepared in Production Example 4 was used as BNBD. Table 2 shows the results.

[Comparative Example 2]
A cyclic olefin copolymer composition (P-5) was obtained in the same manner as in Example 1 except that the BNBD prepared in Production Example 5 was used as BNBD. Table 2 shows the results.

[Comparative Example 3]
In a nitrogen atmosphere, 4.5 g of the cyclic olefin copolymer composition (P-1) obtained in Example 1 was dissolved in 900 mL of cyclohexane. A solution of 0.16 g of BNBD prepared in Preparation 6 in 100 mL of cyclohexane was added to this polymer solution. After stirring for 30 minutes, the solution was transferred to a Teflon bat and the solvent was volatilized at room temperature under a nitrogen atmosphere. Vacuum drying was performed at 130° C. for 10 hours. 4.38 g of a white powdery ethylene/tetracyclododecene/BNBD copolymer composition containing an oxidized BNBD was obtained. Thus, a cyclic olefin copolymer composition (P-6) was obtained. Table 2 shows the results. In Comparative Example 3, the BNBD prepared in Production Example 6 was mixed with the composition (P-1) obtained in Example 1, and the BNBD prepared in Production Example 6 was involved in copolymerization. activity ratio was not described.

[Comparative Example 4]
The procedure of Example 1 was repeated except that the mixture of BNBD obtained in Production Example 6 and the BNBD oxide compound was used as BNBD, but a cyclic olefin copolymer could not be polymerized.

<Comparison between Examples and Comparative Examples>
According to Examples 1 to 3, when the content of the BNBD oxidant is in the range of 0.01 ppm to 2.2 ppm, good transmittance is exhibited, and while satisfying various properties required for optical lenses, high refractive index and showed a low Abbe number. On the other hand, according to Comparative Examples 1 to 3, when the content of the BNBD oxide compound was 2.3 ppm or more, the transmittance deteriorated and the optical properties were inferior.

Claims (23)

Step a of purifying a composition containing an aromatic ring-containing cyclic olefin (d) and an oxidant (B) of the aromatic ring-containing cyclic olefin (d) to reduce the amount of the oxidant (B) When,
After step a, α-olefin (a) having 2 to 20 carbon atoms and tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene (b) and/or norbornene (c) and the aromatic ring-containing cyclic olefin (d) contained in the composition are copolymerized to obtain a cyclic olefin copolymer. and a step b of manufacturing (A);
A method for producing a cyclic olefin copolymer composition comprising 0.01 ppm to 2.2 ppm of the oxidant (B) relative to the cyclic olefin copolymer (A). The method for producing a cyclic olefin copolymer composition according to claim 1, wherein the cyclic olefin (d) having an aromatic ring has a norbornene structure. 3. The method for producing a cyclic olefin copolymer composition according to claim 2, wherein said oxidant (B) contains an epoxynorbornene structure. In the step a, the amount of the oxidant (B) in the composition containing the aromatic ring-containing cyclic olefin (d) and the oxidant (B) is reduced to 150 ppm or less relative to the composition. The method for producing a cyclic olefin copolymer composition according to any one of claims 1 to 3. Claims 1 to 4, wherein the content of the structural unit (a1) is in the range of 40 to 80 mol% in the total 100 mol% of the structural unit (a1), the structural unit (bc1), and the structural unit (d1). A method for producing a cyclic olefin copolymer composition according to any one of the above. 6. The cyclic olefin according to any one of claims 1 to 5, wherein the content of the structural unit (d1) is in the range of 5 to 95 mol% based on the total 100 mol% of the structural unit (bc1) and the structural unit (d1). A method for making a system copolymer composition. The method for producing a cyclic olefin copolymer composition according to any one of claims 1 to 6, wherein the structural unit (bc1) contains the structural unit (b1). The cyclic olefin (d) containing an aromatic ring consists of a compound represented by the following formula (D-1), a compound represented by the following formula (D-2), and a compound represented by the following formula (D-3). The method for producing a cyclic olefin copolymer composition according to any one of claims 1 to 7, comprising one or more selected from the group.

(In the above formula (D-1), n and q are each independently 0, 1 or 2, and R ¹ to R ¹⁷ are each independently a hydrogen atom, a halogen atom other than a fluorine atom, or 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. , the monocyclic ring or the polycyclic ring may be an aromatic ring.)

(In formula (D-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 (D-3) above, q is 1, 2 or 3, and each of R ³² to R ³⁹ is 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. ) The oxidant (B) is selected from the group consisting of a compound represented by the following formula (B-1), a compound represented by the following formula (B-2), and a compound represented by the following formula (B-3) 9. The method for producing a cyclic olefin copolymer composition according to claim 8, comprising one or more.

(In formula (B-1) above, n, q, and R ¹ to R ¹⁷ have the same meanings as in general formula (D-1).)

(In formula (B-2) above, n, m, q, and R ¹⁸ to R ³¹ have the same meanings as in general formula (D-2).)

(In formula (B-3) above, q and R ³² to R ³⁹ have the same meanings as in general formula (D-3).) of claims 1 to 9, wherein the cyclic olefin (d) containing an aromatic ring is 1,4-dihydro-1,4-methanonaphthalene or 1,4,4a,9a-tetrahydro-1,4-methanofluorene A method for producing a cyclic olefin copolymer composition according to any one of the above. A cyclic olefin-based copolymer comprising the following structural unit (a1), a structural unit (bc1) containing at least one selected from structural units (b1) and structural units (c1), and a structural unit (d1) Union (A);
and an oxidized product (B) of a cyclic olefin (d) containing the following aromatic ring,
A cyclic olefin copolymer composition containing 0.01 ppm to 2.2 ppm of an oxidant (B) relative to the cyclic olefin copolymer (A).
Structural unit (a1): structural unit derived from α-olefin (a) having 2 to 20 carbon atoms Structural unit (b1): tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene (b)-derived structural unit Structural unit (c1): Norbornene (c)-derived structural unit Structural unit (d1): Aromatic ring-containing cyclic olefin (d)-derived structural unit 12. The cyclic olefin copolymer composition according to claim 11, wherein the cyclic olefin (d) having an aromatic ring has a norbornene structure. 13. The cyclic olefin copolymer composition according to claim 12, wherein the oxidant (B) contains an epoxynorbornene structure. Claims 11 to 13, wherein the content of the structural unit (a1) is in the range of 40 to 80 mol% in the total 100 mol% of the structural unit (a1), the structural unit (bc1), and the structural unit (d1). The cyclic olefin copolymer composition according to any one of the above. The cyclic olefin (d) containing an aromatic ring consists of a compound represented by the following formula (D-1), a compound represented by the following formula (D-2), and a compound represented by the following formula (D-3). The cyclic olefin copolymer composition according to any one of claims 11 to 14, comprising one or more selected from the group.

(In the above formula (D-1), n and q are each independently 0, 1 or 2, and R ¹ to R ¹⁷ are each independently a hydrogen atom, a halogen atom other than a fluorine atom, or 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. , the monocyclic ring or the polycyclic ring may be an aromatic ring.)

(In formula (D-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 (D-3) above, q is 1, 2 or 3, and each of R ³² to R ³⁹ is 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. ) The oxidant (B) is selected from the group consisting of a compound represented by the following formula (B-1), a compound represented by the following formula (B-2), and a compound represented by the following formula (B-3) 16. The cyclic olefin copolymer composition according to claim 15, comprising one or more.

(In formula (B-1) above, n, q, and R ¹ to R ¹⁷ have the same meanings as in general formula (D-1).)

(In formula (B-2) above, n, m, q, and R ¹⁸ to R ³¹ have the same meanings as in general formula (D-2).)

(In formula (B-3) above, q and R ³² to R ³⁹ have the same meanings as in general formula (D-3).) Any one of claims 11 to 16, wherein when an injection-molded sheet having a thickness of 1.0 mm is produced from the cyclic olefin copolymer composition, the Abbe number ν of the injection-molded sheet is in the range of 35 to 55. The cyclic olefin copolymer composition according to . 18. The cyclic polymer according to any one of claims 11 to 17, wherein when an injection-molded sheet having a thickness of 1.0 mm is produced from the cyclic olefin-based copolymer composition, the birefringence of the injection-molded sheet is less than 40 nm. Olefinic copolymer composition. The method according to any one of claims 11 to 18, wherein when an injection-molded sheet having a thickness of 1.0 mm is produced from the cyclic olefin copolymer composition, the parallel light transmittance of the injection-molded sheet at a wavelength of 450 nm is 85% or more. The cyclic olefin copolymer composition according to any one of the above. of claims 11 to 19, wherein the cyclic olefin (d) containing an aromatic ring is 1,4-dihydro-1,4-methanonaphthalene or 1,4,4a,9a-tetrahydro-1,4-methanofluorene The cyclic olefin copolymer composition according to any one of the above. A molded article comprising the cyclic olefin copolymer composition according to any one of claims 11 to 20. A cyclic olefin-based copolymer comprising the following structural unit (a1), a structural unit (bc1) containing at least one selected from structural units (b1) and structural units (c1), and a structural unit (d1) Union (A);
and an oxidized product (B) of a cyclic olefin (d) containing the following aromatic ring,
A molded body, comprising a step of molding a cyclic olefin copolymer composition containing 0.01 ppm to 2.2 ppm of the oxidized product (B) in a mold with respect to the cyclic olefin copolymer (A). Production method.
Structural unit (a1): structural unit derived from α-olefin (a) having 2 to 20 carbon atoms Structural unit (b1): tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene (b)-derived structural unit Structural unit (c1): Norbornene (c)-derived structural unit Structural unit (d1): Aromatic ring-containing cyclic olefin (d)-derived structural unit An optical lens comprising the molded article according to claim 21.