JP2018172665A - Cyclic olefinic resin composition, molding and optical component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cyclic olefin resin composition which is excellent in optical performance and can realize an optical component in which deterioration of optical performance and generation of weld lines are suppressed under high temperature and high humidity conditions. The cyclic olefin resin composition of the present invention contains a cyclic olefin polymer (A) and a triglycerin fatty acid ester. [Selection diagram] None

Description

  The present invention relates to a cyclic olefin-based resin composition, a molded body, and an optical component.

Since the cyclic olefin resin composition is excellent in optical performance, it is used, for example, as an optical component such as an optical lens.
Examples of the technology related to the cyclic olefin resin composition used for optical parts include those described in Patent Document 1 (Japanese Patent Laid-Open 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 when such a cyclic olefin-based resin composition is used, a molded article having excellent optical performance and further suppressing deterioration of optical performance under high temperature and high humidity conditions can be obtained.

Japanese Unexamined Patent Publication No. 2015-199939

According to the study by 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, the optical performance is excellent. Although it is possible to realize an optical component in which deterioration of optical performance under high-temperature and high-humidity conditions is suppressed, depending on the shape of the optical component to be manufactured, a weld line (in the resin molding, the flow of molten resin joins in the mold) It was thought that there was room for improvement in the thin line generated in the fused part.
Specifically, the aim was to reduce the weld line generated when an optical component having a large ratio between the maximum thickness and the minimum thickness (hereinafter also referred to as an uneven thickness ratio) is produced. When a weld line is generated and an optical defect is generated, there is a possibility that image quality deterioration such as a flare phenomenon or a ghost phenomenon may be caused. Therefore, it is preferable that the weld line is small.

  The present invention has been made in view of the above circumstances, and is a cyclic olefin-based resin composition that can realize an optical component that is excellent in optical performance and further suppressed in optical performance deterioration and weld line generation under high temperature and high humidity conditions. Is to provide.

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

  The present invention is as follows.

（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 comprising a cyclic olefin polymer (A) and a triglycerin fatty acid ester.
[2]
In the cyclic olefin-based resin composition according to the above [1],
Cyclic olefin-based resin composition containing at least one selected from the above-mentioned cyclic olefin-based polymer (A) selected from ethylene or α-olefin and cyclic olefin copolymer (A1) and cyclic olefin ring-opening polymer (A2) object.
[3]
In the cyclic olefin-based resin composition according to the above [2],
The cyclic olefin polymer (A) includes the copolymer (A1),
The copolymer (A1) is
A repeating unit (a) derived from at least one olefin represented by the following general formula (I):
At least one cyclic olefin selected from the group consisting of a repeating unit represented by the following general formula (II), a repeating unit represented by the following general formula (III), and a repeating unit represented by the following general formula (IV) A repeating unit (b) derived from,
The cyclic olefin-type resin composition containing the cyclic olefin copolymer containing this.

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

(In the general formula (II), 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 as each other. However, they may be 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 6 carbon atoms. -20 aromatic hydrocarbon groups, and R ^{75 to} R ⁷⁸ may be bonded to each other to form a monocyclic or polycyclic ring.)

(In the general formula (III), x and d are 0 or an integer of 1 or more, y and z are 0, 1 or 2, and R ^{81 to} R ⁹⁹ may be the same as or different from each other, An aliphatic hydrocarbon group which is a hydrogen atom, a halogen atom, 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. 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. Good.)

(In the above general formula (IV), R ¹⁰⁰ and R ¹⁰¹ may be the same as or different from each other, and each represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and f is 1 ≦ f ≦ 18. .)
[4]
In the cyclic olefin-based resin composition according to the above [3],
The cyclic olefin-derived repeating unit (b) in the copolymer (A1) is bicyclo [2.2.1] -2-heptene and tetracyclo [4.4.0.1 ^2,5 . 1 ^<7,10 ] -3-cyclic olefin resin composition containing the repeating unit derived from the at least 1 sort (s) of compound chosen from dodecene.
[5]
In the cyclic olefin-based resin composition according to the above [3] or [4],
The cyclic olefin resin composition in which the repeating unit (a) derived from the olefin in the copolymer (A1) includes a repeating unit derived from ethylene.
[6]
In the cyclic olefin-based resin composition according to any one of [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. Cyclic olefin resin composition.
[7]
In the cyclic olefin-based resin composition according to any one of [1] to [6],
The cyclic olefin resin composition in which the triglycerin fatty acid ester includes an ester of triglycerin and a saturated or unsaturated fatty acid having 8 to 24 carbon atoms.
[8]
In the cyclic olefin-based resin composition according to any one of [1] to [7],
The cyclic olefin resin composition in which the glass transition temperature of the cyclic olefin resin composition is in the range of 130 ° C or higher and 160 ° C or lower.
[9]
The molded object containing the cyclic olefin resin composition as described in any one of said [1] thru | or [8].
[10]
An optical component comprising the molded article according to the above [9].
[11]
In the optical component according to [10] above,
An optical component that is an fθ lens, an imaging lens, a sensor lens, a prism, or a light guide plate.
[12]
In the optical component according to the above [10] or [11],
The maximum thickness of the optical component and T _max, when the minimum thickness of the optical component was T _min,
An optical component having an uneven thickness ratio represented by T _max / T _min of 2.0 or more.

  ADVANTAGE OF THE INVENTION According to this invention, the cyclic olefin resin composition which can implement | achieve the optical component which was excellent in optical performance, and also the deterioration of the optical performance in high temperature, high humidity conditions, and generation | occurrence | production of the weld line was suppressed can be provided.

It is sectional drawing which showed typically an example of the structure of the optical component of embodiment which concerns on this invention.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. In all the drawings, similar constituent elements are denoted by common reference numerals, and description thereof is omitted as appropriate. Moreover, the figure is a schematic diagram and does not match the actual dimensional ratio. Further, “A to B” indicating a numerical range represents A or more and B or less unless otherwise specified.

[Cyclic olefin resin composition]
First, the cyclic olefin-type resin composition of embodiment which concerns on this invention is demonstrated.
The cyclic olefin resin composition according to this embodiment includes a cyclic olefin polymer (A) and a triglycerin fatty acid ester.

According to the cyclic olefin resin composition according to the present embodiment, it is possible to realize an optical component that is excellent in optical performance and further suppressed in optical performance deterioration and weld line generation under high temperature and high humidity conditions.
The reason for this is not clear, but the triglycerin fatty acid ester has an appropriate amount of hydrophilic groups and contains a fatty acid-derived hydrophobic group, so that it has excellent compatibility with the cyclic olefin polymer (A) and excellent optical performance. Optical components can be obtained. Furthermore, the triglycerin fatty acid ester has a hydrophilic functional group such as a hydroxyl group, an ether group, or a carbonyl group. Therefore, even when molded under high-temperature and high-humidity conditions, it is surmised that water absorbed in the resin composition is dispersed and aggregation of water that causes deterioration of optical performance is suppressed. Furthermore, since triglycerin fatty acid ester has a higher molecular weight than diglycerin fatty acid ester, monoglycerin fatty acid ester, etc., it can suppress gasification when molding optical components, and as a result, weld lines are generated in optical components. Can be suppressed.
Furthermore, according to the study by the present inventors, a molded body using 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. When continuous molding is performed, dirt may adhere to the mold, and it is clear that conventional resin compositions have room for improvement in terms of reducing adhesion of mold dirt during continuous molding. became. The present inventors diligently studied to solve the above problems. As a result, it has been found that by using a resin composition in which a triglycerin fatty acid ester is blended with a cyclic olefin polymer, adhesion of mold stains during continuous molding can be reduced. That is, according to the cyclic olefin-based resin composition according to the present embodiment, adhesion of mold stains during continuous molding can be reduced.

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, further preferably 90% by mass or more, and particularly preferably 95% by mass or more. When 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 equal to or higher than the lower limit, the optical performance can be further improved. .
Although the upper limit of 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, for example, it is 100% by mass or less.

  Hereinafter, each component will be specifically described.

(Cyclic olefin polymer (A))
The cyclic olefin polymer (A) according to this embodiment is a polymer having a repeating unit derived from a cyclic olefin as an essential constituent unit.
Examples of the cyclic olefin polymer (A) include at least one selected from a copolymer (A1) of ethylene or an α-olefin and a cyclic olefin and a ring-opened polymer (A2) of the cyclic olefin.

  Although the cyclic olefin compound which comprises the copolymer (A1) which concerns on this embodiment is not specifically limited, For example, the cyclic olefin monomer etc. as described in Paragraph 0037-0063 of international publication 2006/118261 etc. can be mentioned. .

  From the standpoint that the copolymer (A1) according to the present embodiment can further improve heat resistance or improve moldability while maintaining a good balance between the transparency and refractive index of the resulting molded article. The repeating unit (a) derived from at least one olefin represented by the general formula (I), the repeating unit represented by the following general formula (II), the repeating unit represented by the following general formula (III), and the following It is preferable to have at least one cyclic olefin-derived repeating unit (b) selected from the group consisting of repeating units represented by the general 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 the above general formula (I), 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 general formula (II), u is 0 or 1, v is 0 or a positive integer, preferably 0 or more and an integer of 2 or less, more preferably 0 or 1, and w is 0 or 1. R ^{61 to} R ⁷⁸ and R ^a1 and R ^b1 may be the same or different from each other, 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, an aromatic hydrocarbon group having a cycloalkyl group or having 6 to 20 carbon atoms carbon atoms 3~15, R ⁷⁵ ~R ⁷⁸ may form a monocyclic or polycyclic bonded to each other.

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 as or different from each other, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an aliphatic hydrocarbon group that is a cycloalkyl group having 3 to 15 carbon atoms, carbon An aromatic hydrocarbon group or an alkoxy group having 6 to 20 atoms, a carbon atom to which R ⁸⁹ and R ⁹⁰ are bonded, a carbon atom to which R ⁹³ is bonded, or a carbon atom to which R ⁹¹ is bonded May be bonded directly or via 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. Single ring It may form an aromatic ring polycyclic.

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 the general formula (IV), R ¹⁰⁰ and R ¹⁰¹ may be the same as or different from each other, and each represents 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 copolymerization raw materials of the copolymer (A1) according to this embodiment is addition-copolymerized to form the structural unit represented by the above 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 the general 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 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-eicocene and the like. From these viewpoints, ethylene and propylene are preferable, and ethylene is particularly preferable from the viewpoint of obtaining a molded body having more excellent heat resistance, mechanical properties, and optical properties. Two or more kinds of olefin monomers represented by the general formula (Ia) may be used.
When the entire constitutional unit constituting the cyclic olefin copolymer according to this embodiment is 100 mol%, the proportion of the olefin-derived repeating unit (a) is preferably 5 mol% or more and 95 mol% or less, more preferably. Is from 20 mol% to 90 mol%, more preferably from 40 mol% to 85 mol%, particularly preferably from 50 mol% to 80 mol%.
In addition, the ratio of the olefin-derived repeating unit (a) can be measured by ¹³ C-NMR.

  The cyclic olefin monomer (b), which is one of the copolymer raw materials of the copolymer (A1) according to this embodiment, is addition-copolymerized to produce the above general formula (II), the above general formula (III), or the above general formula ( The repeating unit (b) derived from the cyclic olefin represented by IV) is formed. Specifically, the cyclic olefin 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. 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 general formula (IIa), u is 0 or 1, v is 0 or a positive integer, preferably 0 or more and an integer of 2 or less, more preferably 0 or 1, and w is 0 or 1. R ^{61 to} R ⁷⁸ and R ^a1 and R ^b1 may be the same or different from each other, 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 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 above 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 as or different from each other, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an aliphatic hydrocarbon group that is a cycloalkyl group having 3 to 15 carbon atoms, carbon An aromatic hydrocarbon group or an alkoxy group having 6 to 20 atoms, a carbon atom to which R ⁸⁹ and R ⁹⁰ are bonded, a carbon atom to which R ⁹³ is bonded, or a carbon atom to which R ⁹¹ is bonded May be bonded directly or via 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. Single ring Others may form an aromatic ring polycyclic.

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

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

  As specific examples of the cyclic olefin monomer (b) represented by the general formula (IIa), (IIIa) or (IVa), the compounds described in paragraphs 0037 to 0063 of International Publication No. 2006/118261 can be used.

  Specifically, bicyclo-2-heptene derivative (bicyclohept-2-ene derivative), tricyclo-3-decene derivative, tricyclo-3-undecene derivative, tetracyclo-3-dodecene derivative, pentacyclo-4-pentadecene derivative, 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 -Heneecocene derivative, octacyclo-5-docosene derivative, nonacyclo-5-pentacocene derivative, nonacyclo-6-hexacocene derivative, cyclopentadiene-acenaphthylene adduct, 1,4 Examples include 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 the general formula (IIa), (IIIa) or (IVa), the cyclic olefin represented by the general formula (IIa) is preferable.

Examples of the cyclic olefin monomer (b) represented by the general formula (IIa) include bicyclo [2.2.1] -2-heptene (also referred to as norbornene), tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene (also referred to as tetracyclododecene) is preferably used, and tetracyclo [4.4.0.1 ^2,5 . It is more preferable to use 1 ^7,10 ] -3-dodecene. Since these cyclic olefins have a rigid ring structure, there is an advantage that the elastic modulus of the copolymer and the molded body can be easily maintained.

  When the total of the structural units constituting the copolymer (A1) according to this embodiment is 100 mol%, the proportion of the repeating unit (b) derived from the cyclic olefin monomer (b) is preferably 5 mol% or more and 95. The mol% or less, more preferably 10 mol% or more and 80 mol% or less, further preferably 15 mol% or more and 60 mol% or less, and particularly preferably 20 mol% or more and 50 mol% or less.

  The copolymer type of the copolymer (A1) according to this embodiment is not particularly limited, and examples thereof include a random copolymer and a block copolymer. In the present embodiment, the copolymer (A1) according to the present embodiment is a random copolymer from the viewpoint that excellent optical properties such as transparency, refractive index and birefringence can be obtained and a highly accurate optical component can be obtained. It is preferable to use a polymer.

Examples of the copolymer (A1) according to this embodiment include ethylene and tetracyclo [4.4.0.1 ^2,5 . ^{17, 10} ] -3-dodecene, and a random copolymer of ethylene and bicyclo [2.2.1] -2-heptene, preferably ethylene and tetracyclo [4.4. 0.1 ^2,5 . Random copolymers with 1 ^7,10 ] -3-dodecene are more preferred.

As the cyclic olefin polymer (A), a cyclic olefin ring-opening polymer (A2) can be used.
Examples of the ring-opening polymer (A2) of the cyclic olefin include, for example, a ring-opening polymer of a norbornene-based monomer and a ring-opening weight of the norbornene-based monomer and other monomers capable of ring-opening copolymerization therewith. And hydrides thereof, and the like.

Examples of the norbornene-based monomer include bicyclo [2.2.1] hept-2-ene (common name: norbornene) and derivatives thereof (having a substituent in the ring), tricyclo [4.3.0 ^{1 , 6} . 1 ^2,5 ] deca-3,7-diene (common name dicyclopentadiene) and derivatives thereof, 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 . ^{17, 10} ] -3-dodecene (common name: tetracyclododecene) and its derivatives.
Examples of the substituent substituted 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, a substituent can have 1 piece or 2 or more pieces. As a derivative having a substituent in such a ring, for example, 8-methoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-methoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethylidene-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene and the like.
These norbornene monomers are 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 another monomer capable of ring-opening copolymerization with a monomer component is a known ring-opening polymerization. It can be obtained by polymerization in the presence of a catalyst.
As the ring-opening polymerization catalyst, for example, a catalyst comprising a metal halide such as ruthenium or osmium, a nitrate or an acetylacetone compound, and a reducing agent; a metal halide such as titanium, zirconium, tungsten or molybdenum or an acetylacetone compound A catalyst comprising an organoaluminum compound; and the like can be used.
Examples of other monomers capable of ring-opening copolymerization with norbornene monomers include monocyclic olefin monomers such as cyclohexene, cycloheptene, and cyclooctene.

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

  In this embodiment, cyclic olefin polymer (A) may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of the copolymer (A1) according to the present embodiment include Japanese Patent Laid-Open Nos. 60-168708, 61-120816, 61-115912, and 61-115916. In accordance with methods such as JP-A 61-271308, JP-A 61-272216, JP-A 62-252406, JP 62-252407, etc. Can do.
Examples of the ring-opening polymer (A2) of the cyclic olefin according to this embodiment include, for example, JP-A-60-26024, JP-A-9-268250, JP-A-63-145324, JP-A-2001-72839. It can manufacture by selecting conditions suitably according to methods, such as gazette.

The molecular weight of the cyclic olefin polymer (A) according to the present embodiment is not particularly limited, but when the intrinsic viscosity [η] is used as an alternative index of the molecular weight, the intrinsic viscosity [η] measured in decalin at 135 ° C. However, the molecular weight is preferably 0.03 dl / g to 10 dl / g, more preferably 0.05 dl / g to 5 dl / g, and still more preferably 0.10 dl / g to 2 dl / g.
When the molecular weight is not less than the above lower limit, the mechanical strength of the molded product can be improved. Moreover, a moldability can be improved as molecular weight is below the said upper limit.

According to ASTM D1238, 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 is the workability 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 further preferably 10 g / 10 minutes or more.
The upper limit of MFR of the cyclic olefin polymer (A) is preferably 60 g / 10 min or less, more preferably 50 g / 10 min or less, from the viewpoint of further suppressing the generation of weld lines. More preferably, it is 40 g / 10 minutes or less, More preferably, it is 35 g / 10 minutes or less, Most preferably, it is 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 in the polymerization reaction 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 in the above range, sufficient heat resistance can be obtained when the molded body is used as an optical component that requires heat resistance such as an in-vehicle camera lens or a camera lens for portable devices. And good moldability can be obtained.

  The glass transition temperature (Tg) of the cyclic olefin-based resin composition according to the present embodiment is increased from room temperature to 200 ° C. at a temperature increase rate of 10 ° C./min under a nitrogen atmosphere using, for example, RDC220 manufactured by SII Nanotechnology. The glass transition temperature is maintained for 5 minutes after the temperature is maintained, then the temperature is decreased to 30 ° C. at a temperature decrease rate of 10 ° C./minute, then maintained for 5 minutes, and then heated to 200 ° C. at a temperature increase rate of 10 ° C./minute Can be measured.

(Triglycerin fatty acid ester)
Triglycerin fatty acid ester is an ester of a fatty acid and triglycerin.
The triglycerin fatty acid ester according to this embodiment is obtained by esterifying at least one of five hydroxy groups contained in triglycerin with a fatty acid.

  As fatty acids, 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, stearic acid; crotonic acid, myristoleic acid, palmitoleic acid Monounsaturated fatty acids such as sapienoic acid, oleic acid, elaidic acid, gadoleic acid, eicosenoic acid; diunsaturated fatty acids such as linoleic acid, eicosadienoic acid, docosadienoic acid; linolenic acid, pinolenic acid, eleostearic acid, eicosatri And 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, Triglycerol trilaurate, Triglycerol monomyristate, Triglycerol dimyristate, Triglycerol trimyristate, Triglycerol monopalmitate, Triglycerol dipalmitate, Triglycerol tripalmylate, Triglycerol monostearate, Triglycerol Distearate, Triglycerin tristearate, Triglycerin monobehenate, Triglycerin dibehenate, Triglycerin tri Triglycerin saturated fatty acid ester such as henate; Triglycerin unsaturated fatty acid ester such as triglycerin monooleate, triglycerin diolate, triglycerin triolate, etc., and the like, or a combination of one or more selected from these Can be used.
The triglycerin fatty acid ester according to this embodiment preferably contains an ester of triglycerin and a saturated or unsaturated fatty acid having 8 to 24 carbon atoms, and the saturated or unsaturated fatty acid having 12 to 18 carbon atoms. It is more preferable that the ester is included.

In the cyclic olefin resin composition according to the present embodiment, when the cyclic olefin polymer (A) contained in the cyclic olefin resin composition is 100 parts by mass, the lower limit of the content of the triglycerin fatty acid ester is high temperature. From the viewpoint of further suppressing deterioration of optical performance under high humidity conditions, it 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. More preferably, it is particularly preferably 0.3 parts by mass or more.
Further, 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 generation of weld lines. Preferably, it is 1.2 parts by mass or less, more preferably 1.0 part by mass or less, still more preferably 0.8 part by mass or less, and 0.7 part by mass or less. It is particularly preferred.
Triglycerin fatty acid esters have a larger amount of hydrophilic groups than diglycerin fatty acid esters, monoglycerin fatty acid esters, and the like, and therefore, it is considered that degradation of optical performance under high temperature and high humidity conditions can be suppressed with a smaller amount of addition. Moreover, since the addition amount can be reduced, the gasification amount of the triglycerin fatty acid ester at the time of molding can be further suppressed, and the generation of weld lines can be further suppressed.

Examples of the triglycerin fatty acid ester according to the present embodiment include monoesters alone, mixtures of monoesters and diesters, mixtures of monoesters, diesters, and triesters.
As such triglycerin fatty acid ester, for example, compounds described in JP-A-2006-232714, JP-A-2002-275308, JP-A-10-165152 and the like can be used.
Since the monoester has a lower molecular weight than that of the diester or triester, if the monoester content is high, the addition amount (weight) required for imparting the same heat-and-moisture resistance can be reduced. If the amount added is small, the amount of generated gas decreases, so it is considered that the effect of suppressing the generation of weld lines can be obtained more effectively.
The total content of the monoester and diester in the triglycerin fatty acid ester according to this 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 content of the triester 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, further preferably 0% by mass or more and 40% by mass or less, and 0% by mass or more and 30% by mass or less. Particularly preferred.
In addition, since the diester has a higher molecular weight than the monoester, the amount of addition (weight) necessary for imparting heat-and-moisture resistance increases, but since the generated gas is reduced, it is considered that the effect of suppressing mold contamination is enhanced. . Therefore, the content of the diester in the triglycerin fatty acid ester is preferably 30% by mass or more and 70% by mass or less, and more preferably 40% by mass or more and 60% by mass or less.
Similarly, the content of the triester in the triglycerin fatty acid ester according to this embodiment is preferably 1% by mass or more and 50% by mass or less, and more preferably 5% by mass or more and 30% by mass or less from the viewpoint of suppressing mold contamination.
The temperature (Td-10%) at which the triglycerin fatty acid ester according to this embodiment is reduced by 10% by weight is 260 ° C. or higher, more preferably 270 ° C. or higher, and further preferably 280 ° C. or higher. Although there is no upper limit in particular, it is usually 320 ° C. or lower. Here, an initial weight shows the weight in 30 degreeC, such as a triglycerol fatty acid ester. Detailed measurement conditions such as heating temperature are as described in the examples. The high weight reduction temperature is considered to suppress the generated gas and to obtain the effect of suppressing mold contamination.

(Other ingredients)
In addition to the cyclic olefin polymer (A) and the triglycerin fatty acid ester, the cyclic olefin resin composition according to this embodiment is within the range that does not impair the good physical properties of the cyclic olefin resin composition according to this embodiment. In addition, a known additive can be contained as an optional component.
Examples of the additives include antioxidants, secondary antioxidants, lubricants, mold release agents, antifogging agents, weathering stabilizers, light stabilizers, ultraviolet absorbers, antistatic agents, metal deactivators, and the like. Can be 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 the triglycerin fatty acid ester using a known kneading apparatus such as an extruder and a Banbury mixer; Method in which polymer (A) and triglycerin fatty acid ester are dissolved in a common solvent and then the solvent is evaporated; Method in which a solution of cyclic olefin polymer (A) and triglycerin fatty acid ester is added to a poor solvent and precipitated It can be obtained by such a method.

[Molded body and optical parts]
Next, the molded object of embodiment which concerns on this invention is demonstrated.
The molded body according to the present embodiment includes the cyclic olefin-based resin composition according to the present embodiment.
Since the molded object which concerns on this embodiment contains the cyclic olefin resin composition which concerns on this embodiment, it is excellent in optical performance. Therefore, it can be suitably used as an optical component in an optical system that needs to identify an image with high accuracy. An optical component is a component used in an optical system device, 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 according to this embodiment. 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 body obtained from the cyclic olefin-based resin composition according to this embodiment having a glass transition temperature in the range of 130 ° C. or higher and 160 ° C. or lower satisfies the moisture and heat resistance while having high heat resistance, and further has a weld. It has a surprising effect that the generation of lines is suppressed.
Therefore, the molded body obtained from the cyclic olefin-based resin composition according to the present embodiment is particularly suitable for optical components that require heat resistance such as in-vehicle camera lenses and camera lenses for mobile devices (mobile phones, smartphones, tablets, etc.). Can be used. Examples of the in-vehicle camera lens and the camera lens for portable devices include a view camera lens, a sensing camera lens, a light convergence lens for a head-up display, and a light diffusion lens for a head-up display.

Here, in recent years, electronic electric devices have been reduced in weight, size, and thickness. Therefore, an optical lens (also referred to as a camera lens) used in a camera has a thin shape and a small diameter, and also has an F value characteristic (aperture value: F-number) and an MTF (Modulation Transfer Function) characteristic in terms of image quality. (Contrast reproduction ratio) is required to be good. Therefore, the camera lens is not only required to be thin, but also has a complicated shape. For this reason, the thickness of the camera lens is not uniform, but a thin portion and a thick portion coexist.
Here, according to the study by the present inventors, it is apparent that an optical component having a large ratio of maximum thickness to minimum thickness (also referred to as uneven thickness ratio) tends to increase the weld line generated. 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 optical component whose thickness ratio represented by T _max / T _min is 2.0 or more is: It became clear that the generated weld line tends to become larger.
Therefore, the cyclic olefin resin composition according to the present embodiment can be suitably used for molding an optical component having an uneven thickness ratio represented by T _max / T _min of 2.5 or more. Thereby, even if it is an optical component whose thickness deviation ratio shown by _Tmax / _Tmin is 2.0 or more, generation | occurrence | production of a weld line can be suppressed effectively.
Here, the optical component having a complicated shape with an uneven thickness ratio equal to or more than the lower limit value is not particularly limited, and examples thereof include those having the shapes of (a) to (d) in FIG. Further, the distance connecting the opposing surfaces of the optical components is taken, and the portion with the longest distance is defined as T _max and the portion with the shortest distance is defined as T _min .
In addition to the concave lens and the convex lens, there are various shapes such as an aspherical lens and a concave surface on one side and a convex surface on the other side.

  The method for obtaining the molded product by molding the cyclic olefin-based resin composition according to the present embodiment is not particularly limited, and a known method can be used. Depending on the application and shape, for example, extrusion molding, injection molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, vacuum molding, powder slush molding, calendar molding, foam molding, etc. are applicable It is. Among these, the injection molding method is preferable from the viewpoints of moldability and productivity. The 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 appropriately selected within the range.

As mentioned above, although embodiment of this invention was described, these are illustrations of this invention and various structures other than the above are also employable.
Further, the present invention is not limited to the above-described embodiments, and modifications, improvements, and the like within a scope that can achieve the object of the present invention are included in the present invention.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not restrict | limited at all by this.

[Example 1]
<Synthesis of Resin A>
(Preparation of catalyst)
Diluted VO a _{(OC 2} H 5) Cl ₂ with cyclohexane, vanadium concentration was prepared vanadium catalyst is 6.7 mmol / L-cyclohexane. Diluted ethylaluminum sesquichloride _{(Al (C 2 H 5)} 1.5 Cl 1.5) in cyclohexane was prepared organoaluminum compound catalyst the aluminum concentration is 107 mmol / L-hexane.

(polymerization)
Using a stirring polymerization vessel (inner diameter 500 mm, reaction volume 100 L), ethylene and tetracyclo [4.4.0.1 ^2,5 . A copolymerization reaction with ^{17, 10} ] -3-dodecene was carried out. Here, ethylene was supplied into the polymerization vessel together with hydrogen gas.
In carrying out this copolymerization reaction, the vanadium catalyst prepared by the above method is used in an amount such that the vanadium catalyst concentration relative to cyclohexane in the polymerization vessel used as the polymerization solvent is 0.6 mmol / L. Supplied in.
Further, ethylaluminum sesquichloride, which is an organoaluminum compound, was supplied into the polymerization vessel in such an amount that Al / V = 18.0. The polymerization 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 extracted from the polymerization vessel [4.4.0.1 ^2,5 . The polymerization reaction was stopped by adding water and a NaOH solution having a concentration of 25% by mass as a pH regulator to the copolymer solution with 17, ¹⁰ ] -3-dodecene. Further, the catalyst residue present in the copolymer was removed (decalcified) from the copolymer solution (polymer solution A).
Ethylene and tetracyclo [4.4.0.1 ^2,5 . A cyclohexane solution of a copolymer with 1 ^7,10 ] -3-dodecene (polymer solution A, polymer concentration 7.7 mass%) as a stabilizer pentaerythrityl-tetrakis [3- (3,5-di-t -Butyl-4-hydroxyphenyl) propionate] was added such that the amount added to the copolymer was 0.4 parts by mass with respect to 100 parts by mass of the copolymer. Subsequently, the mixture was once mixed for 1 hour using a stirring tank having an effective volume of 1.0 m ³ before entering the flash drying step.

(Desolvation)
In a double tube heater (outer tube diameter 2B, inner tube diameter 3 / 4B, length 21 m) using water vapor of 20 kg / cm ² G as a heat source, the concentration of the copolymer in the cyclohexane solution is 5% by mass. A cyclohexane solution of the above copolymer was supplied in an amount of 150 kg / h and heated to 180 ° C.
Using a double tube flash dryer (outer tube diameter 2B, inner tube diameter 3 / 4B, length 27 m) and flash hopper (volume 200 L) using 25 kg / cm ² G of water vapor as a heat source, the above heating By removing most of the unreacted monomer together with cyclohexane as a polymerization solvent from the cyclohexane solution of the copolymer that has undergone the process, flash-dried 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 biaxial kneading extruder with a vent, the molten resin A was charged from the resin charging portion of the extruder. Next, for the purpose of removing volatiles from the vent part, the conditions of the extruder are set so that the difference between the maximum value and the minimum value of the resin temperature of the extruder diverter part is within 3 ° C while sucking with a vacuum pump through a trap. It was adjusted. Subsequently, it pelletized with the underwater pelletizer attached to the extruder exit, and the obtained pellet was dried with the hot air of the temperature of 100 degreeC for 4 hours. Furthermore, in order to suppress the mixing of iron atoms (Fe), the polymer production equipment uses stainless steel pipes and polymerization equipment, and further, the resin amount is about 3 to 5 times the resin amount calculated from the average residence time in the polymerization vessel. Pellet-shaped resin A was obtained by performing an operation of flowing 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 minutes (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 described in Table 1, the peak area ratio of the gas chromatogram) is heated at 100 ° C. for 4 hours. Thus, a resin composition A comprising a distilled product of an ester of resin A, triglycerin and oleic acid was directly charged into an extruder in an amount of 0.3 part by mass with respect to 100 parts by mass of resin A. .
Specifically, using a twin screw extruder of L / D = 30 with the same direction rotation, screw diameter of 44 mmφ, and a vent hole at a position of L / D = 24 from the resin charging portion, resin A is added to the resin charging portion. Then, the above-mentioned triglycerin fatty acid ester heated and melted at 80 to 120 ° C. is charged from the vent hole, and melt kneaded under the conditions of a screw speed of 150 rpm and a motor power of 30 kW to obtain a resin composition. It was.

[Example 2]
As shown in Table 1, as triglycerin fatty acid ester, triglycerin oleate which is an ester of triglycerin and oleic acid (mixture of monoester, diester and triester, ester ratio is listed in Table 1, gas chromatogram A resin composition was prepared in the same manner as in Example 1 except that the peak area ratio was 0.5 parts by mass with respect to 100 parts by mass of the resin A.

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

[Example 4]
As shown in Table 1, the following resin B was used in place of resin A, and a triglycerin oleate distillate which was an ester of triglycerin and oleic acid as the triglycerin ester (the ester ratio is listed in Table 1, gas chromatograph) A resin composition was prepared in the same manner as in Example 1 except that 0.4 part by mass of the peak area ratio of the togram was used.

[Example 5]
As shown in Table 1, as triglycerin fatty acid ester, triglycerin oleate which is an ester of triglycerin and oleic acid (mixture of monoester, diester and triester, ester ratio is listed in Table 1, gas chromatogram A resin composition was prepared in the same manner as in Example 1, except that 1.0 part by mass of the peak area ratio) was used in an amount of 1.0 part by mass with respect to 100 parts by mass of the resin A.

[Example 6]
As shown in Table 1, as triglycerin fatty acid ester, triglycerin oleate which is an ester of triglycerin and oleic acid (mixture of monoester, diester and triester, ester ratio is listed in Table 1, gas chromatogram A resin composition was prepared in the same manner as in Example 1 except that the peak area ratio was 1.4 parts by mass with respect to 100 parts by mass of the resin A.

<Synthesis of Resin B>
Ethylene and tetracyclo [4.4.0.1 ^2,5 . The glass transition temperature (Tg) is 151 ° C. and the MFR is 20 g / 10 minutes (260 ° C., 2.degree. C.) by adjusting the ratio of the ratio of ^{17 7,10} ] -3-dodecene and the amount of hydrogen feed to the amount of ethylene feed. The cyclic olefin random copolymer (resin B) was obtained in the same manner as the resin A except that the load was adjusted to 16 kg.

[Comparative Example 1]
As described in Table 1, a resin composition was prepared in the same manner as in Example 1 except that triglycerin fatty acid ester was not used.

[Comparative Example 2]
As shown in Table 1, instead of triglycerin fatty acid ester, a diglycerin and oleic acid ester (diglycerin fatty acid ester) distillate (Riquemar DO-100: manufactured by Riken Vitamin Co., Ltd.) was used as resin A100 parts by mass. A resin composition was prepared in the same manner as in Example 1 except that it was used in an amount of 0.6 parts by mass.

[Comparative Example 3]
As shown in Table 1, instead of triglycerin fatty acid ester, distilled product of diglycerin and oleic acid (diglycerin fatty acid ester) (Riquemar DO-100: manufactured by Riken Vitamin Co., Ltd.) is used as resin B100 parts by mass. A resin composition was prepared in the same manner as in Example 4 except that 0.8 part by mass was used.

About the molded object obtained from the resin composition of Examples 1-6 and Comparative Examples 1-3, it evaluated with the following evaluation methods. The evaluation results are shown in Table 1.
Here, since the optical components of Examples 5 and 6 contain a triglycerin fatty acid ester as in Examples 1 to 4, evaluation of the weld line described later is good.

(Method for evaluating molded product)
(1) Haze Using the injection molding machine (ROBOSHOT S2000i-30α manufactured by FANUC), the resin compositions obtained in Examples and Comparative Examples were injection-molded at a cylinder temperature of 275 ° C., and the optical size was 35 mm × 65 mm × thickness 3 mmt. Each test piece having a surface was produced. The mold temperature was set to 120 ° C. when resin A was used, and 130 ° C. when resin B was used. The internal haze of the molded body was measured based on JIS K-7105 using benzyl alcohol.

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

(3) Weld line evaluation test The outer diameter is 6.2 mm, the lens portion diameter is 5.0 mm, the center thickness (minimum thickness) is 0.35 mm, the maximum thickness is 0.944 mm, the maximum thickness T _max and the minimum thickness are T _Using a mold for forming a lens having a _min ratio (T _max / T _min, thickness deviation ratio) of 2.7 and an injection molding machine (ROBOSHOT S2000i-30α manufactured by FANUC), holding pressure of 100 MPa and injection speed of 50 mm. The resin compositions obtained in the examples and comparative examples were injection molded under the conditions of / s, and 10 molded bodies were produced. When resin A was used, the cylinder temperature was set to 275 ° C. and the mold temperature was set to 135 ° C., and when resin B was used, the cylinder temperature was set to 285 ° C. and the mold temperature was set to 145 ° C.
The obtained molded body was observed with a laser microscope (VK-X100 manufactured by Keyence Corporation), the weld line length generated on the side opposite to the gate was measured, and evaluated according to the following criteria. If the length of the weld line is 1200 μm or more, it enters a portion (optical effective surface) used as a lens, which affects 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), the resin compositions obtained in the examples and comparative examples were injection molded at a cylinder temperature of 275 ° C., and were 35 mm × 65 mm × 3 mm thick. Test pieces each having an optical surface were produced. The mold temperature was set to 120 ° C. when resin A was used, and 130 ° C. when resin B was used.
As for the refractive index of the molded article, the refractive index (nd) at 25 ° C. and a wavelength of 589 nm was measured according to ASTM D542 using a refractometer (KPR200, manufactured by Shimadzu Science Co., Ltd.).

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

(6) Mold dirt Mold and injection molding machine (ROBOSHOT S2000i-30α manufactured by FANUC) for forming a meniscus lens having an outer diameter of 6.0 mm, a lens part diameter of 4.1 mm, and a lens part thickness of 0.5 mm The resin compositions obtained in the examples and comparative examples were injection molded under the conditions of a cylinder temperature of 285 ° C., a mold temperature of 120 ° C. when using resin A, and 130 ° C. when using resin B. Then, 6000 shots were continuously formed. Next, after the 6000 shot molding, the stain on the mold vent adhered to the outer periphery of the lens outer diameter of the mold was observed with a stereo microscope SZX16 (manufactured by Olympus Corporation) at a magnification of 3.5 times.
Ratings were given from low to high dirt. Evaluation was made in 4 grades, with 1 point being the least stained and 4 points having the most dirty.

(7) Analysis method of monoester, diester and triester in triglycerol fatty acid ester or diglycerol fatty acid ester The analysis method of triglycerol fatty acid ester or diglycerol fatty acid ester used in Examples and Comparative Examples is shown below. .
The content of monoester, diester and triester in triglycerin fatty acid ester or diglycerin fatty acid ester was determined by the following method.
(Quantitative method)
Measurement method Measuring instrument: GCMS-QP2010Plus (manufactured by Shimadzu Corporation)
Column: DB-1HT, 0.32 mmφ × 15 m
temperature:
Column: 120 ° C. → Temperature rise at 9 ° C./min→Hold for 10 min at 390 ° C. Inlet temperature: 350 ° C.
Detector temperature: 400 ° C
Carrier gas: He
Split ratio: 10: 1
Injection volume: 1 μm
Detector: FID
-Preparation of measurement sample [1] 0.0130 g of an internal standard (n-butyl phthalate, special grade manufactured by Tokyo Chemical Industry Co., Ltd.) was weighed into a 50 mL volumetric flask and diluted with pyridine to prepare an internal standard solution.
[2] 0.025 g of the sample was precisely weighed in a 50 mL volumetric flask, 5 mL of cyclohexane was added, and the volume was adjusted to 25 mL with acetone.
[3] After collecting 500 μL of the sample solution prepared in step (2) and drying, add 50 μL of internal standard solution and 200 μL of trimethylsilylating agent (BSTFA, manufactured by Tokyo Chemical Industry Co., Ltd.), and heat on a block heater heated to 90 ° C. The trimethylsilylation reaction was carried out for 1 hour.
[4] After step (3), the mixture was air-cooled to room temperature, measured under the above conditions, and the monoester, diester and triester contents were determined from the area ratio of the chart.

(8) Measuring method of temperature (Td-10%) at which weight is reduced by 10% by heating Thermogravimetric differential thermal analysis (TG-DTA) of triglycerin fatty acid ester or diglycerin fatty acid ester is performed, and the weight is reduced by 10% by heating. The temperature (Td-10%) was measured by the following method. Here, an initial weight shows the weight in 30 degreeC, such as a triglycerol fatty acid ester.
Measurement method Measuring device: TG-DTA7300 (manufactured by SII Nanotechnology)
Measurement temperature range: 30 ℃ → 400 ℃
Temperature increase rate: 10 ° C / min
Measurement atmosphere: Air (200 mL / min)
Sample pan used: Aluminum pan (φ5.2mm H5.0mm)
Sample weight: 10mg

Claims (12)

  A cyclic olefin resin composition comprising a cyclic olefin polymer (A) and a triglycerin fatty acid ester. In the cyclic olefin resin composition according to claim 1,
Cyclic olefin-based resin composition containing at least one selected from cyclic olefin-based polymer (A) selected from ethylene or α-olefin-cyclic olefin copolymer (A1) and cyclic olefin ring-opening polymer (A2) object. In the cyclic olefin resin composition according to claim 2,
The cyclic olefin polymer (A) includes the copolymer (A1),
The copolymer (A1) is
A repeating unit (a) derived from at least one olefin represented by the following general formula (I):
At least one cyclic olefin selected from the group consisting of a repeating unit represented by the following general formula (II), a repeating unit represented by the following general formula (III), and a repeating unit represented by the following general formula (IV) A repeating unit (b) derived from,
A cyclic olefin-based resin composition having:

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

(In the general formula (II), 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 as each other. However, they may be 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 6 carbon atoms. -20 aromatic hydrocarbon groups, and R ^{75 to} R ⁷⁸ may be bonded to each other to form a monocyclic or polycyclic ring.)

(In the general formula (III), x and d are 0 or an integer of 1 or more, y and z are 0, 1 or 2, and R ^{81 to} R ⁹⁹ may be the same as or different from each other, An aliphatic hydrocarbon group which is a hydrogen atom, a halogen atom, 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. 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. Good.)

(In the above general formula (IV), R ¹⁰⁰ and R ¹⁰¹ may be the same as or different from each other, and each represents 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 cyclic olefin-derived repeating unit (b) in the copolymer (A1) is bicyclo [2.2.1] -2-heptene and tetracyclo [4.4.0.1 ^2,5 . 1 ^<7,10 ] -3-cyclic olefin resin composition containing the repeating unit derived from the at least 1 sort (s) of compound chosen from dodecene. In the cyclic olefin system resin composition according to claim 3 or 4,
The cyclic olefin resin composition in which the repeating unit (a) derived from the olefin in the copolymer (A1) contains a repeating unit derived from ethylene. In the cyclic olefin system 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. Cyclic olefin resin composition. In the cyclic olefin system resin composition according to any one of claims 1 to 6,
The cyclic olefin resin composition in which the triglycerin fatty acid ester includes an ester of triglycerin and a saturated or unsaturated fatty acid having 8 to 24 carbon atoms. In the cyclic olefin system resin composition according to any one of claims 1 to 7,
The cyclic olefin resin composition which has the glass transition temperature of the said cyclic olefin resin composition in the range of 130 degreeC or more and 160 degrees C or less.   The molded object containing the cyclic olefin resin composition as described in any one of Claims 1 thru | or 8.   An optical component comprising the molded article according to claim 9. The optical component according to claim 10,
An optical component that is an fθ lens, an imaging lens, a sensor lens, a prism, or a light guide plate. The optical component according to claim 10 or 11,
When the maximum thickness of the optical component and T _max, the minimum thickness of the optical component was T _min,
An optical component having an uneven thickness ratio represented by T _max / T _min of 2.0 or more.

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