JP7195058B2 - Cyclic olefin resin composition, molded article and optical part - Google Patents

Description

TECHNICAL FIELD The present invention relates to a cyclic olefin resin composition, a molded article and an optical component.

Cyclic olefin-based resin compositions are excellent in optical performance, and are therefore used as optical components such as optical lenses.
Techniques related to cyclic olefin-based resin compositions used in optical components include, for example, those described in Patent Document 1 (Japanese Unexamined Patent Application Publication No. 2015-199939).

Patent Document 1 discloses a cyclic olefin resin composition containing a cyclic olefin polymer and a diglycerin fatty acid ester. Patent Document 1 describes that the use of such a cyclic olefin-based resin composition provides a molded article having excellent optical performance and suppressing deterioration of optical performance under high-temperature and high-humidity conditions.

JP 2015-199939 A

According to the studies of the present inventors, when a cyclic olefin-based resin composition containing a cyclic olefin-based polymer and a diglycerin fatty acid ester, as described in Examples of Patent Document 1, is used, optical performance is excellent. Furthermore, although it is possible to realize optical components that suppress the deterioration of optical performance under high temperature and high humidity conditions, depending on the shape of the optical component to be manufactured, weld lines (in resin molding, where molten resin flows join together in the mold) It was thought that there is room for improvement in the thin line that occurs in the fused part).
Specifically, the inventors aimed to further reduce the weld line that occurs when an optical component having a large ratio of maximum thickness to minimum thickness (hereinafter also referred to as thickness deviation ratio) is produced. If a weld line occurs and an optical defect occurs, there is a possibility that deterioration of image quality such as a flare phenomenon or a ghost phenomenon may occur, so the weld line is preferably as small as possible.

The present invention has been made in view of the above circumstances, and provides a cyclic olefin resin composition capable of realizing an optical component that is excellent in optical performance and suppresses the deterioration of optical performance and the occurrence of weld lines under high temperature and high humidity conditions. It provides

The present inventors have diligently studied to solve the above problems. As a result, by using a resin composition in which a triglycerol fatty acid ester is blended with a cyclic olefin polymer, the optical performance is excellent, and the deterioration of the optical performance and the occurrence of weld lines under high temperature and high humidity conditions are suppressed. The present inventors have completed the present invention by discovering that an optical component can be realized.

The present invention is as described below.

（上記一般式（Ｉ）において、Ｒ^３００は水素原子又は炭素原子数１～２９の直鎖状または分岐状の炭化水素基を示す。）

（上記一般式（ＩＩ）において、ｕは０または１であり、ｖは０または正の整数であり、ｗは０または１であり、Ｒ^６１～Ｒ^７８ならびにＲ^ａ１および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または炭素原子数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または多環を形成していてもよい。）

（上記一般式（ＩＩＩ）において、ｘおよびｄは０または１以上の整数であり、ｙおよびｚは０、１または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またはアルコキシ基であり、Ｒ^８９および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または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またはＲ^９５とＲ^９９とは互いに結合して単環または多環の芳香族環を形成していてもよい。）

（上記一般式（ＩＶ）において、Ｒ^１００、Ｒ^１０１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１～５の炭化水素基を示し、ｆは１≦ｆ≦１８である。）
［４］
上記［３］に記載の環状オレフィン系樹脂組成物において、
上記共重合体（Ａ１）中の上記環状オレフィン由来の繰り返し単位（ｂ）が、ビシクロ［２．２．１］－２－ヘプテンおよびテトラシクロ［４．４．０．１^２，５．１^７，１０］－３－ドデセンから選ばれる少なくとも一種の化合物に由来する繰り返し単位を含む環状オレフィン系樹脂組成物。
［５］
上記［３］または［４］に記載の環状オレフィン系樹脂組成物において、
上記共重合体（Ａ１）中の上記オレフィン由来の繰り返し単位（ａ）が、エチレンに由来する繰り返し単位を含む環状オレフィン系樹脂組成物。
［６］
上記［１］乃至［５］のいずれか一つに記載の環状オレフィン系樹脂組成物において、
上記環状オレフィン系樹脂組成物に含まれる上記環状オレフィン系重合体（Ａ）を１００質量部としたとき、上記トリグリセリン脂肪酸エステルの含有量が０．０５質量部以上１．５質量部以下である環状オレフィン系樹脂組成物。
［７］
上記［１］乃至［６］のいずれか一つに記載の環状オレフィン系樹脂組成物において、
上記トリグリセリン脂肪酸エステルが、トリグリセリンと炭素数８以上２４以下の飽和または不飽和脂肪酸とのエステルを含む環状オレフィン系樹脂組成物。
［８］
上記［１］乃至［７］のいずれか一つに記載の環状オレフィン系樹脂組成物において、
上記環状オレフィン系樹脂組成物のガラス転移温度が１３０℃以上１６０℃以下の範囲にある環状オレフィン系樹脂組成物。
［９］
上記［１］乃至［８］のいずれか一つに記載の環状オレフィン系樹脂組成物を含む成形体。
［１０］
上記［９］に記載の成形体を含む光学部品。
［１１］
上記［１０］に記載の光学部品において、
ｆθレンズ、撮像レンズ、センサーレンズ、プリズムまたは導光板である光学部品。
［１２］
上記［１０］または［１１］に記載の光学部品において、
上記光学部品の最大厚みをＴ_ｍａｘとし、上記光学部品の最小厚みをＴ_ｍｉｎとしたとき、
Ｔ_ｍａｘ／Ｔ_ｍｉｎで示される偏肉比が２．０以上である光学部品。 [1]
A cyclic olefin resin composition containing a cyclic olefin polymer (A) and a triglycerin fatty acid ester.
[2]
In the cyclic olefin resin composition described in [1] above,
A cyclic olefin-based resin composition in which the cyclic olefin-based polymer (A) contains at least one selected from a copolymer (A1) of ethylene or an α-olefin and a cyclic olefin and a ring-opening polymer of a cyclic olefin (A2). thing.
[3]
In the cyclic olefin resin composition described in [2] above,
The cyclic olefin polymer (A) contains the copolymer (A1),
The copolymer (A1) is
at least one olefin-derived repeating unit (a) represented by the following general formula (I);
At least one cyclic olefin selected from the group consisting of repeating units represented by the following general formula (II), repeating units represented by the following general formula (III), and repeating units represented by the following general formula (IV) a repeating unit (b) derived from
A cyclic olefin resin composition containing a cyclic olefin copolymer containing

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

(In general formula (II) above, u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, and R ⁶¹ to R ⁷⁸ and R ^a1 and R ^b1 are the same hydrogen atom, halogen atom, alkyl group having 1 to 20 carbon atoms, halogenated alkyl group having 1 to 20 carbon atoms, cycloalkyl group having 3 to 15 carbon atoms or 6 carbon atoms to 20 aromatic hydrocarbon groups, and R ⁷⁵ to R ⁷⁸ may be bonded together to form a monocyclic or polycyclic ring.)

(In the above general 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, 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 and the carbon atom to which R ⁹³ is bonded or the carbon atom to which R ⁹¹ is bonded are directly or an alkylene group having 1 to 3 carbon atoms 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. good.)

(In general formula (IV) above, 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 1 ≤ f ≤ 18. .)
[4]
In the cyclic olefin resin composition described in [3] above,
The repeating unit (b) derived from the cyclic olefin in the copolymer (A1) is bicyclo[2.2.1]-2-heptene and tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene A cyclic olefin resin composition containing a repeating unit derived from at least one compound selected from the group consisting of:
[5]
In the cyclic olefin resin composition according to [3] or [4] above,
A cyclic olefin resin composition in which the olefin-derived repeating unit (a) in the copolymer (A1) contains a repeating unit derived from ethylene.
[6]
In the cyclic olefin resin composition according to any one of [1] to [5] above,
When the cyclic olefin polymer (A) contained in the cyclic olefin resin composition is 100 parts by mass, the content of the triglycerin fatty acid ester is 0.05 parts by mass or more and 1.5 parts by mass or less. A cyclic olefin resin composition.
[7]
In the cyclic olefin resin composition according to any one of [1] to [6] above,
A cyclic olefin resin composition in which the triglycerin fatty acid ester contains an ester of triglycerin and a saturated or unsaturated fatty acid having 8 to 24 carbon atoms.
[8]
In the cyclic olefin resin composition according to any one of [1] to [7] above,
A cyclic olefin resin composition having a glass transition temperature in the range of 130° C. or higher and 160° C. or lower.
[9]
A molded article comprising the cyclic olefin resin composition according to any one of [1] to [8] above.
[10]
An optical component comprising the molded article according to [9] above.
[11]
In the optical component described in [10] above,
An optical component that is an f-theta lens, an imaging lens, a sensor lens, a prism, or a light guide plate.
[12]
In the optical component according to [10] or [11] above,
When the maximum thickness of the optical component is T _max and the minimum thickness of the optical component is T _min ,
An optical component having a thickness deviation ratio represented by T _max /T _min of 2.0 or more.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a cyclic olefin-based resin composition capable of realizing an optical component that is excellent in optical performance and suppresses the deterioration of optical performance and the occurrence of weld lines under high-temperature and high-humidity conditions.

It is a sectional view showing typically an example of structure of an optical component of an embodiment concerning the present invention.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described with reference to the drawings. In addition, in all the drawings, the same constituent elements are denoted by the same reference numerals, and the explanation thereof is omitted as appropriate. Also, the drawings are schematic diagrams and do not correspond to actual dimensional ratios. In addition, "A to B" indicating a numerical range represents A or more and B or less unless otherwise specified.

[Cyclic olefin resin composition]
First, a cyclic olefin-based resin composition according to an embodiment of the present invention will be described.
The cyclic olefin resin composition according to this embodiment contains a cyclic olefin polymer (A) and a triglycerol fatty acid ester.

According to the cyclic olefin-based resin composition of the present embodiment, it is possible to realize an optical component that is excellent in optical performance and that suppresses the deterioration of optical performance and the occurrence of weld lines under high temperature and high humidity conditions.
The reason for this is not clear, but since the triglycerol fatty acid ester has a moderate amount of hydrophilic groups and contains hydrophobic groups derived from fatty acids, it has excellent compatibility with the cyclic olefin polymer (A) and excellent optical performance. optical components can be obtained. Furthermore, triglycerin fatty acid esters have hydrophilic functional groups such as hydroxyl groups, ether groups, and carbonyl groups. Therefore, even when molding is performed under high-temperature and high-humidity conditions, water absorbed in the resin composition is dispersed, presumably suppressing aggregation of water that causes deterioration of optical performance. Furthermore, since triglycerin fatty acid ester has a higher molecular weight than diglycerin fatty acid ester or monoglycerin fatty acid ester, gasification during molding of optical parts can be suppressed, and as a result, the occurrence of weld lines in optical parts can be prevented. can be suppressed.
Furthermore, according to the studies of the present inventors, a molded article using a cyclic olefin resin composition containing a cyclic olefin polymer and a diglycerin fatty acid ester, as described in Examples of Patent Document 1, When continuously molding, dirt may adhere to the mold, and it is clear that conventional resin compositions have room for improvement from the viewpoint of reducing the adhesion of mold dirt during continuous molding. became. The present inventors have diligently studied to solve the above problems. As a result, the inventors have found that by using a resin composition containing a triglycerol fatty acid ester blended with a cyclic olefin polymer, adhesion of mold contamination during continuous molding can be reduced. That is, according to the cyclic olefin-based resin composition according to the present embodiment, it is possible to reduce adhesion of mold contamination during continuous molding.

The lower limit of the content of the cyclic olefin polymer (A) and the triglycerin fatty acid ester in the cyclic olefin resin composition according to the present embodiment is preferably when the entire cyclic olefin resin composition is 100% by mass. is 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and particularly preferably 95% by mass or more. When the contents of the cyclic olefin polymer (A) and the triglycerin fatty acid ester in the cyclic olefin resin composition according to the present embodiment are at least the above lower limit values, the optical performance can be further improved. .
Although the upper limit of the content of the cyclic olefin polymer (A) and the triglycerin fatty acid ester in the cyclic olefin resin composition according to the present embodiment is not particularly limited, it is, for example, 100% by mass or less.

Each component will be specifically described below.

(Cyclic olefin polymer (A))
The cyclic olefin polymer (A) according to the present embodiment is a polymer having repeating units derived from a cyclic olefin as essential structural units.
Examples of the cyclic olefin polymer (A) include at least one selected from copolymers (A1) of ethylene or α-olefins and cyclic olefins and ring-opening polymers of cyclic olefins (A2).

The cyclic olefin compound constituting the copolymer (A1) according to the present embodiment is not particularly limited. .

The copolymer (A1) according to the present embodiment is capable of further improving heat resistance and improving moldability while maintaining a good performance balance of transparency and refractive index of the resulting molded product. At least one olefin-derived repeating unit (a) represented by the general formula (I), a repeating unit represented by the following general formula (II), a repeating unit represented by the following general formula (III), and the following and at least one cyclic olefin-derived repeating unit (b) selected from the group consisting of repeating units represented by formula (IV).

上記一般式（Ｉ）において、Ｒ^３００は水素原子または炭素原子数１～２９の直鎖状または分岐状の炭化水素基を示す。

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

上記一般式（ＩＩ）において、ｕは０または１であり、ｖは０または正の整数、好ましくは０以上２以下の整数、より好ましくは０または１であり、ｗは０または１であり、Ｒ^６１～Ｒ^７８ならびにＲ^ａ１および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または炭素原子数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または多環を形成していてもよい。

In the above general formula (II), u is 0 or 1, v is 0 or a positive integer, preferably an integer of 0 or more and 2 or less, more preferably 0 or 1, w is 0 or 1, R ⁶¹ to R ⁷⁸ , R ^a1 and R ^b1 may be the same or different, and may be 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, It is 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 combine with each other to form a monocyclic or polycyclic ring.

上記一般式（ＩＩＩ）において、ｘおよびｄは０または１以上の整数、好ましくは０以上２以下の整数、より好ましくは０または１であり、ｙおよびｚは０、１または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またはアルコキシ基であり、Ｒ^８９および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または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またはＲ^９５とＲ^９９とは互いに結合して単環または多環の芳香族環を形成していてもよい。

In the general formula (III), 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, and R ⁸¹ to R ⁹⁹ may be the same or different, and may be 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, carbon an aromatic hydrocarbon group or an alkoxy group having 6 to 20 atoms, the carbon atom to which R ⁸⁹ and R ⁹⁰ are bonded and the carbon atom to which R ⁹³ is bonded or the carbon atom to which R ⁹¹ is bonded may be bonded directly or through an alkylene group having 1 to 3 carbon atoms, and when y = z = 0, R ⁹⁵ and R ⁹² or R ⁹⁵ and R ⁹⁹ are bonded to each other It may form a monocyclic or polycyclic aromatic ring.

上記一般式（ＩＶ）において、Ｒ^１００、Ｒ^１０１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１～５の炭化水素基を示し、ｆは１≦ｆ≦１８である。

In general formula (IV) above, 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 1≦f≦18.

The olefin monomer, which is one of the raw materials for copolymerization of the copolymer (A1) according to the present embodiment, undergoes addition copolymerization to form the structural unit represented by the general formula (I). Specifically, an olefin monomer represented by the following general formula (Ia) corresponding to the above general formula (I) is used.

上記一般式（Ｉａ）において、Ｒ^３００は水素原子または炭素原子数１～２９の直鎖状または分岐状の炭化水素基を示す。上記一般式（Ｉａ）で表されるオレフィンモノマーとしては、例えば、エチレン、プロピレン、１－ブテン、１－ペンテン、１－ヘキセン、３－メチル－１－ブテン、３－メチル－１－ペンテン、３－エチル－１－ペンテン、４－メチル－１－ペンテン、４－メチル－１－ヘキセン、４，４－ジメチル－１－ヘキセン、４，４－ジメチル－１－ペンテン、４－エチル－１－ヘキセン、３－エチル－１－ヘキセン、１－オクテン、１－デセン、１－ドデセン、１－テトラデセン、１－ヘキサデセン、１－オクタデセン、１－エイコセン等が挙げられる。より優れた耐熱性、機械的特性および光学特性を有する成形体を得る観点から、これらのなかでも、エチレンとプロピレンが好ましく、エチレンが特に好ましい。上記一般式（Ｉａ）で表されるオレフィンモノマーは２種類以上を用いてもよい。
本実施形態に係る環状オレフィン共重合体を構成する構成単位の全体を１００モル％としたとき、オレフィン由来の繰り返し単位（ａ）の割合が、好ましくは５モル％以上９５モル％以下、より好ましくは２０モル％以上９０モル％以下、さらに好ましくは４０モル％以上８５モル％以下、特に好ましくは５０モル％以上８０モル％以下である。
なお、オレフィン由来の繰り返し単位（ａ）の割合は、^１３Ｃ－ＮＭＲによって測定することができる。

In general formula (Ia) above, 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 general 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, 1-eicosene and the like. Among these, ethylene and propylene are preferred, and ethylene is particularly preferred, from the viewpoint of obtaining molded articles having superior heat resistance, mechanical properties and optical properties. Two or more kinds of olefin monomers represented by the general formula (Ia) may be used.
The ratio of the olefin-derived repeating unit (a) is preferably 5 mol% or more and 95 mol% or less, and more preferably 100 mol% of the total structural units constituting the cyclic olefin copolymer according to the present embodiment. is 20 mol % or more and 90 mol % or less, more preferably 40 mol % or more and 85 mol % or less, and particularly preferably 50 mol % or more and 80 mol % or less.
The proportion of olefin-derived repeating units (a) can be measured by ¹³ C-NMR.

The cyclic olefin monomer (b), which is one of the raw materials for copolymerization of the copolymer (A1) according to the present embodiment, is addition-copolymerized to give the above general formula (II), the above general formula (III), or the above general formula ( It forms the repeating unit (b) derived from the cyclic olefin represented by IV). Specifically, the cyclic olefins represented by the general formulas (IIa), (IIIa), and (IVa) corresponding to the general formula (II), the general formula (III), and the general formula (IV), respectively A monomer (b) is used.

上記一般式（ＩＩａ）において、ｕは０または１であり、ｖは０または正の整数、好ましくは０以上２以下の整数、より好ましくは０または１であり、ｗは０または１であり、Ｒ^６１～Ｒ^７８ならびにＲ^ａ１および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、または炭素原子数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または多環を形成していてもよい。

In the above general formula (IIa), u is 0 or 1, v is 0 or a positive integer, preferably an integer of 0 or more and 2 or less, more preferably 0 or 1, w is 0 or 1, R ⁶¹ to R ⁷⁸ , R ^a1 and R ^b1 may be the same or different, and may be 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 together to form a monocyclic or polycyclic ring; .

上記一般式（ＩＩＩａ）において、ｘおよびｄは０または１以上の整数、好ましくは０以上２以下の整数、より好ましくは０または１であり、ｙおよびｚは０、１または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またはアルコキシ基であり、Ｒ^８９および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または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またはＲ^９５とＲ^９９とは互いに結合して単環または多環の芳香族環を形成していてもよい。

In the general 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, and R ⁸¹ to R ⁹⁹ may be the same or different, and may be 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, carbon an aromatic hydrocarbon group or an alkoxy group having 6 to 20 atoms, the carbon atom to which R ⁸⁹ and R ⁹⁰ are bonded and the carbon atom to which R ⁹³ is bonded or the carbon atom to which R ⁹¹ is bonded may be bonded directly or through an alkylene group having 1 to 3 carbon atoms, and when y = z = 0, R ⁹⁵ and R ⁹² or R ⁹⁵ and R ⁹⁹ are bonded to each other It may form a monocyclic or polycyclic aromatic ring.

上記一般式（ＩＶａ）において、Ｒ^１００、Ｒ^１０１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１～５の炭化水素基を示し、ｆは１≦ｆ≦１８である。

In general formula (IVa) above, R ¹⁰⁰ and R ¹⁰¹ may be the same or different, each represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and f satisfies 1≦f≦18.

By using the olefin monomer represented by the general formula (Ia) or the cyclic olefin monomer (b) represented by the general formula (IIa), (IIIa) or (IVa) as a copolymerization component, a cyclic olefin-based Since the solubility of the polymer (A) in the solvent is further improved, the moldability is improved, and the product yield is improved.

As specific examples of the cyclic olefin monomer (b) represented by general formula (IIa), (IIIa) or (IVa), compounds described in paragraphs 0037 to 0063 of WO 2006/118261 can be used.

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, pentacyclo pentadecadiene derivative, pentacyclo-3-pentadecene derivative, pentacyclo-4-hexadecene derivative, pentacyclo-3-hexadecene derivative, hexacyclo-4-heptadecene derivative, heptacyclo-5-eicosene derivative, heptacyclo-4-eicosene derivative, 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 having 3 to 20 carbon atoms, and the like.

Among the cyclic olefin monomers (b) represented by general formula (IIa), (IIIa) or (IVa), cyclic olefins represented by general formula (IIa) are preferred.

Bicyclo[2.2.1]-2-heptene (also referred to as norbornene), tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene (also called tetracyclododecene) is preferably used, and tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene is more preferably used. Since these cyclic olefins have a rigid ring structure, there is an advantage that the elastic modulus of the copolymer and molded article can be easily maintained.

The ratio of the repeating unit (b) derived from the cyclic olefin monomer (b) is preferably 5 mol% or more and 95 mol % or less, more preferably 10 mol % or more and 80 mol % or less, still more preferably 15 mol % or more and 60 mol % or less, and particularly preferably 20 mol % or more and 50 mol % or less.

Although the copolymerization type of the copolymer (A1) according to the present embodiment is not particularly limited, examples thereof include random copolymers and block copolymers. In the present embodiment, the copolymer (A1) according to the present embodiment has excellent optical properties such as transparency, refractive index, and birefringence, and is capable of obtaining a highly accurate optical component. It is preferred to use polymers.

As the copolymer (A1) according to the present embodiment, ethylene and tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene and random copolymers of ethylene and bicyclo[2.2.1]-2-heptene, preferably ethylene and tetracyclo[4.4. 0.1 ^2,5 . A random copolymer with 1 ^7,10 ]-3-dodecene is more preferred.

As the cyclic olefin polymer (A), a ring-opening polymer (A2) of cyclic olefin can be used.
Examples of the cyclic olefin ring-opening polymer (A2) include ring-opening polymers of norbornene-based monomers and ring-opening weights of norbornene-based monomers and other monomers capable of ring-opening copolymerization thereof. coalescence, hydrides thereof, and the like.

Examples of norbornene-based monomers include, for example, bicyclo[2.2.1]hept-2-ene (common name: norbornene) and derivatives thereof (having a substituent on the ring), tricyclo[ ^{4.3.01 , 6} . 1 ^2,5 ]deca-3,7-diene (common name dicyclopentadiene) and its derivatives, 7,8-benzotricyclo[4.3.0.1 ^2,5 ]dec-3-ene (common name methanotetrahydrofluorene: 1,4-methano-1,4,4a,9a-tetrahydrofluorene) and its derivatives, tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene (common name: tetracyclododecene) and derivatives thereof, and the like.
Examples of substituents on the ring of these derivatives include an alkyl group, an alkylene group, a vinyl group, an alkoxycarbonyl group, and an alkylidene group. In addition, the substituent can have 1 or 2 or more. Derivatives having a substituent on such a ring include, for example, 8-methoxycarbonyl-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodeca-3-ene, 8-methyl-8-methoxycarbonyl-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodeca-3-ene, 8-ethylidene-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodeca-3-ene and the like.
These norbornene-based monomers may be used alone or in combination of two or more.

A ring-opening polymer of a norbornene-based monomer, or a ring-opening polymer of a norbornene-based monomer and other monomers capable of ring-opening copolymerization with the monomer component is prepared by a known ring-opening polymerization. It can be obtained by polymerization in the presence of a catalyst.
The ring-opening polymerization catalyst includes, for example, a metal halide such as ruthenium and osmium, a nitrate or an acetylacetone compound, and a reducing agent; , an organoaluminum compound; and the like.
Other monomers capable of ring-opening copolymerization with norbornene monomers include, for example, monocyclic cyclic olefin monomers such as cyclohexene, cycloheptene, and cyclooctene.

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

In the present embodiment, the cyclic olefin polymer (A) may be used singly or in combination of two or more.

The copolymer (A1) according to the present embodiment is, for example, JP-A-60-168708, JP-A-61-120816, JP-A-61-115912, JP-A-61-115916. , JP-A-61-271308, JP-A-61-272216, JP-A-62-252406, JP-A-62-252407, etc. Producing by appropriately selecting conditions according to the method can be done.
The ring-opening polymer (A2) of a cyclic olefin according to the present embodiment is, for example, JP-A-60-26024, JP-A-9-268250, JP-A-63-145324, JP-A-2001-72839. It can be produced by appropriately selecting the conditions according to the method disclosed in JP-A-2003-203215.

The molecular weight of the cyclic olefin polymer (A) according to the present embodiment is not particularly limited. is preferably 0.03 dl/g to 10 dl/g, more preferably 0.05 dl/g to 5 dl/g, even more preferably 0.10 dl/g to 2 dl/g.
When the molecular weight is at least the above lower limit, the mechanical strength of the molded article can be improved. Moreover, moldability can be improved as molecular weight is below the said upper limit.

The lower limit of the melt flow rate (MFR) of the cyclic olefin polymer (A) measured at 260°C and a load of 2.16 kg in accordance with ASTM D1238 is determined by the processability and production of the cyclic olefin polymer (A). From the viewpoint of easiness, etc., it is preferably 5 g/10 minutes or more, more preferably 8 g/10 minutes or more, and still more preferably 10 g/10 minutes or more.
In addition, the upper limit of the MFR of the cyclic olefin polymer (A) is preferably 60 g/10 minutes or less, more preferably 50 g/10 minutes or less, from the viewpoint of further suppressing the occurrence of weld lines. It is more preferably 40 g/10 minutes or less, still more preferably 35 g/10 minutes or less, and particularly preferably 30 g/10 minutes or less.
The MFR of the cyclic olefin polymer (A) can be adjusted by adjusting the ratio of the hydrogen feed amount to the ethylene feed amount during the polymerization reaction, which will be described later.

The glass transition temperature (Tg) of the cyclic olefin resin composition according to this embodiment is preferably in the range of 130°C or higher and 160°C or lower. When the glass transition temperature (Tg) of the cyclic olefin-based resin composition is within the above range, sufficient heat resistance is obtained when the molded product is used as an optical component that requires heat resistance, such as an in-vehicle camera lens or a camera lens for mobile devices. It is possible to obtain good moldability as well as good moldability.

The glass transition temperature (Tg) of the cyclic olefin-based resin composition according to the present embodiment is, for example, raised from room temperature to 200°C at a rate of 10°C/min under a nitrogen atmosphere using RDC220 manufactured by SII Nanotechnology. After heating, the temperature was held for 5 minutes, then the temperature was lowered to 30°C at a temperature drop rate of 10°C/min, held for 5 minutes, and then heated to 200°C at a temperature increase rate of 10°C/min. can be measured.

(Triglycerol fatty acid ester)
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.

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.

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

In the cyclic olefin-based resin composition according to the present embodiment, when the cyclic olefin-based polymer (A) contained in the cyclic olefin-based resin composition is 100 parts by mass, the lower limit of the content of the triglycerin fatty acid ester is From the viewpoint of further suppressing deterioration of optical performance under high humidity conditions, the amount is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, and 0.2 parts by mass or more. is more preferable, and 0.3 parts by mass or more is particularly preferable.
In addition, the upper limit of the content of the triglycerin fatty acid ester is 1.5 parts by mass or less from the viewpoint of suppressing the gasification amount of the triglycerin fatty acid ester during molding and further suppressing the occurrence of weld lines. Preferably, it is 1.2 parts by mass or less, more preferably 1.0 parts by mass or less, even more preferably 0.8 parts by mass or less, and 0.7 parts by mass or less. is particularly preferred.
Since triglycerin fatty acid esters have a larger amount of hydrophilic groups than diglycerin fatty acid esters or monoglycerin fatty acid esters, it is thought that deterioration of optical performance under high-temperature and high-humidity conditions can be suppressed with a smaller addition amount. In addition, since the amount added can be reduced, the gasification amount of the triglycerol fatty acid ester during molding can be further suppressed, and the occurrence of weld lines can be further suppressed.

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.
Since monoesters have a lower molecular weight than diesters and triesters, a higher monoester content requires a smaller amount (weight) to be added to impart equivalent moisture and heat resistance. It is thought that the effect of suppressing the occurrence of weld lines can be obtained more effectively because the generated gas is less when the added amount is small.
The total content of monoester and diester in the triglycerol fatty acid ester according to the present embodiment is preferably 30% by mass or more and 100% by mass or less, more preferably 40% by mass or more and 100% by mass or less, and 60% by mass or more and 100% by mass. % or less is more preferable, and 70% by mass or more and 100% by mass or less is particularly preferable. Therefore, the triester content is preferably 0% by mass or more and 70% by mass or less, more preferably 0% by mass or more and 60% by mass or less, even more preferably 0% by mass or more and 40% by mass or less, and 0% by mass or more and 30% by mass or less. Especially preferred.
In addition, since diesters have a higher molecular weight than monoesters, the amount (weight) required for imparting moist heat resistance increases, but the amount of generated gas is reduced, so it is thought that the effect of suppressing mold contamination will be higher. . Therefore, the diester content in the triglycerin fatty acid ester is preferably 30% by mass or more and 70% by mass or less, more preferably 40% by mass or more and 60% by mass or less.
Similarly, from the viewpoint of suppressing mold contamination, the tri-ester content in the triglycerol fatty acid ester according to the present embodiment is preferably 1% by mass or more and 50% by mass or less, more preferably 5% by mass or more and 30% by mass or less.
The temperature (Td-10%) at which the weight of the triglycerol fatty acid ester according to the present embodiment decreases by 10% by heating is 260° C. or higher, preferably 270° C. or higher, and still more preferably 280° C. or higher. Although there is no particular upper limit, it is usually 320° C. or less. Here, the initial weight indicates the weight at 30° C. of the triglycerol fatty acid ester or the like. Detailed measurement conditions such as heating temperature are as described in Examples. It is believed that the high weight loss temperature suppresses the generation of gas and thus suppresses mold contamination.

(other ingredients)
The cyclic olefin resin composition according to the present embodiment contains, in addition to the cyclic olefin polymer (A) and the triglycerin fatty acid ester, within a range that does not impair the good physical properties of the cyclic olefin resin composition according to the present embodiment. can contain known additives as optional components.
Examples of additives include antioxidants, secondary antioxidants, lubricants, release agents, antifog agents, weather stabilizers, light stabilizers, ultraviolet absorbers, antistatic agents, metal deactivators, and the like. mentioned.

The cyclic olefin-based resin composition according to the present embodiment is a method of melt-kneading the cyclic olefin-based polymer (A) and triglycerin fatty acid ester using a known kneading device such as an extruder and a Banbury mixer; A method of dissolving the polymer (A) and the triglycerol fatty acid ester in a common solvent and then evaporating the solvent; a method of adding a solution of the cyclic olefin-based polymer (A) and the triglycerol fatty acid ester to a poor solvent to cause precipitation. ; can be obtained by a method such as

[Molded products and optical components]
Next, a molded article according to an embodiment of the present invention will be described.
The molded article according to this embodiment contains the cyclic olefin resin composition according to this embodiment.
Since the molded article according to this embodiment contains the cyclic olefin resin composition according to this embodiment, it has excellent optical performance. Therefore, it can be suitably used as an optical component in an optical system that needs to identify an image with high precision. An optical component is a component used in an optical device or the like, and specifically includes a sensor lens, a pickup lens, a projector lens, a prism, an fθ lens, an imaging lens, a light guide plate, and the like. From the viewpoint of effects, it can be suitably used for an fθ lens, an imaging lens, a sensor lens, a prism, or a light guide plate.
In particular, the molded article obtained from the cyclic olefin-based resin composition according to the present embodiment, which has a glass transition temperature in the range of 130° C. or higher and 160° C. or lower, has high heat resistance and satisfies heat and humidity resistance. It has the surprising effect of suppressing the generation of lines.
Therefore, the molded article obtained from the cyclic olefin-based resin composition according to the present embodiment is particularly suitable for optical parts that require heat resistance, such as vehicle-mounted camera lenses and camera lenses for mobile devices (mobile phones, smartphones, tablets, etc.). can be used. Vehicle-mounted camera lenses and mobile device camera lenses include, for example, view camera lenses, sensing camera lenses, light converging lenses for head-up displays, and light diffusion lenses for head-up displays.

Here, in recent years, electronic and electric devices have become lighter, smaller, and thinner. Therefore, an optical lens (also called a camera lens) used in a camera has a thin shape and a small diameter. (contrast reproduction ratio) is required to be good. Therefore, not only are camera lenses required to be thin, but also their shapes are complicated. For this reason, camera lenses do not have a uniform thickness, but are becoming uneven in thickness, in which thin portions and thick portions coexist.
Here, according to the studies of the present inventors, it is clear that an optical component with a large ratio of maximum thickness to minimum thickness (also called thickness deviation ratio) tends to have a large weld line. became. More specifically, when the maximum thickness of the optical component is T _max and the minimum thickness of the optical component is T _min , the thickness variation ratio indicated by T _max /T _min is 2.0 or more. It became clear that the generated weld line tends to become large.
Therefore, the cyclic olefin-based resin composition according to the present embodiment can be suitably used for molding an optical component having a thickness deviation ratio of 2.5 or more, which is indicated by T _max /T _min . As a result, it is possible to effectively suppress the occurrence of weld lines even in an optical component having a thickness variation ratio of 2.0 or more, which is indicated by T _max /T _min .
Here, the optical component having a complicated shape with a thickness deviation ratio equal to or higher than the above lower limit is not particularly limited, but examples thereof include shapes shown in (a) to (d) of FIG. Also, the distance connecting the opposing surfaces of the optical components is taken, and the longest distance is defined as T _max and the shortest distance is defined as T _min .
Lenses include not only concave lenses and convex lenses, but also various shapes such as aspherical lenses and one-sided concave and one-sided convex lenses.

The method for molding the cyclic olefin-based resin composition according to the present embodiment to obtain a molded body is not particularly limited, and known methods can be used. Depending on the application and shape, for example, extrusion molding, injection molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, vacuum molding, powder slush molding, calendar molding, foam molding, etc. can be applied. is. Among these, the injection molding method is preferable from the viewpoint of moldability and productivity. Molding conditions are appropriately selected depending on the purpose of use or the molding method. For example, the resin temperature in injection molding is usually 150°C to 400°C, preferably 200°C to 350°C, more preferably 230°C to 330°C. It is selected appropriately within the range.

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

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited by these examples.

[Example 1]
<Synthesis of Resin A>
(Preparation of catalyst)
VO(OC ₂ H ₅ )Cl ₂ was diluted with cyclohexane to prepare a vanadium catalyst with a vanadium concentration of 6.7 mmol/L-cyclohexane. Ethyl aluminum sesquichloride (Al(C ₂ H ₅ ) _1.5 Cl _1.5 ) was diluted with cyclohexane to prepare an organoaluminum compound catalyst having an aluminum concentration of 107 mmol/L-hexane.

(polymerization)
Ethylene and tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene was copolymerized. Here, ethylene was supplied into the polymerization vessel together with hydrogen gas.
When carrying out this copolymerization reaction, the vanadium catalyst prepared by the above method was added to the polymerization vessel in such an amount that the vanadium catalyst concentration relative to cyclohexane in the polymerization vessel used as the polymerization solvent was 0.6 mmol/L. supplied inside.
Further, ethylaluminum sesquichloride, which is an organoaluminum compound, was fed into the polymerization vessel in such an amount that Al/V=18.0. The copolymerization reaction was continuously carried out at a polymerization temperature of 8°C and a polymerization pressure of 1.8 kg/cm ² G.

(Decalcification)
Ethylene and tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene was added with water and a NaOH solution having a concentration of 25 mass % as a pH adjuster to terminate the polymerization reaction. Further, catalyst residues present in the copolymer were removed (deashed) from this copolymer solution (polymer solution A).
Ethylene and tetracyclo[4.4.0.1 ^2,5 . ^{Pentaerythrityl} -tetrakis[3-(3,5-di-t -Butyl-4-hydroxyphenyl)propionate] was added in an amount of 0.4 parts by mass per 100 parts by mass of the copolymer. Then, they were once mixed for 1 hour using a stirring tank with an effective volume of 1.0 m ³ before entering the flash drying process.

(Desolvation)
A double-tube heater (outer tube diameter 2B, inner tube diameter 3/4B, length 21m) using steam of 20 kg/cm ² G as a heat source was used to heat the copolymer in the cyclohexane solution to a concentration of 5% by mass. 150 kg/h of the cyclohexane solution of the above copolymer was supplied and heated to 180°C.
A double-tube flash dryer (outer tube diameter: 2B, inner tube diameter: 3/4B, length: 27m) using steam of 25 kg/cm ² G as a heat source and a flash hopper (volume: 200 L) were used to perform the above heating. Ethylene and tetracyclo[4.4.0.1 ^2,5 . A random copolymer (resin A) with 1 ^7,10 ]-3-dodecene was obtained.

(Extrusion)
Using a vented twin-screw kneading extruder, the melted resin A was charged from the resin charging port of the extruder. Next, for the purpose of removing volatile matter from the vent portion, while sucking with a vacuum pump through a trap, the extruder conditions were adjusted so that the difference between the maximum value and the minimum value of the resin temperature in the extruder diverter part was within 3 ° C. It was adjusted. Then, it was pelletized by an underwater pelletizer attached to the outlet of the extruder, and the obtained pellets were dried with hot air at a temperature of 100°C for 4 hours. Furthermore, in order to suppress the contamination of iron atoms (Fe), the polymer production equipment uses stainless steel pipes and polymerization equipment, and the amount of resin that is calculated from the average residence time in the polymerization vessel is about 3 to 5 times. Pellet-shaped Resin A was obtained by carrying out an operation of pouring for washing (purging) and then collecting a sample. Resin A had a glass transition temperature (Tg) of 140° C. and an MFR of 29 g/10 min (260° C., 2.16 kg load).

<Preparation of resin composition>
As a triglycerin fatty acid ester, a distilled product of triglycerin oleate, which is an ester of triglycerin and oleic acid (the ester ratio is shown in Table 1 and is the peak area ratio in the gas chromatogram), was heated at 100 ° C. for 4 hours in a molten state. Then, an amount of 0.3 parts by mass based on 100 parts by mass of Resin A was directly charged into an extruder to obtain a resin composition A containing a distilled product of resin A and an ester of triglycerin and oleic acid. .
Specifically, using a twin-screw extruder with co-rotation, a screw diameter of 44 mmφ, and L/D = 30 having a vent hole at a position of L/D = 24 from the resin charging part, resin A is added to the resin charging part. Then, the above triglycerol fatty acid ester heated and melted at 80 to 120° C. is charged through the vent hole and melt-kneaded under conditions of a screw rotation speed of 150 rpm and a motor power of 30 kW to obtain a resin composition. rice field.

[Example 2]
As shown in Table 1, the triglycerin fatty acid ester is triglycerin oleate (a mixture of monoester, diester and triester, the ester ratio is shown in Table 1), which is an ester of triglycerin and oleic acid. A resin composition was prepared in the same manner as in Example 1, except that 0.5 parts by mass of 100 parts by mass of Resin A was used.

[Example 3]
As shown in Table 1, as a triglycerin fatty acid ester, triglycerin stearate (a mixture of monoester, diester and triester, ester ratio is shown in Table 1, gas chromatogram), which is an ester of triglycerin and stearic acid A resin composition was prepared in the same manner as in Example 1, except that 0.6 parts by mass of 100 parts by mass of Resin A was used.

[Example 4]
As shown in Table 1, the following resin B was used in place of resin A, and triglycerin oleate, which is an ester of triglycerin and oleic acid, was distilled as a triglycerin ester (the ester ratio is shown in Table 1; A resin composition was prepared in the same manner as in Example 1, except for using 0.4 parts by mass of 0.4 parts by mass of 0.4 parts by mass of 0.4 parts by mass of 0.4 parts by mass.

[Example 5]
As shown in Table 1, the triglycerin fatty acid ester is triglycerin oleate (a mixture of monoester, diester and triester, the ester ratio is shown in Table 1), which is an ester of triglycerin and oleic acid. A resin composition was prepared in the same manner as in Example 1, except that 1.0 parts by mass of 1.0 parts by mass of 100 parts by mass of Resin A was used.

[Example 6]
As shown in Table 1, the triglycerin fatty acid ester is triglycerin oleate (a mixture of monoester, diester and triester, the ester ratio is shown in Table 1), which is an ester of triglycerin and oleic acid. A resin composition was prepared in the same manner as in Example 1, except that 1.4 parts by mass of 100 parts by mass of Resin A was used.

<Synthesis of Resin B>
Ethylene and tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene and the ratio of the hydrogen feed amount to the ethylene feed amount, the glass transition temperature (Tg) was 151° C. and the MFR was 20 g/10 min (260° C., 2. A cyclic olefin random copolymer (resin B) was obtained in the same manner as resin A, except that the load was adjusted to 16 kg.

[Comparative Example 1]
As shown in Table 1, a resin composition was prepared in the same manner as in Example 1 except that no triglycerol fatty acid ester was used.

[Comparative Example 2]
As shown in Table 1, instead of triglycerin fatty acid ester, a distilled product (Rikemar DO-100: manufactured by Riken Vitamin Co., Ltd.) of an ester of diglycerin and oleic acid (diglycerin fatty acid ester) was added to 100 parts by mass of Resin A. A resin composition was prepared in the same manner as in Example 1, except that 0.6 parts by mass was used.

[Comparative Example 3]
As shown in Table 1, instead of triglycerin fatty acid ester, a distilled product (Rikemar DO-100: manufactured by Riken Vitamin Co., Ltd.) of an ester of diglycerin and oleic acid (diglycerin fatty acid ester) was added to 100 parts by mass of resin B. A resin composition was prepared in the same manner as in Example 4, except that 0.8 parts by mass was used.

Molded bodies obtained from the resin compositions of Examples 1 to 6 and Comparative Examples 1 to 3 were evaluated by the following evaluation methods. Table 1 shows the evaluation results.
Here, since the optical components of Examples 5 and 6 contain triglycerin fatty acid ester as in Examples 1 to 4, the evaluation of the weld line, which will be described later, is good.

(Evaluation method for compact)
(1) Using a haze injection molding machine (ROBOSHOT S2000i-30α manufactured by Fanuc Corporation), the resin compositions obtained in Examples and Comparative Examples are injection molded at a cylinder temperature of 275 ° C., and an optical of 35 mm × 65 mm × thickness 3 mmt A test piece having a surface was produced. The mold temperature was set to 120° C. when resin A was used and to 130° C. when resin B was used. The internal haze of the molded product was measured using benzyl alcohol according to JIS K-7105.

(2) Environmental Test The test piece having an optical surface of 35 mm×65 mm×thickness 3 mmt obtained above was left in an atmosphere of 80° C. temperature and 90% relative humidity for 48 hours. Then, the haze was measured 3 hours after taking out.

(3) Weld line evaluation test Outer diameter 6.2 mm, lens part diameter 5.0 mm, center thickness (minimum thickness) 0.35 mm, maximum thickness 0.944 mm, maximum thickness T _max and minimum thickness T Using a mold and an injection molding machine (ROBOSHOT S2000i-30α manufactured by Fanuc Co., Ltd.) for forming a lens with a ratio of _min (T _max /T _min, thickness deviation ratio) of 2.7, a holding pressure of 100 MPa and an injection speed of 50 mm The resin compositions obtained in Examples and Comparative Examples were injection molded under the condition of /s to prepare 10 molded bodies. When resin A was used, the cylinder temperature and mold temperature were set at 275°C and 135°C, and when resin B was used, the cylinder temperature and mold temperature were set at 285°C and 145°C, respectively.
The molded product obtained was observed with a laser microscope (VK-X100 manufactured by Keyence Corporation), and the length of the weld line formed on the opposite side of the gate was measured and evaluated according to the following criteria. If the length of the weld line is 1200 μm or more, it will enter the portion used as the lens (optically effective surface), which will affect the optical performance.
A: The length of the weld line is less than 1200 μm B: The length of the weld line is 1200 μm or more

(4) Refractive index Using an injection molding machine (ROBOSHOT S2000i-30α manufactured by FANUC CORPORATION), the resin compositions obtained in Examples and Comparative Examples were injection molded at a cylinder temperature of 275 ° C., and 35 mm × 65 mm × 3 mm thick. A test piece having an optical surface was produced for each. The mold temperature was set to 120° C. when resin A was used and to 130° C. when resin B was used.
The refractive index of the molded article was determined by measuring the refractive index (nd) at 25° C. and a wavelength of 589 nm according to ASTM D542 using a refractometer (KPR200 manufactured by Shimadzu Science Co., Ltd.).

(5) Birefringence Using an injection molding machine (FANUC ROBOSHOT S2000i-30α), the cylinder temperature is 275 ° C., the mold temperature is 120 ° C. when using resin A, and 130 ° C. when using resin B. The resin compositions obtained in Examples and Comparative Examples were injection molded under the conditions to prepare test pieces each having an optical surface of 35 mm×65 mm×thickness of 3 mm. The phase difference was measured using a KOBRA CCD manufactured by Oji Scientific Instruments at a measurement wavelength of 650 nm, and the average value of the phase difference at the central portion of the test piece (a portion 30 to 45 mm from the gate in the gate direction) was obtained.
Then, each birefringence was evaluated according to the following criteria.
A: The average value of retardation is less than 30 nm B: The average value of retardation is 30 nm or more and less than 40 nm C: The average value of retardation is 40 nm or more

(6) Mold contamination Mold and injection molding machine for forming a meniscus lens with an outer diameter of 6.0 mm, a lens portion diameter of 4.1 mm, and a lens portion thickness of 0.5 mm (ROBOSHOT S2000i-30α manufactured by Fanuc) The resin compositions obtained in Examples and Comparative Examples were injection molded under the conditions of a cylinder temperature of 285 ° C., a mold temperature of 120 ° C. when resin A was used, and a mold temperature of 130 ° C. when resin B was used. Then, 6000 shots were continuously molded. Next, after molding 6000 shots, dirt on the mold vent attached to the outer periphery of the lens outside diameter of the mold was observed with a stereoscopic microscope SZX16 (manufactured by Olympus) at a magnification of 3.5 times.
Scores were given from those with little dirt to those with much dirt. The evaluation was made on a 4-point scale, with 1 point indicating the least staining and 4 points indicating the most staining.

(7) Methods for analyzing monoesters, diesters and triesters in triglycerin fatty acid esters or diglycerin fatty acid esters Analysis methods for triglycerin fatty acid esters or diglycerin fatty acid esters used in Examples and Comparative Examples are shown below. .
The content of monoester, diester and triester in triglycerin fatty acid ester or diglycerin fatty acid ester was quantified by the following method.
(quantification method)
・Measurement method Measurement equipment: GCMS-QP2010Plus (manufactured by Shimadzu Corporation)
Column: DB-1HT, 0.32mmφ×15m
temperature:
Column: 120°C → temperature rise at 9°C/min → hold at 390°C for 10 min Inlet temperature: 350°C
Detector temperature: 400°C
Carrier gas: He
Split ratio: 10:1
Injection volume: 1 μm
Detector: FID
-Preparation of sample for measurement [1] 0.0130 g of internal standard (n-butyl phthalate, special grade manufactured by Tokyo Kasei Co., Ltd.) was weighed into a 50 mL volumetric flask and diluted with pyridine to obtain an internal standard solution.
[2] 0.025 g of a sample was accurately weighed into a 50 mL volumetric flask, 5 mL of cyclohexane was added, and the volume was adjusted to 25 mL with acetone.
[3] Collect 500 μL of the sample solution prepared in step (2) and dry it, add 50 μL of internal standard solution and 200 μL of trimethylsilylating agent (BSTFA, manufactured by Tokyo Kasei Co., Ltd.), and heat to 90 ° C. on a block heater. The trimethylsilylation reaction was carried out at rt for 1 hour.
[4] After step (3), the sample was air-cooled to room temperature, and then measured under the above conditions to determine the contents of monoester, diester and triester from the area ratio of the chart.

(8) Measurement method of temperature (Td-10%) at which weight decreases by 10% by heating Perform thermogravimetric differential thermal analysis (TG-DTA) of triglycerin fatty acid ester or diglycerin fatty acid ester, and reduce 10% weight by heating. Temperature (Td-10%) was measured by the following method. Here, the initial weight indicates the weight at 30° C. of the triglycerol fatty acid ester or the like.
・Measurement method Measurement equipment: TG-DTA7300 (manufactured by SII Nanotechnology)
Measurement temperature range: 30℃→400℃
Heating rate: 10°C/min
Measurement atmosphere: air (200 mL/min)
Sample pan used: Aluminum pan (φ5.2mm H5.0mm)
Sample weight: 10mg

Claims (13)

including a cyclic olefin polymer (A) and a triglycerin fatty acid ester,
The triglycerin fatty acid ester is a mixture (y) of triglycerin fatty acid monoester, triglycerin fatty acid diester and triglycerin fatty acid triester ,
A cyclic olefin resin composition, wherein the triglycerin fatty acid triester content in the triglycerin fatty acid ester is 5% by mass or more and 30% by mass or less . In the cyclic olefin resin composition according to claim 1,
Cyclic olefin resin composition in which the cyclic olefin polymer (A) contains at least one selected from copolymers of ethylene or α-olefin and cyclic olefins (A1) and ring-opening polymers of cyclic olefins (A2). thing. In the cyclic olefin resin composition according to claim 2,
The cyclic olefin polymer (A) contains the copolymer (A1),
The copolymer (A1) is
at least one olefin-derived repeating unit (a) represented by the following general formula (I);
At least one cyclic olefin selected from the group consisting of repeating units represented by the following general formula (II), repeating units represented by the following general formula (III), and repeating units represented by the following general formula (IV) a repeating unit (b) derived from
A cyclic olefin resin composition having

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

(In general formula (II) above, u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, and R ⁶¹ to R ⁷⁸ and R ^a1 and R ^b1 are the same hydrogen atom, halogen atom, alkyl group having 1 to 20 carbon atoms, halogenated alkyl group having 1 to 20 carbon atoms, cycloalkyl group having 3 to 15 carbon atoms or 6 carbon atoms to 20 aromatic hydrocarbon groups, and R ⁷⁵ to R ⁷⁸ may be bonded together to form a monocyclic or polycyclic ring.)

(In the above general 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, 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 and the carbon atom to which R ⁹³ is bonded or the carbon atom to which R ⁹¹ is bonded are directly or an alkylene group having 1 to 3 carbon atoms 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. good.)

(In general formula (IV) above, 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 1 ≤ f ≤ 18. .) In the cyclic olefin resin composition according to claim 3,
The repeating unit (b) derived from the cyclic olefin in the copolymer (A1) is bicyclo[2.2.1]-2-heptene and tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene A cyclic olefin resin composition containing a repeating unit derived from at least one compound selected from the group consisting of: In the cyclic olefin resin composition according to claim 3 or 4,
A cyclic olefin resin composition in which the olefin-derived repeating unit (a) in the copolymer (A1) contains a repeating unit derived from ethylene. In the cyclic olefin resin composition according to any one of claims 1 to 5,
When the cyclic olefin polymer (A) contained in the cyclic olefin resin composition is 100 parts by mass, the content of the triglycerin fatty acid ester is 0.05 parts by mass or more and 1.5 parts by mass or less. A cyclic olefin resin composition. In the cyclic olefin resin composition according to any one of claims 1 to 6,
The cyclic olefin resin composition, wherein the triglycerin fatty acid ester contains an ester of triglycerin and a saturated or unsaturated fatty acid having 8 to 24 carbon atoms. In the cyclic olefin resin composition according to any one of claims 1 to 7,
A cyclic olefin resin composition having a glass transition temperature in the range of 130° C. or higher and 160° C. or lower. In the cyclic olefin resin composition according to any one of claims 1 to 8,
The cyclic olefin resin composition, wherein the content of the triglycerin fatty acid diester in the triglycerin fatty acid ester is 30% by mass or more and 70% by mass or less. A molded article comprising the cyclic olefin resin composition according to any one of claims 1 to 9 . An optical component comprising the molded article according to claim 10 . An optical component according to claim 11 , wherein
An optical component that is an f-theta lens, an imaging lens, a sensor lens, a prism, or a light guide plate. 13. The optical component according to claim 11 or 12 ,
When the maximum thickness of the optical component is T _max and the minimum thickness of the optical component is T _min ,
An optical component having a thickness deviation ratio represented by T _max /T _min of 2.0 or more.

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