JP2024075160A - Regenerated cyclic olefinic resin composition, molded article and optical component - Google Patents

Abstract

To provide a regenerated cyclic olefinic resin composition that yields a molded article and an optical component with mitigated transparency reduction and yellowing, and to provide a molded article and an optical component with mitigated transparency reduction and yellowing.SOLUTION: A regenerated cyclic olefinic resin composition contains a cyclic olefinic resin (A), a phenolic antioxidant (B), and a phosphorous stabilizer (C). The cyclic olefinic resin (A) contains a recovered cyclic olefin resin (A1). The phosphorous stabilizer (C) has a 10% mass loss temperature in the air of 275°C or higher, as measured with a calorimeter.SELECTED DRAWING: None

Description

The present invention relates to recycled cyclic olefin resin compositions, molded articles, and optical components.

It has been disclosed that cyclic olefin resins are used, for example, in transparent containers for food and medicine; optical lenses such as eyeglass lenses, pickup lenses, fθ lenses, and smartphone camera lenses; and optical recording media such as MOs, DVDs, and CDs (see, for example, Patent Document 1).
Molded articles for such applications are molded using molding machines such as injection molding machines, and large amounts of processing waste materials such as sprues and runners are generated during molding. Most of these processing waste materials are currently incinerated, but the incineration of plastics such as cyclic olefin resins generates large amounts of carbon dioxide gas, which is problematic from the perspective of protecting the global environment.
In recent years, recycled plastics obtained by collecting waste molded bodies made of thermoplastic resin, pulverizing them as necessary, and forming them into pellets have been widely used (see, for example, Patent Document 2).

Patent Document 1 describes a resin composition that contains a polymer containing an alicyclic structure in at least a portion of the repeating structural units, and a fatty acid ester of a fatty acid and a polyhydric alcohol having one or more ether groups, with the aim of providing a resin composition that can produce a molded product that has excellent optical performance and that further suppresses deterioration of the optical performance under high temperature and high humidity conditions.

Patent Document 2 describes a method for treating cyclic olefin resin molded bodies, which is characterized by contacting a molded body made of a specific cyclic olefin resin with a liquid hydrocarbon compound to soften or fluidize the cyclic olefin resin, with the aim of providing a method for treating cyclic olefin resin molded bodies that can easily soften or fluidize the cyclic olefin resin molded bodies.

JP 2015-199939 A JP 2000-169621 A

However, when waste molded products containing cyclic olefin resins are reused, the resulting molded products and optical components may turn yellow or lose transparency, making it impossible to use them for their intended purposes.

The present invention has been made in consideration of the above circumstances, and provides a recycled cyclic olefin resin composition that can produce molded articles and optical parts in which the decrease in transparency and yellowing are suppressed, as well as molded articles and optical parts in which the decrease in transparency and yellowing are suppressed.

According to the present invention, the following recycled cyclic olefin resin composition, molded body, and optical component are provided.

（前記式（１）において、Ｒ^５０１～Ｒ^５０５は、互いに同一でも異なっていてもよく、水素原子または炭素原子数１～２０のアルキル基である。）

（前記式（３）において、Ｒ^７００は炭素原子数１～２９の炭化水素基であり、Ｒ^７０１～Ｒ^７０８は、互いに同一でも異なっていてもよく、水素原子または炭素原子数１～２０のアルキル基である。）
［６］
前記フェノール系酸化防止剤（Ｂ）は、ペンタエリトリトールテトラキス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオナート］、１，３，５－トリス（３，５－ジ－ｔｅｒｔ‐ブチル－４－ヒドロキシベンジル）‐１，３，５‐トリアジン－２，４，６（１Ｈ，３Ｈ，５Ｈ）－トリオン、３，９－ビス｛２－［３－（３－ｔｅｒｔ‐ブチル－４－ヒドロキシ－５－メチルフェニル）プロピオニルオキシ］‐１，１－ジメチルエチル｝‐２，４，８，１０－テトラオキサスピロ［５．５］ウンデカン、および１，３，５－トリス（３，５－ジ－ｔｅｒｔ‐ブチル－４－ヒドロキシフェニルメチル）－２，４，６－トリメチルベンゼンからなる群から選択される少なくも一種を含む、前記［１］～［５］のいずれかに記載の再生環状オレフィン系樹脂組成物。
［７］
前記環状オレフィン系樹脂（Ａ）が、
下記式（Ｉ）で表される少なくとも１種のオレフィン由来の繰り返し単位（ａ）と、
下記式（ＩＩ）で表される繰り返し単位（ＡＡ）、下記式（ＩＩＩ）で表される繰り返し単位（ＡＢ）及び下記式（ＩＶ）で表される繰り返し単位（ＡＣ）からなる群から選ばれる少なくとも１種の環状オレフィンモノマー由来の繰り返し単位（ｂ）と、
を有する環状オレフィン系共重合体（Ｐ１）を含む、前記［１］～［６］のいずれかに記載の再生環状オレフィン系樹脂組成物。

（前記式（Ｉ）において、Ｒ^３００は水素原子又は炭素原子数１～２９の直鎖状又は分岐状の炭化水素基を示す。）

（前記式（ＩＩ）において、ｕは０又は１であり、ｖは０又は正の整数であり、ｗは０又は１であり、Ｒ^６１～Ｒ^７８並びにＲ^ａ１及びＲ^ｂ１は、互いに同一でも異なっていてもよく、水素原子、ハロゲン原子、炭素原子数１～２０のアルキル基、炭素原子数１～２０のハロゲン化アルキル基、炭素原子数３～１５のシクロアルキル基又は炭素原子数６～２０の芳香族炭化水素基であり、Ｒ^７５～Ｒ^７８は、互いに結合して単環又は多環を形成していてもよい。）

（前記式（ＩＩＩ）において、ｘ及びｄは０又は１以上の整数であり、ｙ及びｚは０、１又は２であり、Ｒ^８１～Ｒ^９９は、互いに同一でも異なっていてもよく、水素原子、ハロゲン原子、炭素原子数１～２０のアルキル基若しくは炭素原子数３～１５のシクロアルキル基である脂肪族炭化水素基、炭素原子数６～２０の芳香族炭化水素基又はアルコキシ基であり、Ｒ^８９及びＲ^９０が結合している炭素原子と、Ｒ^９３が結合している炭素原子又はＲ^９１が結合している炭素原子とは、直接あるいは炭素原子数１～３のアルキレン基を介して結合していてもよく、またｙ＝ｚ＝０のとき、Ｒ^９５とＲ^９２又はＲ^９５とＲ^９９とは互いに結合して単環又は多環の芳香族環を形成していてもよい。）

（前記式（ＩＶ）において、Ｒ^１００及びＲ^１０１は、互いに同一でも異なっていてもよく、水素原子又は炭素原子数１～５の炭化水素基を示し、ｆは１≦ｆ≦１８の整数である。）
［８］
前記環状オレフィン系樹脂（Ａ）が、下記式（ＩＩ）で表される繰り返し単位（ＡＡ）及び芳香環を有する環状オレフィン由来の繰り返し単位（Ｃ）を有する環状オレフィン系共重合体（Ｐ２）を含み、
前記繰り返し単位（ＡＡ）が芳香環を含まず、
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、及び下記式（Ｃ－３）で示される化合物からなる群から選択される少なくとも一種を含む、前記［１］～［７］のいずれかに記載の再生環状オレフィン系樹脂組成物。

（前記式（ＩＩ）において、ｕは０又は１であり、ｖは０又は正の整数であり、ｗは０又は１であり、Ｒ^６１～Ｒ^７８並びにＲ^ａ１及びＲ^ｂ１は、互いに同一でも異なっていてもよく、水素原子、ハロゲン原子、炭素原子数１～２０のアルキル基、炭素原子数１～２０のハロゲン化アルキル基又は炭素原子数３～１５のシクロアルキル基であり、Ｒ^７５～Ｒ^７８は、互いに結合して単環又は多環を形成していてもよい。）

（前記式（Ｃ－１）において、ｎ及びｑはそれぞれ独立に０、１又は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、又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又は多環を形成していてもよく、またｑ＝１又は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又は多環を形成していてもよく、また前記単環又は前記多環が二重結合を有していてもよく、前記単環又は前記多環が芳香族環であってもよい。）

（前記式（Ｃ－２）において、ｎ及びｍはそれぞれ独立に０、１又は２であり、ｑは１、２又は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、又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又は多環を形成していてもよく、またｑ＝２又は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又は多環を形成していてもよく、前記単環又は前記多環が二重結合を有していてもよく、また前記単環又は前記多環が芳香族環であってもよい。）

（前記式（Ｃ－３）において、ｑは１、２又は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、又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又は多環を形成していてもよく、またｑ＝２又は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又は多環を形成していてもよく、前記単環又は前記多環が二重結合を有していてもよく、また前記単環又は前記多環が芳香族環であってもよい。）
［９］
ペレット状である、前記［１］～［８］のいずれかに記載の再生環状オレフィン系樹脂組成物。
［１０］
前記［１］～［９］のいずれかに記載の再生環状オレフィン系樹脂組成物を含む成形体。
［１１］
前記［１０］に記載の成形体を含む光学部品。 [1]
A recycled cyclic olefin resin composition comprising a cyclic olefin resin (A), a phenol-based antioxidant (B), and a phosphorus-based stabilizer (C),
The cyclic olefin resin (A) contains a recycled cyclic olefin resin (A1),
The phosphorus-based stabilizer (C) is a recycled cyclic olefin resin composition having a 10% mass loss temperature in air of 275°C or higher as measured by a calorimeter.
[2]
The recycled cyclic olefin resin composition according to [1], wherein the content of the phosphorus-based stabilizer (C) is 0.01 parts by mass or more and 1.00 parts by mass or less per 100 parts by mass of the cyclic olefin resin (A).
[3]
The recycled cyclic olefin resin composition according to [1] or [2], wherein the content of the phenol-based antioxidant (B) is 0.01 parts by mass or more and 0.50 parts by mass or less per 100 parts by mass of the cyclic olefin resin (A).
[4]
The recycled cyclic olefin resin composition according to any one of [1] to [3], wherein the mass ratio (C/B) of the content of the phosphorus-based stabilizer (C) to the content of the phenol-based antioxidant (B) is 0.1 or more and 2.5 or less.
[5]
The recycled cyclic olefin resin composition according to any one of [1] to [4], wherein the phosphorus-based stabilizer (C) comprises at least one selected from the group consisting of phosphorus-based stabilizers represented by the following formula (1) and phosphorus-based stabilizers represented by the following formula (3).

(In the formula (1), R ⁵⁰¹ to R ⁵⁰⁵ may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.)

(In the formula (3), R ⁷⁰⁰ is a hydrocarbon group having 1 to 29 carbon atoms, and R ⁷⁰¹ to R ⁷⁰⁸ may be the same or different and are a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.)
[6]
The recycled cyclic olefin resin composition according to any one of [1] to [5], wherein the phenol-based antioxidant (B) is at least one selected from the group consisting of pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5.5]undecane, and 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene.
[7]
The cyclic olefin resin (A) is
At least one olefin-derived repeating unit (a) represented by the following formula (I);
A repeating unit (b) derived from at least one cyclic olefin monomer selected from the group consisting of a repeating unit (AA) represented by the following formula (II), a repeating unit (AB) represented by the following formula (III), and a repeating unit (AC) represented by the following formula (IV),
The recycled cyclic olefin resin composition according to any one of [1] to [6] above, comprising a cyclic olefin copolymer (P1) having the following formula:

(In the above formula (I), R ³⁰⁰ represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms.)

(In the formula (II), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, R ⁶¹ to R ⁷⁸ as well as R ^a1 and R ^b1 may be the same or different and are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and R ⁷⁵ to R ⁷⁸ may be bonded to each other to form a monocycle or multiple cycles.)

(In the formula (III), x and d are 0 or an integer of 1 or more, y and z are 0, 1 or 2, R ⁸¹ to R ⁹⁹ may be the same or different and are a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group which is an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or an alkoxy group, and the carbon atom to which R ⁸⁹ and R ⁹⁰ are bonded may be bonded directly or via an alkylene group having 1 to 3 carbon atoms to the carbon atom to which R ⁹³ is bonded or the carbon atom to which R ⁹¹ is bonded, and when y=z=0, R ⁹⁵ and R ⁹² or R ⁹⁵ and R ⁹⁹ may be bonded to each other to form a monocyclic or polycyclic aromatic ring.)

(In the formula (IV), R ¹⁰⁰ and R ¹⁰¹ may be the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and f is an integer satisfying 1≦f≦18.)
[8]
The cyclic olefin resin (A) contains a cyclic olefin copolymer (P2) having a repeating unit (AA) represented by the following formula (II) and a repeating unit (C) derived from a cyclic olefin having an aromatic ring,
The repeating unit (AA) does not contain an aromatic ring,
The recycled cyclic olefin resin composition according to any one of [1] to [7] above, wherein the cyclic olefin having an aromatic ring comprises at least one 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):

(In the formula (II), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, R ⁶¹ to R ⁷⁸ as well as R ^a1 and R ^b1 may be the same or different and each represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms, and R ⁷⁵ to R ⁷⁸ may be bonded to each other to form a monocycle or polycycle.)

(In the formula (C-1), n and q are each independently 0, 1 or 2; 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 which may be substituted with a halogen atom other than a fluorine atom; one of R ¹⁰ to R ¹⁷ is a bond; when q=0, R ¹⁰ and R ¹¹ , R ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , and R ¹⁵ and R ¹⁰ may be bonded to each other to form a monocyclic or polycyclic ring; 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 , and R ¹⁴ and R ¹⁵ , R ¹⁵ and R ¹⁶ , R ¹⁶ and R ¹⁶ , and R ¹⁶ and R ¹⁰ may be bonded to each other to form a monocycle or polycycle, and the monocycle or polycycle may have a double bond, or the monocycle or polycycle may be an aromatic ring.

(In the formula (C-2), n and m are each independently 0, 1 or 2; q is 1, 2 or 3; R ¹⁸ to R ³¹ are each 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; when q=1, R ²⁸ and R ²⁹ , R ²⁹ and R ³⁰ , and R ³⁰ and R ³¹ may be bonded to each other to form a monocycle or a polycycle; when q=2 or 3, R ²⁸ and R ²⁸ , R ²⁸ and R ²⁹ , R ²⁹ and R ³⁰ , R ³⁰ and R ³¹ , and R ³¹ and R ³¹ may be bonded to each other to form a monocycle or a polycycle, the monocycle or the polycycle may have a double bond, and the monocycle or the polycycle may be an aromatic ring.)

(In the formula (C-3), q is 1, 2 or 3, R ³² to R ³⁹ are each 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, and when q=1, R ³⁶ and R ³⁷ , R ³⁷ and R ³⁸ , and R ³⁸ and R ³⁹ may be bonded to each other to form a monocycle or a polycycle, 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 , and R ³⁹ and R ³⁹ may be bonded to each other to form a monocycle or a polycycle, the monocycle or the polycycle may have a double bond, and the monocycle or the polycycle may be an aromatic ring.)
[9]
The recycled cyclic olefin resin composition according to any one of [1] to [8] above, which is in the form of pellets.
[10]
A molded article comprising the recycled cyclic olefin resin composition according to any one of [1] to [9] above.
[11]
An optical component comprising the molded article according to [10] above.

The present invention provides a recycled cyclic olefin resin composition that can produce molded articles and optical parts with reduced loss of transparency and reduced yellowing, as well as molded articles and optical parts with reduced loss of transparency and reduced yellowing.

The present invention will be described below based on an embodiment. In this embodiment, "A to B" indicating a numerical range indicates A or more and B or less unless otherwise specified.

[Recycled cyclic olefin resin composition]
The recycled cyclic olefin resin composition of this embodiment is a recycled cyclic olefin resin composition comprising a cyclic olefin resin (A), a phenol-based antioxidant (B), and a phosphorus-based stabilizer (C), wherein the cyclic olefin resin (A) comprises a recovered cyclic olefin resin (A1), and the phosphorus-based stabilizer (C) has a 10% mass loss temperature in air of 275°C or higher as measured by a calorimeter.
In this specification, a cyclic olefin resin recovered from a used molded body, product, or waste material according to a known method is called a recovered cyclic olefin resin (A1). A cyclic olefin resin composition containing the recovered cyclic olefin resin (A1) is called a recycled cyclic olefin resin composition.
Hereinafter, unless otherwise specified, "10% mass loss temperature" means "10% mass loss temperature in air measured by a calorimeter."

As described above, when waste materials of molded bodies containing cyclic olefin resins are reused, the resulting molded bodies or optical components may become yellowed or the transparency of the resulting molded bodies or optical components may decrease, making it impossible to use them for their intended purposes.
In addition, the cyclic olefin resin composition may be molded into a pellet shape, a film shape, etc. When the cyclic olefin resin composition is molded, a step of heating the cyclic olefin resin composition to a molten state may be included, but the cyclic olefin resin composition may be yellowed and its transparency may be reduced due to thermal oxidative deterioration.
As a result of extensive research, the present inventors have found that a cyclic olefin resin composition containing a specific phosphorus-based stabilizer (C) can produce molded articles and optical components in which the decrease in transparency and yellowing are suppressed, even when the cyclic olefin resin composition contains recovered cyclic olefin resin (A1).

The cyclic olefin resin (A) of the present embodiment includes a recycled cyclic olefin resin (A1). The cyclic olefin resin (A) may also include a virgin cyclic olefin resin.
Hereinafter, the "content of cyclic olefin resin (A)" means the sum of the content of recovered cyclic olefin resin (A1) and the content of unused cyclic olefin resin, unless otherwise specified. In addition, "100 parts by mass of cyclic olefin resin (A)" means the sum of the parts by mass of recovered cyclic olefin resin (A1) and the parts by mass of unused cyclic olefin resin, which is 100 parts by mass, unless otherwise specified.

The content of the cyclic olefin resin (A) in the recycled cyclic olefin resin composition of this embodiment, when the entire recycled cyclic olefin resin composition is taken as 100% by mass, is preferably 95.0% by mass or more, more preferably 96.0% by mass or more, even more preferably 97.0% by mass or more, even more preferably 98.0% by mass or more, even more preferably 98.5% by mass or more, even more preferably 98.8% by mass or more, even more preferably 99.0% by mass or more, even more preferably 99.2% by mass or more, even more preferably 99.5% by mass or more, even more preferably 99.7% by mass or more, and preferably 99.98% by mass or less, more preferably 99.90% by mass or less, from the viewpoint of further improving the performance balance of moldability and transparency.
The content of the recovered cyclic olefin resin (A1) in the recycled cyclic olefin resin composition of this embodiment, when the entire recycled cyclic olefin resin composition is taken as 100% by mass, is preferably 30.0% by mass or more, more preferably 50.0% by mass or more, even more preferably 70.0% by mass or more, even more preferably 80.0% by mass or more, even more preferably 90.0% by mass or more, even more preferably 95.0% by mass or more, even more preferably 96.0% by mass or more, even more preferably 97.0% by mass or more, even more preferably 98.0% by mass or more, even more preferably 98.5% by mass or more, even more preferably 98.8% by mass or more, even more preferably 99.0% by mass or more, even more preferably 99.2% by mass or more, even more preferably 99.5% by mass or more, even more preferably 99.7% by mass or more, and preferably 99.98% by mass or less, more preferably 99.90% by mass or less, from the viewpoint of protecting the global environment.

The content of the phenolic antioxidant (B) in the recycled cyclic olefin resin composition of this embodiment is preferably 0.01 parts by mass or more, more preferably 0.03 parts by mass or more, even more preferably 0.05 parts by mass or more, even more preferably 0.07 parts by mass or more, and even more preferably 0.09 parts by mass or more, per 100 parts by mass of the cyclic olefin resin (A), from the viewpoint of further suppressing the decrease in transparency and yellowing, and is preferably 0.50 parts by mass or less, more preferably 0.40 parts by mass or less, even more preferably 0.30 parts by mass or less, even more preferably 0.20 parts by mass or less, and even more preferably 0.15 parts by mass or less, from the viewpoint of further suppressing the decrease in transparency and yellowing.

The content of the phosphorus-based stabilizer (C) in the recycled cyclic olefin resin composition of this embodiment is preferably 0.01 parts by mass or more, more preferably 0.02 parts by mass or more, and even more preferably 0.04 parts by mass or more, per 100 parts by mass of the cyclic olefin resin (A), from the viewpoint of further suppressing the decrease in transparency and yellowing, and is preferably 1.00 parts by mass or less, more preferably 0.80 parts by mass or less, even more preferably 0.50 parts by mass or less, even more preferably 0.30 parts by mass or less, even more preferably 0.20 parts by mass or less, even more preferably 0.10 parts by mass or less, and even more preferably 0.07 parts by mass or less, from the viewpoint of further suppressing the decrease in transparency and yellowing.

In the recycled cyclic olefin resin composition of this embodiment, the mass ratio (C/B) of the content of the phosphorus-based stabilizer (C) to the content of the phenol-based antioxidant (B) is preferably 0.1 or more, more preferably 0.2 or more, and even more preferably 0.4 or more, from the viewpoint of further suppressing the decrease in transparency and yellowing, and is preferably 2.5 or less, more preferably 2.0 or less, even more preferably 1.5 or less, even more preferably 1.0 or less, and even more preferably 0.7 or less, from the viewpoint of further suppressing the decrease in transparency and yellowing.

When the entire recycled cyclic olefin resin composition is taken as 100% by mass, from the viewpoint of further improving the performance balance between moldability and transparency, it is preferable that the content of cyclic olefin resin (A) in the recycled cyclic olefin resin composition of this embodiment is 95.0% by mass or more and 99.9% by mass or less, the content of phenol-based antioxidant (B) is 0.01% by mass or more and 0.50% by mass or less, and the content of phosphorus-based stabilizer (C) is 0.01% by mass or more and 1.00% by mass or less.
In addition, the total content of the cyclic olefin resin (A), the phenol-based antioxidant (B), and the phosphorus-based stabilizer (C) in the recycled cyclic olefin resin composition of this embodiment, when the entire recycled cyclic olefin resin composition is taken as 100 mass%, is preferably 80.0 mass% or more, more preferably 90.0 mass% or more, even more preferably 93.0 mass% or more, even more preferably 95.0 mass% or more, even more preferably 97.0 mass% or more, and preferably 100 mass% or less, from the viewpoint of further improving the performance balance of moldability and transparency.

The melt flow rate (MFR) of the recycled cyclic olefin resin composition measured in accordance with ASTM D1238 at 260°C and a load of 2.16 kg is preferably 5 g/10 min or more, more preferably 8 g/10 min or more, even more preferably 10 g/10 min or more, and even more preferably 20 g/10 min or more, from the viewpoint of further improving moldability, and the upper limit is not particularly limited, but may be, for example, 100 g/10 min or less, or 50 g/10 min or less.

The glass transition temperature (Tg) of the recycled cyclic olefin resin composition is, from the viewpoint of improving the performance balance of moldability, transparency and heat resistance, preferably 70°C or higher, more preferably 80°C or higher, even more preferably 90°C or higher, even more preferably 100°C or higher, even more preferably 110°C or higher, even more preferably 120°C or higher, even more preferably 130°C or higher, and even more preferably 140°C or higher, from the viewpoint of improving the performance balance of moldability, transparency and heat resistance, and is preferably 250°C or lower, more preferably 200°C or lower, even more preferably 180°C or lower, even more preferably 170°C or lower, and even more preferably 160°C or lower.
The glass transition temperature (Tg) of the recycled cyclic olefin resin composition can be measured, for example, by the method described in the Examples.

Below, we will explain each component of the recycled cyclic olefin resin composition of this embodiment.

(Cyclic Olefin Resin (A))
The cyclic olefin resin (A) of the present embodiment includes a recycled cyclic olefin resin (A1). The cyclic olefin resin (A) may also include a virgin cyclic olefin resin.

When the entire cyclic olefin resin (A) of this embodiment is taken as 100% by mass, the content of the recovered cyclic olefin resin (A1) in the cyclic olefin resin (A) is, from the viewpoint of protecting the global environment, preferably 30.0% by mass or more, more preferably 50.0% by mass or more, even more preferably 70.0% by mass or more, even more preferably 80.0% by mass or more, even more preferably 90.0% by mass or more, even more preferably 95.0% by mass or more, even more preferably 97.0% by mass or more, even more preferably 99.0% by mass or more, even more preferably 99.5% by mass or more, even more preferably 99.8% by mass or more, and preferably 100% by mass or less.

The cyclic olefin resin (A) of this embodiment is not particularly limited, and may be a cyclic olefin homopolymer or a cyclic olefin copolymer. In addition, the cyclic olefin resin (A) of this embodiment may be used alone or in combination of two or more types.

The preferred form of the cyclic olefin resin (A) is described below. The preferred form of the recovered cyclic olefin resin (A1) is the same as the preferred form of the cyclic olefin resin (A).

From the viewpoint of further improving heat resistance while maintaining a good balance between the transparency and refractive index of the resulting molded body and optical component, and from the viewpoint of further improving moldability, it is preferable that the cyclic olefin resin (A) contains a cyclic olefin copolymer (P1) having at least one olefin-derived repeating unit (a) represented by the following formula (I) and at least one cyclic olefin monomer-derived repeating unit (b) selected from the group consisting of repeating units (AA) represented by the following formula (II), repeating units (AB) represented by the following formula (III), and repeating units (AC) represented by the following formula (IV).

In the above formula (I), R ³⁰⁰ represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms.

In the formula (II), u is 0 or 1, v is 0 or a positive integer, preferably an integer of 0 to 2, more preferably 0 or 1, w is 0 or 1, R ⁶¹ to R ⁷⁸ as well as R ^a1 and R ^b1 may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and R ⁷⁵ to R ⁷⁸ may be bonded to each other to form a monocycle or polycycle.

In the formula (III), x and d are 0 or an integer of 1 or more, y and z are 0, 1 or 2, R ⁸¹ to R ⁹⁹ may be the same or different and are a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group which is an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms, an aromatic hydrocarbon group or an alkoxy group having 6 to 20 carbon atoms, the carbon atom to which R ⁸⁹ and R ⁹⁰ are bonded may be bonded directly or via an alkylene group having 1 to 3 carbon atoms to the carbon atom to which R ⁹³ is bonded or the carbon atom to which R ⁹¹ is bonded, and when y=z=0, R ⁹⁵ and R ⁹² or R ⁹⁵ and R ⁹⁹ may be bonded to each other to form a monocyclic or polycyclic aromatic ring.

In the formula (IV), R ¹⁰⁰ and R ¹⁰¹ may be the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and f is an integer satisfying 1≦f≦18.

The olefin monomer, which is one of the copolymerization raw materials for the cyclic olefin copolymer (P1), undergoes addition copolymerization to form the repeating unit (a) represented by the above formula (I). Specifically, the olefin monomer represented by the following formula (Ia) corresponding to the above formula (I) is used.

In the formula (Ia), R ³⁰⁰ represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms. Examples of the olefin monomer represented by the formula (Ia) include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. From the viewpoint of obtaining a molded product having better heat resistance, mechanical properties, and optical properties, at least one selected from the group consisting of ethylene and propylene is preferable, and ethylene is more preferable. Two or more kinds of olefin monomers represented by the formula (Ia) may be used.
When the total number of repeating units constituting the cyclic olefin copolymer (P1) is taken as 100 mol %, the proportion of the repeating units (a) derived from an olefin is preferably 5 mol % or more and 95 mol % or less, more preferably 20 mol % or more and 90 mol % or less, even more preferably 40 mol % or more and 85 mol % or less, and even more preferably 50 mol % or more and 80 mol % or less.
The proportion of the repeating unit (a) derived from an olefin can be measured by ¹³ C-NMR.

The cyclic olefin monomer, which is one of the copolymerization raw materials for the cyclic olefin copolymer (P1), undergoes addition copolymerization to form the repeating unit (b) derived from the cyclic olefin monomer represented by the formula (II), the formula (III), or the formula (IV). Specifically, the cyclic olefin monomers represented by the formulas (IIa), (IIIa), and (IVa), which correspond to the formulas (II), (III), and (IV), respectively, are used.

In the formula (IIa), u is 0 or 1, v is 0 or a positive integer, preferably an integer of 0 to 2, more preferably 0 or 1, w is 0 or 1, R ⁶¹ to R ⁷⁸ as well as R ^a1 and R ^b1 may be the same or different and are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and R ⁷⁵ to R ⁷⁸ may be bonded to each other to form a monocycle or polycycle.

In the formula (IIIa), x and d are 0 or an integer of 1 or more, preferably an integer of 0 or more and 2 or less, more preferably 0 or 1; y and z are 0, 1, or 2; R ⁸¹ to R ⁹⁹ may be the same or different from one another and are a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group which is an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms, an aromatic hydrocarbon group or an alkoxy group having 6 to 20 carbon atoms; the carbon atom to which R ⁸⁹ and R ⁹⁰ are bonded may be bonded directly or via an alkylene group having 1 to 3 carbon atoms to the carbon atom to which R ⁹³ is bonded or the carbon atom to which R ⁹¹ is bonded; and when y=z=0, R ⁹⁵ and R ⁹² or R ⁹⁵ and R ⁹⁹ may be bonded to each other to form a monocyclic or polycyclic aromatic ring.

In the formula (IVa), R ¹⁰⁰ and R ¹⁰¹ may be the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and f is an integer satisfying 1≦f≦18.

Specific examples of cyclic olefin monomers represented by formula (IIa), (IIIa) or (IVa) include the compounds described in paragraphs 0037 to 0063 of WO 2006/118261.

Specifically, bicyclo-2-heptene derivatives (bicyclohept-2-ene derivatives), tricyclo-3-decene derivatives, tricyclo-3-undecene derivatives, tetracyclo-3-dodecene derivatives, pentacyclo-4-pentadecene derivatives, pentacyclopentadecadiene derivatives, pentacyclo-3-pentadecene derivatives, pentacyclo-4-hexadecene derivatives, pentacyclo-3-hexadecene derivatives, hexacyclo-4-heptadecene derivatives, heptacyclo-5-eicosene derivatives Conductors, heptacyclo-4-eicosene derivatives, heptacyclo-5-heneicosene derivatives, octacyclo-5-docosene derivatives, nonacyclo-5-pentacosene derivatives, nonacyclo-6-hexacosene derivatives, cyclopentadiene-acenaphthylene adducts, 1,4-methano-1,4,4a,9a-tetrahydrofluorene derivatives, 1,4-methano-1,4,4a,5,10,10a-hexahydroanthracene derivatives, cycloalkylene derivatives with 3 to 20 carbon atoms, etc.

Among the cyclic olefin monomers represented by formula (IIa), (IIIa) or (IVa), the cyclic olefin monomer represented by formula (IIa) is preferred.
It is also preferable to use a cyclic olefin represented by formula (IIa) and either a cyclic olefin represented by formula (IIIa) or (IVa).

As the cyclic olefin monomer represented by the formula (IIa), it is preferable to use at least one selected from the group consisting of bicyclo[2.2.1]-2-heptene (also referred to as "norbornene" in this specification) and tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene (also referred to as "tetracyclododecene" in this specification), and it is more preferable to use tetracyclo[4.4.0.1 ^2,5 . ^{1 7,10} ]-3-dodecene. These cyclic olefins have a rigid ring structure, which has the advantage that the elastic modulus of the copolymer and the molded article is easily maintained.

When the total number of repeating units constituting the cyclic olefin copolymer (P1) is taken as 100 mol %, the proportion of the repeating units (b) derived from the cyclic olefin monomer is preferably 5 mol % or more and 95 mol % or less, more preferably 10 mol % or more and 80 mol % or less, even more preferably 15 mol % or more and 60 mol % or less, and still more preferably 20 mol % or more and 50 mol % or less.
In this embodiment, the proportion of the repeating unit (b) derived from a cyclic olefin monomer can be measured, for example, by ¹ H-NMR or ¹³ C-NMR.

The copolymer type of the cyclic olefin copolymer (P1) is not particularly limited, but examples include random copolymers and block copolymers. From the viewpoint of further improving optical properties such as transparency, refractive index, and birefringence, and obtaining optical components with higher precision, it is preferable to use a random copolymer as the cyclic olefin copolymer (P1).

The cyclic olefin copolymer (P1) is preferably at least one selected from the group consisting of a random copolymer of ethylene and tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene, a random copolymer of ethylene and bicyclo[2.2.1]-2-heptene, and a random copolymer of ethylene, tetracyclo[4.4.0.1 ^2,5 . ^{1 7,10} ]-3-dodecene, and benzonorbornadiene, more preferably at least one selected from the group consisting of a random copolymer of ethylene and tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene, and a random copolymer of ethylene, tetracyclo[4.4.0.1 ^{2,5 . 1 7,10 ]-3-dodecene, and benzonorbornadiene, and more preferably at least one selected from the group consisting of a random copolymer of ethylene and tetracyclo[4.4.0.1 2,5} . 1 ^7,10 ]-3-dodecene, and a random copolymer of ethylene and tetracyclo[4.4.0.1 ^2,5 . A random copolymer with ^17,10 ]-3-dodecene is more preferred.

The cyclic olefin copolymer (P1) may be used alone or in combination of two or more kinds.

The cyclic olefin copolymer (P1) can be produced by appropriately selecting the conditions according to the methods described in, for example, JP-A-60-168708, JP-A-61-120816, JP-A-61-115912, JP-A-61-115916, JP-A-61-271308, JP-A-61-272216, JP-A-62-252406, JP-A-62-252407, etc.

From the viewpoint of further improving heat resistance while maintaining a good balance of the transparency and refractive index of the resulting molded article and optical component, and from the viewpoint of further improving moldability, the cyclic olefin resin (A) preferably contains a repeating unit (AA) represented by the following formula (II) and a repeating unit (C) derived from a cyclic olefin having an aromatic ring, the repeating unit (AA) does not contain an aromatic ring, and the cyclic olefin having an aromatic ring contains at least one compound 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).

In the formula (II), u is 0 or 1, v is 0 or a positive integer, preferably an integer of 0 to 2, more preferably 0 or 1, w is 0 or 1, R ⁶¹ to R ⁷⁸ as well as R ^a1 and R ^b1 may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms, and R ⁷⁵ to R ⁷⁸ may be bonded to each other to form a monocycle or polycycle.

In the formula (C-1), n and q are each independently 0, 1 or 2, 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 which may be substituted with a halogen atom other than a fluorine atom, one of R ¹⁰ to R ¹⁷ is a bond, and when q=0, R ¹⁰ and R ¹¹ , R ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , and R ¹⁵ and R ¹⁰ may be bonded to each other to form a monocyclic or polycyclic ring, and when q=1 or 2, R ¹⁰ and R ¹¹ , R ¹¹ and R ¹⁷ , R ¹⁷ and R ¹⁷ , R ¹⁷ and R ¹² , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , and R ¹⁵ and R ¹⁶ , R ¹⁶ and R ¹⁶ , and R ¹⁶ and R ¹⁰ may be bonded to each other to form a monocycle or a polycycle, and the monocycle or the polycycle may have a double bond, or the monocycle or the polycycle may be an aromatic ring.

In the formula (C-2), n and m are each independently 0, 1 or 2; q is 1, 2 or 3; R ¹⁸ to R ³¹ are each 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; when q=1, R ²⁸ and R ²⁹ , R ²⁹ and R ³⁰ , and R ³⁰ and R ³¹ may be bonded to each other to form a monocycle or a polycycle; when q=2 or 3, R ²⁸ and R ²⁸ , R ²⁸ and R ²⁹ , R ²⁹ and R ³⁰ , R ³⁰ and R ³¹ , and R ³¹ and R ³¹ may be bonded to each other to form a monocycle or a polycycle, the monocycle or the polycycle may have a double bond, and the monocycle or the polycycle may be an aromatic ring.

In the formula (C-3), q is 1, 2 or 3, R ³² to R ³⁹ each independently represent 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, and when q=1, R ³⁶ and R ³⁷ , R ³⁷ and R ³⁸ , and R ³⁸ and R ³⁹ may be bonded to each other to form a monocycle or a polycycle, 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 , and R ³⁹ and R ³⁹ may be bonded to each other to form a monocycle or a polycycle, the monocycle or the polycycle may have a double bond, and the monocycle or the polycycle may be an aromatic ring.

The cyclic olefin copolymer (P2) contains the repeating unit (AA) represented by the formula (II) and the repeating unit (C) derived from a cyclic olefin having an aromatic ring, and thus can improve the moist heat resistance while maintaining good transparency.

(Repeating unit (AA) derived from cyclic olefin)
The repeating unit (AA) is a repeating unit represented by the formula (II). By including the repeating unit (AA), the refractive index of the obtained molded article can be further improved.
In addition, the repeating unit (AA) in the cyclic olefin copolymer (P2) does not contain an aromatic ring. When the repeating unit (AA) does not contain an aromatic ring, the moldability of the obtained molded article can be further improved.

When the total content of the repeating unit (AA) and the repeating unit (C) in the cyclic olefin copolymer (P2) is taken as 100 mol%, the content of the repeating unit (AA) in the cyclic olefin copolymer (P2) is preferably 5 mol% or more and 95 mol% or less, more preferably 30 mol% or more and 95 mol% or less, and even more preferably 50 mol% or more and 95 mol% or less.
In this embodiment, the content of the repeating unit (AA) can be measured, for example, by ¹ H-NMR or ¹³ C-NMR.

(Repeating Unit (C) Derived from Cyclic Olefin Having an Aromatic Ring)
The repeating unit (C) is a repeating unit derived from a cyclic olefin having an aromatic ring.
Examples of the cyclic olefin having an aromatic ring include 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), etc. These cyclic olefins having an aromatic ring may be used alone or in combination of two or more.

In the formula (C-1), n and q each independently represent 0, 1, or 2. n is preferably 0 or 1, and more preferably 0. q is preferably 0 or 1, and more preferably 0.
R ¹ to R ¹⁷ each independently represent 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, and it is preferable that one of R ¹⁰ to R ¹⁷ is a bond, and that R ¹⁵ is a bond.
R ¹ to R ¹⁷ are each preferably independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrogen atom.
When q = 0, ^R10 and ^R11 , ^R11 and ^R12 , ^R12 and ^R13 , ^R13 and ^R14 , ^R14 and ^R15 , and ^R15 and ^R10 may be bonded to each other to form a monocycle or polycycle, and when q = 1 or 2, ^R10 and ^R11 , ^R11 and ^R17 , R17 and ^R17 , ^R17 and ^R12 , ^R12 and ^R13 , ^R13 and R14, ^R14 and ^R15 , ^R15 and ^R16 , ^R16 and ^R16 , and ^R16 and ^R10 may be bonded to each other to form a monocycle or polycycle, and the monocycle or ^polycycle may have a double bond, ^and the monocycle or polycycle may be an aromatic ring.
Among the compounds represented by formula (C-1), the compound represented by formula (C-1A) below is preferred.

In the formula (C-1A), n is 0, 1 or 2, preferably 0 or 1, and more preferably 0.

In the formula (C-2), n and m are each independently 0, 1 or 2, and q is 1, 2 or 3. m is preferably 0 or 1, and more preferably 1. n is preferably 0 or 1, and more preferably 0. q is preferably 1 or 2, and more preferably 1.
R ¹⁸ to R ³¹ each independently represent 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.
R ¹⁸ to R ³¹ are each preferably independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrogen atom.
When q=1, ^R28 and ^R29 , ^R29 and ^R30 , and ^R30 and ^R31 may be bonded to each other to form a monocycle or a polycycle, and when q=2 or 3, ^R28 and ^R28 , ^R28 and ^R29 , ^R29 and ^R30 , ^R30 and ^R31 , and ^R31 and ^R31 may be bonded to each other to form a monocycle or a polycycle, the monocycle or the polycycle may have a double bond, or the monocycle or the polycycle may be an aromatic ring.

In the formula (C-3), q is 1, 2 or 3, preferably 1 or 2, and more preferably 1.
R ³² to R ³⁹ each independently represent 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.
R ³² to R ³⁹ are each preferably independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrogen atom.
When q=1, ^R36 and ^R37 , ^R37 and ^R38 , and ^R38 and ^R39 may be bonded to each other to form a monocycle or polycycle, and when q=2 or 3, ^R36 and ^R36 , ^R36 and ^R37 , ^R37 and ^R38 , ^R38 and ^R39 , and ^R39 and ^R39 may be bonded to each other to form a monocycle or polycycle, the monocycle or polycycle may have a double bond, and the monocycle or polycycle may be an aromatic ring.

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

Among these, the cyclic olefin having an aromatic ring is preferably at least one selected from the group consisting of benzonorbornadiene, indenenorbornene, and methylphenylnorbornene.

When the total content of the repeating unit (AA) and the repeating unit (C) in the cyclic olefin copolymer (P2) is taken as 100 mol%, the content of the repeating unit (C) in the cyclic olefin copolymer (P2) is preferably 5 mol% or more and 95 mol% or less, more preferably 5 mol% or more and 70 mol% or less, and even more preferably 5 mol% or more and 50 mol% or less.
In this embodiment, the contents of the repeating unit (AA) and the repeating unit (C) can be measured, for example, by ¹ H-NMR or ¹³ C-NMR.

The copolymer type of the cyclic olefin copolymer (P2) is not particularly limited, but examples thereof include random copolymers and block copolymers. In this embodiment, from the viewpoint of obtaining optical components having excellent transparency and heat resistance, it is preferable that the cyclic olefin copolymer (P2) is a random copolymer.

The cyclic olefin copolymer (P2) can be produced by appropriately selecting the conditions according to the methods described in, for example, JP-A-60-168708, JP-A-61-120816, JP-A-61-115912, JP-A-61-115916, JP-A-61-271308, JP-A-61-272216, JP-A-62-252406, JP-A-62-252407, JP-A-2007-314806, JP-A-2010-241932, etc.

It is preferable that the cyclic olefin resin (A) does not contain any carbon-carbon double bonds, but if it does contain any, it is preferable that the amount is 0.5 g or less per 100 g of the cyclic olefin resin (A). By being substantially free of carbon-carbon double bonds, deterioration of the resin composition can be suppressed, which is preferable. The content of carbon-carbon double bonds in the cyclic olefin resin (A) is determined by the iodine value method (titration method) in accordance with JIS K0070.

The melt flow rate (MFR) of the cyclic olefin resin (A), measured in accordance with ASTM D1238 at 260°C under a load of 2.16 kg, is preferably 5 g/10 min or more, more preferably 8 g/10 min or more, even more preferably 10 g/10 min or more, and even more preferably 20 g/10 min or more, from the viewpoint of further improving moldability, and the upper limit is not particularly limited, but may be, for example, 100 g/10 min or less, or 50 g/10 min or less.

The glass transition temperature (Tg) of the cyclic olefin resin (A) is, from the viewpoint of improving the performance balance of moldability, transparency and heat resistance, preferably 70° C. or higher, more preferably 80° C. or higher, even more preferably 90° C. or higher, even more preferably 100° C. or higher, even more preferably 110° C. or higher, even more preferably 120° C. or higher, even more preferably 130° C. or higher, and even more preferably 140° C. or higher, and from the viewpoint of improving the performance balance of moldability, transparency and heat resistance, it is preferably 250° C. or lower, more preferably 200° C. or lower, even more preferably 180° C. or lower, even more preferably 170° C. or lower, and even more preferably 160° C. or lower.
The glass transition temperature (Tg) of the cyclic olefin resin (A) can be measured, for example, by the method described in the Examples.

The intrinsic viscosity η [dl/g] (in decalin at 135° C.) of the cyclic olefin resin (A) is, from the viewpoint of further improving the performance balance between moldability and optical properties, preferably 0.05 dl/g or more, more preferably 0.1 dl/g or more, even more preferably 0.2 dl/g or more, and even more preferably 0.3 dl/g or more, and from the same viewpoint, is preferably 5.0 dl/g or less, more preferably 4.0 dl/g or less, even more preferably 2.0 dl/g or less, and even more preferably 1.0 dl/g or less.
The intrinsic viscosity η [dl/g] of the cyclic olefin resin (A) can be measured in accordance with ASTM J1601.

(Phenol-based antioxidant (B))
The recycled cyclic olefin resin composition of the present embodiment contains a phenol-based antioxidant (B). The phenol-based antioxidant (B) may be used alone or in combination of two or more kinds.
By including a phenol-based antioxidant (B) in the recycled cyclic olefin resin composition, yellowing during molding of the recycled cyclic olefin resin composition can be suppressed, and a decrease in the transparency of the molded body can be suppressed.

The phenol-based antioxidant (B) is not particularly limited, and for example, a known phenol-based antioxidant can be used, but it is preferable that the antioxidant contains at least one selected from the group consisting of pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5.5]undecane, and 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene.

(Phosphorus-based stabilizer (C))
The phosphorus-based stabilizer (C) has a 10% mass loss temperature in the air of 275° C. or higher as measured by a calorimeter.
The 10% mass loss temperature of the phosphorus-based stabilizer (C) is preferably 280°C or higher, more preferably 285°C or higher, and more preferably 290°C or higher. The upper limit is not particularly limited, but may be, for example, 310°C or lower, 305°C or lower, or 300°C or lower.
When the 10% mass loss temperature of the phosphorus-based stabilizer (C) is equal to or higher than the lower limit, yellowing during molding of the recycled cyclic olefin resin composition can be suppressed, and a decrease in the transparency of the molded body can be suppressed.
The 10% mass loss temperature of the phosphorus-based stabilizer (C) means a temperature measured by the method described in the examples.

If the recycled cyclic olefin resin composition contains a phosphorus-based stabilizer having a 10% mass loss temperature of less than 275°C, yellowing of the recycled cyclic olefin resin composition during molding may be promoted.
Therefore, the content of the phosphorus-based stabilizer having a 10% mass loss temperature of less than 275°C per 100 parts by mass of the cyclic olefin resin (A) is preferably less than 0.05 parts by mass, more preferably less than 0.03 parts by mass, even more preferably less than 0.01 parts by mass, and even more preferably 0.00 parts by mass.

In other words, the inventors have discovered that it is important to set the 10% mass loss temperature of the phosphorus-based stabilizer contained in the recycled cyclic olefin resin composition within a specific range in order to obtain molded bodies and optical components in which the decrease in transparency and yellowing are suppressed.

The phosphorus-based stabilizer (C) is not particularly limited as long as the 10% mass loss temperature is within the range of the present invention, but it is preferable that the phosphorus-based stabilizer (C) contains at least one type selected from the group consisting of phosphorus-based stabilizers represented by the following formula (1) and phosphorus-based stabilizers represented by the following formula (3).

In the above formula (1), R ⁵⁰¹ to R ⁵⁰⁵ may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
In R ⁵⁰¹ to R ⁵⁰⁵ , specific examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, and a nonyl group.

The phosphorus-based stabilizer represented by (1) above is, for example, triphenyl phosphite, tris(4-methylphenyl) phosphite, tris(4-tert-butylphenyl) phosphite, tris(2-methyl-4-ethylphenyl) phosphite, tris(2-methyl-4-tert-butylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, tris(2,6-di-tert-butylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, It contains at least one selected from the group consisting of tris(2,4-di-tert-butylphenyl)phosphite, tris(nonylphenyl)phosphite, and tris(di-nonylphenyl)phosphite, and preferably contains one or two selected from the group consisting of tris(2,6-di-tert-butylphenyl)phosphite, and more preferably contains tris(2,4-di-tert-butylphenyl)phosphite.

In the formula (3), R ⁷⁰⁰ is a hydrocarbon group having 1 to 29 carbon atoms, and R ⁷⁰¹ to R ⁷⁰⁸ may be the same or different and are a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
In R ⁷⁰⁰ , examples of the hydrocarbon group having 1 to 29 carbon atoms include an alkyl group having 1 to 29 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms. More specifically, examples of the alkyl group include an octyl group, a hexyl group, and an octadecyl group. Examples of the cycloalkyl group include a cyclohexyl group. Examples of the aromatic hydrocarbon group include a phenyl group and a benzyl group.
In R ⁷⁰¹ to R ⁷⁰⁸ , examples of the alkyl group having 1 to 20 include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, and a nonyl group.

Examples of the phosphorus stabilizer represented by the formula (3) include 2,2'-methylenebis(4,6-di-tert-butylphenyl)-2-ethylhexyl phosphite, 2,2'-methylenebis(4,6-dimethylphenyl)octyl phosphite, 2,2'-methylenebis(4-tert-butyl-6-methylphenyl)octyl phosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite, 2,2'-methylenebis(4,6-dimethylphenyl)hexyl phosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)hexyl phosphite, ) hexyl phosphite, and 2,2'-methylene bis (4,6-di-tert-butylphenyl) stearyl phosphite, etc., preferably one or two selected from the group consisting of 2,2'-methylene bis (4,6-di-tert-butylphenyl) -2-ethylhexyl phosphite, and 2,2'-methylene bis (4,6-di-tert-butylphenyl) octyl phosphite, more preferably 2,2'-methylene bis (4,6-di-tert-butylphenyl) -2-ethylhexyl phosphite.

The phosphorus-based stabilizer (C) may be used alone or in combination of two or more types.

(Other ingredients)
In addition to the cyclic olefin resin (A), the phenol-based antioxidant (B), and the phosphorus-based stabilizer (C), the recycled cyclic olefin resin composition of this embodiment may contain other known optional components within a range that does not impair the good physical properties of the recycled cyclic olefin resin composition.
Examples of other components include resins other than the cyclic olefin resin (A), surfactants, hydrophilic agents, weather stabilizers, heat stabilizers, antistatic agents, flame retardants, slip agents, antiblocking agents, antifogging agents, lubricants, dyes, pigments, natural oils, synthetic oils, waxes, organic or inorganic fillers, etc. The amount of other components to be blended is an appropriate amount.

[Method of producing recycled cyclic olefin resin composition]
The recycled cyclic olefin resin composition of the present embodiment is obtained by mixing each component. The order of mixing each component is not particularly limited, and it can be mixed in any manner such as all at once or in portions. The device for mixing each component is also not particularly limited, and it can be mixed in any device capable of stirring and mixing, such as a batch type or a continuous type.

The recycled cyclic olefin resin composition of this embodiment can also be in the form of pellets. The recycled cyclic olefin resin composition in the form of pellets can be obtained, for example, by kneading the resin in an extruder, and molding the mixture into pellets by water cooling and cutting.

[Molded body and optical component]
The molded article of this embodiment contains the recycled cyclic olefin resin composition of this embodiment.
Since the molded article of the present embodiment contains the recycled cyclic olefin resin composition of the present embodiment, it has a good balance of heat resistance, chemical resistance, low moisture absorption, etc., and is suppressed from decreasing transparency and yellowing. In addition, since the molded article of the present embodiment contains the recycled cyclic olefin resin composition of the present embodiment, it is also preferable from the viewpoint of protecting the global environment.

From the viewpoint of further improving the performance balance between moldability and optical properties, the content of the recycled cyclic olefin resin composition of this embodiment in the molded product of this embodiment is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, even more preferably 98% by mass or more, even more preferably 99% by mass or more, and preferably 100% by mass or less, when the entire molded product is taken as 100% by mass.

The molded article of this embodiment can be obtained by molding the recycled cyclic olefin resin composition of this embodiment into a predetermined shape in a mold. The method of molding the recycled cyclic olefin resin composition of this embodiment to obtain a molded article is not particularly limited, and any known method 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. can be applied. Among these, injection molding and extrusion molding are preferred from the viewpoint of moldability and productivity, and injection molding is more preferred. In addition, molding conditions are appropriately selected depending on the purpose of use or molding method, and for example, the resin temperature in injection molding is appropriately selected within the range of, for example, 150°C to 400°C, preferably 200°C to 350°C, more preferably 230°C to 330°C.

The molded product of this embodiment can be used in various forms, such as lens, sphere, rod, plate, column, cylinder, tube, fiber, film, or sheet.

In addition to the recycled cyclic olefin resin composition of this embodiment, the molded article of this embodiment may contain other known components as optional components within a range that does not impair the good physical properties of the molded article.
Examples of other components include resins other than the cyclic olefin resin (A), surfactants, hydrophilic agents, weather stabilizers, heat stabilizers, antistatic agents, flame retardants, slip agents, antiblocking agents, antifogging agents, lubricants, dyes, pigments, natural oils, synthetic oils, waxes, organic or inorganic fillers, etc. The amount of other components to be blended is an appropriate amount.

The optical component of this embodiment includes the molded article of this embodiment.
The molded article of the present embodiment has good transparency and can therefore be suitably used as an optical component.
Optical components are components used in optical devices and the like, and specifically, they can be particularly suitably used in optical components that require heat resistance and transparency, such as sensor lenses, pickup lenses, projector lenses, prisms, fθ lenses, imaging lenses, light guide plates, in-vehicle camera lenses, and camera lenses for mobile devices (mobile phones, smartphones, tablets, etc.). Examples of in-vehicle camera lenses and camera lenses for mobile devices include view camera lenses; sensing camera lenses; lenses for light convergence in head-up displays; lenses for light diffusion in head-up displays; lenses in various optical devices such as cameras for personal computers, cameras for mobile phones, cameras for smartphones, cameras for tablet terminals, cameras for mobile devices, digital cameras, and cameras for medical devices. Other uses include automobile interior panels, automobile lamp lenses, automobile inner lenses, automobile lens protective covers, automobile light guides, etc.

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 also be adopted.
Furthermore, the present invention is not limited to the above-described embodiment, and modifications and improvements within the scope of the present invention that can achieve the object of the present invention are included in the present invention.

The present embodiment will be described in detail below with reference to examples. Note that the present embodiment is not limited to the description of these examples.

First, we will explain the measurement and evaluation methods used in the examples and comparative examples.

[Measurement and evaluation methods]
(1) Melt flow rate (MFR) of cyclic olefin resin (A)
The MFR of the cyclic olefin resin (A) was measured at 260° C. under a load of 2.16 kg in accordance with ASTM D1238.

(2) Glass transition temperature (Tg) of cyclic olefin resin (A)
The glass transition temperature (Tg) of the cyclic olefin resin (A) was measured under a nitrogen atmosphere using a Discovery DSC-2500 manufactured by TA Instruments. The cyclic olefin resin (A) was heated from room temperature (23°C) to 200°C at a heating rate of 10°C/min and then held for 5 minutes. Then, the temperature was lowered to -20°C at a heating rate of 10°C/min and then held for 5 minutes. The glass transition temperature (Tg) of the cyclic olefin resin (A) was obtained from the endothermic curve when the temperature was raised to 200°C at a heating rate of 10°C/min.

(3) Content of repeating unit (b) derived from cyclic olefin monomer in cyclic olefin resin (A) ¹ H-NMR or ¹³ C-NMR of cyclic olefin resin (A) was measured using a nuclear magnetic resonance apparatus (manufactured by Bruker Biospin, ADVANCEIII cryo-500). The content of repeating unit (b) derived from cyclic olefin monomer in cyclic olefin resin (A) was calculated from the integral ratio of the obtained spectrum.

(4) 10% Mass Reduction Temperature of Phosphorus-Based Stabilizer (C) Using a TG-DTA device (TG/DTA7300, manufactured by Hitachi High-Tech Science Corporation) as a calorimeter, 5 mg of phosphorus-based stabilizer (C) was weighed into a sample pan and heated from 30°C to 500°C at a heating rate of 10°C/min in an air atmosphere to measure the mass reduction of the sample. From the thermogravimetric curve, the temperature at which the weight was reduced by 10% was determined as the 10% mass reduction temperature of the phosphorus-based stabilizer (C).
Here, the atmospheric atmosphere means an atmosphere using atmospheric air containing 21 mass % oxygen and 78 mass % nitrogen under atmospheric pressure.

(5) Light transmittance of molded body at a wavelength of 450 nm Using an injection molding machine (SE30DUZ, manufactured by Sumitomo Heavy Industries, Ltd.), pellet-shaped recycled cyclic olefin resin composition was injection molded under conditions of a cylinder temperature of 270°C and a mold temperature of 126°C to produce a test piece with an optical surface of 65 mm length x 35 mm width x 3 mm thickness.
The light transmittance at a wavelength of 450 nm of the obtained test pieces was measured using a UV-Vis-NIR spectrophotometer UH4150 (manufactured by Hitachi High-Tech Science Corp.) In terms of the evaluation of transparency, a light transmittance at a wavelength of 450 nm of 87.0% or more was rated as A (good), and a light transmittance of less than 87.0% was rated as B (poor).

(6) Evaluation of Yellowing The test pieces obtained in (5) were visually observed. The evaluation of yellowing was rated as A (good) when no yellowing was observed on the test pieces, and as B (poor) when yellowing was observed on the test pieces.

[Example 1]
<Synthesis of Cyclic Olefin Resin (A)>
(Catalyst Preparation)
Ethyl aluminum sesquichloride (Al(C ₂ H ₅ ) _1.5 Cl _1.5 ) was diluted with cyclohexane to prepare an organoaluminum compound catalyst solution.

(polymerization)
In a stirred polymerization vessel, ethylene and ^tetracyclo [ ^{4.4.0.12,5.17,10} ]-3-dodecene (hereinafter also referred to as "TD") were copolymerized using the organoaluminum compound catalyst solution prepared by the above method as a catalyst to obtain a copolymer solution. Here, ethylene was supplied into the polymerization vessel together with hydrogen gas.

(Demineralization)
Water and an aqueous solution of sodium hydroxide were added to the obtained copolymer solution to terminate the polymerization reaction and to remove (demine) the catalyst residue present in the copolymer solution. Also, the catalyst residue present in the copolymer was removed (demine) from the copolymer solution.

(Removal of Solvent)
A stabilizer was added to the deashed copolymer solution, mixed, and heated to 180°C to remove the solvent and unreacted monomers, thereby obtaining a molten random copolymer of ethylene and tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]-3-dodecene as the cyclic olefin resin (A).

(Pelletization)
The obtained molten cyclic olefin resin (A) was charged into a vented twin-screw kneading extruder through a resin charging section of the extruder, and then pelletized with an underwater pelletizer attached to the outlet of the extruder. The pellets were dried with hot air at a temperature of 100° C. for 4 hours to obtain a pelletized cyclic olefin resin (A).
The obtained pellet-shaped cyclic olefin resin (A) had a glass transition temperature (Tg) of 151° C. and an MFR of 28 g/10 min (260° C., 2.16 kg load). The content of the repeating unit derived from TD (corresponding to the repeating unit (b) derived from the cyclic olefin monomer) in the cyclic olefin resin (A) was 37 mol%.

<Preparation of Recycled Cyclic Olefin Resin (A1)>
The sprue and runner of the pellet-shaped cyclic olefin resin (A) (injection molded product) obtained in the above <Synthesis of cyclic olefin resin (A)> were crushed with a crusher to prepare a 3 mm square recovered cyclic olefin resin (A1). The recovered cyclic olefin resin (A1) had a glass transition temperature (Tg) of 151° C. and an MFR of 30 g/10 min (260° C., 2.16 kg load).

<Preparation of Recycled Cyclic Olefin Resin Composition>
0.10 part by mass of pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (manufactured by ADEKA Corporation, Adeka STAB (registered trademark) AO-60) as a phenol-based antioxidant (B1) and 0.05 part by mass of tris(2,4-di-tert-butylphenyl)phosphite (manufactured by ADEKA Corporation, Adeka STAB 2112) as a phosphorus-based stabilizer (C1) were added and mixed with 100 parts by mass of the recovered cyclic olefin resin (A1).
The mixture was charged into the resin charging section of a twin-screw extruder (manufactured by Japan Steel Works, Ltd., TEX44) with unidirectional rotation, screw diameter: 44 mm, and L/D = 30, and melt-kneaded under conditions of screw rotation speed: 150 rpm, motor power: 30 kW. The extruded strands were cut with a pelletizer to obtain a pellet-shaped recycled cyclic olefin resin composition containing the recovered cyclic olefin resin (A1), a phenol-based antioxidant (B1), and a phosphorus-based stabilizer (C1).

[Example 2]
In the above <Preparation of Recycled Cyclic Olefin Resin Composition>, a pellet-shaped recycled cyclic olefin resin composition was obtained in the same manner as in Example 1, except that 2,2'-methylenebis(4,6-di-tert-butylphenyl)-2-ethylhexyl phosphite (ADEKA Corporation, Adekastab HP-10) was used as the phosphorus-based stabilizer (C2) instead of the phosphorus-based stabilizer (C1).

[Comparative Example 1]
In the above <Preparation of recycled cyclic olefin resin composition>, a pellet-shaped recycled cyclic olefin resin composition was obtained in the same manner as in Example 1, except that tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene-diphosphite (Hostanox (registered trademark) P-EPQ, manufactured by Clariant Chemicals) was used as the phosphorus-based stabilizer (C3) instead of the phosphorus-based stabilizer (C1).

[Comparative Example 2]
A pellet-shaped recycled cyclic olefin resin composition was obtained in the same manner as in Example 1, except that in the above <Preparation of recycled cyclic olefin resin composition>, 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane (ADEKA Corporation, Adekastab PEP-8) was used as the phosphorus-based stabilizer (C4) instead of the phosphorus-based stabilizer (C1).

[Comparative Example 3]
A pellet-shaped recycled cyclic olefin resin composition was obtained in the same manner as in Example 1, except that in the above <Preparation of recycled cyclic olefin resin composition>, no phosphorus-based stabilizer was used.

The 10% mass loss temperature was measured for each of the phosphorus-based stabilizers (C1) to (C4) used in the examples and comparative examples, and the results are shown in Table 1.
The evaluation of transparency and yellowing of the molded articles containing the recycled cyclic olefin resin compositions obtained in Examples 1 and 2 and Comparative Examples 1 to 3 are shown in Table 2.

From Table 2, it can be seen that the molded body containing the recycled cyclic olefin resin composition of the example has good evaluations of both transparency and yellowing. In other words, it can be seen that the recycled cyclic olefin resin composition of this embodiment can provide molded bodies and optical parts in which the decrease in transparency and yellowing are suppressed.

Claims (11)

A recycled cyclic olefin resin composition comprising a cyclic olefin resin (A), a phenol-based antioxidant (B), and a phosphorus-based stabilizer (C),
The cyclic olefin resin (A) contains a recycled cyclic olefin resin (A1),
The phosphorus-based stabilizer (C) is a recycled cyclic olefin resin composition having a 10% mass loss temperature in air of 275°C or higher as measured by a calorimeter. The recycled cyclic olefin resin composition according to claim 1, wherein the content of the phosphorus-based stabilizer (C) is 0.01 parts by mass or more and 1.00 parts by mass or less per 100 parts by mass of the cyclic olefin resin (A). The recycled cyclic olefin resin composition according to claim 1 or 2, wherein the content of the phenol-based antioxidant (B) is 0.01 parts by mass or more and 0.50 parts by mass or less per 100 parts by mass of the cyclic olefin resin (A). The recycled cyclic olefin resin composition according to any one of claims 1 to 3, wherein the mass ratio (C/B) of the content of the phosphorus-based stabilizer (C) to the content of the phenol-based antioxidant (B) is 0.1 or more and 2.5 or less. The recycled cyclic olefin resin composition according to any one of claims 1 to 4, wherein the phosphorus-based stabilizer (C) comprises at least one selected from the group consisting of phosphorus-based stabilizers represented by the following formula (1) and phosphorus-based stabilizers represented by the following formula (3).

(In the formula (1), R ⁵⁰¹ to R ⁵⁰⁵ may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.)

(In the formula (3), R ⁷⁰⁰ is a hydrocarbon group having 1 to 29 carbon atoms, and R ⁷⁰¹ to R ⁷⁰⁸ may be the same or different and are a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.) The recycled cyclic olefin resin composition according to any one of claims 1 to 5, wherein the phenol-based antioxidant (B) includes at least one selected from the group consisting of pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5.5]undecane, and 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene. The cyclic olefin resin (A) is
At least one olefin-derived repeating unit (a) represented by the following formula (I);
At least one repeating unit (b) derived from a cyclic olefin monomer selected from the group consisting of a repeating unit (AA) represented by the following formula (II), a repeating unit (AB) represented by the following formula (III), and a repeating unit (AC) represented by the following formula (IV),
The recycled cyclic olefin resin composition according to any one of claims 1 to 6, comprising a cyclic olefin copolymer (P1) having the formula:

(In the above formula (I), R ³⁰⁰ represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms.)

(In the formula (II), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, R ⁶¹ to R ⁷⁸ as well as R ^a1 and R ^b1 may be the same or different and are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and R ⁷⁵ to R ⁷⁸ may be bonded to each other to form a monocycle or multiple cycles.)

(In the formula (III), x and d are 0 or an integer of 1 or more, y and z are 0, 1 or 2, R ⁸¹ to R ⁹⁹ may be the same or different and are a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group which is an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or an alkoxy group, and the carbon atom to which R ⁸⁹ and R ⁹⁰ are bonded may be bonded directly or via an alkylene group having 1 to 3 carbon atoms to the carbon atom to which R ⁹³ is bonded or the carbon atom to which R ⁹¹ is bonded, and when y=z=0, R ⁹⁵ and R ⁹² or R ⁹⁵ and R ⁹⁹ may be bonded to each other to form a monocyclic or polycyclic aromatic ring.)

(In the formula (IV), R ¹⁰⁰ and R ¹⁰¹ may be the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and f is an integer satisfying 1≦f≦18.) The cyclic olefin resin (A) contains a cyclic olefin copolymer (P2) having a repeating unit (AA) represented by the following formula (II) and a repeating unit (C) derived from a cyclic olefin having an aromatic ring,
The repeating unit (AA) does not contain an aromatic ring,
The recycled cyclic olefin resin composition according to any one of claims 1 to 7, wherein the cyclic olefin having an aromatic ring comprises at least one 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):

(In the formula (II), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, R ⁶¹ to R ⁷⁸ as well as R ^a1 and R ^b1 may be the same or different and each represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms, and R ⁷⁵ to R ⁷⁸ may be bonded to each other to form a monocycle or polycycle.)

(In the formula (C-1), n and q are each independently 0, 1 or 2; 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 which may be substituted with a halogen atom other than a fluorine atom; one of R ¹⁰ to R ¹⁷ is a bond; when q=0, R ¹⁰ and R ¹¹ , R ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , and R ¹⁵ and R ¹⁰ may be bonded to each other to form a monocyclic or polycyclic ring; 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 , and R ¹⁴ and R ¹⁵ , R ¹⁵ and R ¹⁶ , R ¹⁶ and R ¹⁶ , and R ¹⁶ and R ¹⁰ may be bonded to each other to form a monocycle or polycycle, and the monocycle or polycycle may have a double bond, or the monocycle or polycycle may be an aromatic ring.

(In the formula (C-2), n and m are each independently 0, 1 or 2; q is 1, 2 or 3; R ¹⁸ to R ³¹ are each 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; when q=1, R ²⁸ and R ²⁹ , R ²⁹ and R ³⁰ , and R ³⁰ and R ³¹ may be bonded to each other to form a monocycle or a polycycle; when q=2 or 3, R ²⁸ and R ²⁸ , R ²⁸ and R ²⁹ , R ²⁹ and R ³⁰ , R ³⁰ and R ³¹ , and R ³¹ and R ³¹ may be bonded to each other to form a monocycle or a polycycle, the monocycle or the polycycle may have a double bond, and the monocycle or the polycycle may be an aromatic ring.)

(In the formula (C-3), q is 1, 2 or 3, R ³² to R ³⁹ are each 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, and when q=1, R ³⁶ and R ³⁷ , R ³⁷ and R ³⁸ , and R ³⁸ and R ³⁹ may be bonded to each other to form a monocycle or a polycycle, 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 , and R ³⁹ and R ³⁹ may be bonded to each other to form a monocycle or a polycycle, the monocycle or the polycycle may have a double bond, and the monocycle or the polycycle may be an aromatic ring.) The recycled cyclic olefin resin composition according to any one of claims 1 to 8, which is in pellet form. A molded article comprising the recycled cyclic olefin resin composition according to any one of claims 1 to 9. An optical component comprising the molded article according to claim 10.