JP2020164624A - Optical component - Google Patents

Abstract

To provide an optical component having excellent long-term reliability of optical performance in a high temperature environment of 130°C.SOLUTION: An optical component contains a cyclic olefinic copolymer (A) with a glass transition temperature of 150°C or higher and 180°C or lower.SELECTED DRAWING: Figure 1

Description

The present invention relates to optical components.

Cyclic olefin copolymers have excellent optical performance, and are therefore used as optical components such as optical lenses.
Examples of the technique relating to the cyclic olefin-based copolymer used for the optical component include those described in Patent Document 1 (Japanese Unexamined Patent Publication No. 2015-199939).

Patent Document 1 discloses a cyclic olefin resin composition containing a cyclic olefin copolymer and a diglycerin fatty acid ester. Patent Document 1 describes that when such a cyclic olefin resin composition is used, a molded product having excellent optical performance and further suppressing deterioration of optical performance under high temperature and high humidity conditions can be obtained.

JP 2015-199939

In recent years, there has been an increasing demand for in-vehicle camera lenses and camera lenses for mobile devices (mobile phones, smartphones, tablets, etc.). High heat resistance is required for in-vehicle camera lenses and camera lenses for mobile devices. Cyclic olefin copolymers are widely used in optical components such as camera lenses because of their excellent optical properties and mechanical properties.
In-vehicle camera lenses are also required to have high heat resistance, specifically, to have little change in lens shape even when exposed at 130 ° C. for a long time, especially for sensing applications.
However, according to the study by the present inventors, when the optical component containing the cyclic olefin copolymer is exposed to a high temperature environment of 130 ° C. for a long time, the lens shape changes and the optical performance deteriorates. It has been found that it may end up.
The present invention has been made in view of the above circumstances, and provides an optical component having excellent long-term reliability of optical performance in a high temperature environment of 130 ° C.

The present inventors have diligently studied to solve the above problems. As a result, they have found that an optical component containing a cyclic olefin copolymer (A) having a specific glass transition temperature is excellent in long-term reliability of optical performance in a high temperature environment, and completed the present invention.

That is, according to the present invention, the following optical components are provided.

（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。）
［７］
［６］に記載の光学部品において、
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光学部品。
［８］
［６］または［７］に記載の光学部品において、
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光学部品。 [1]
An optical component containing a cyclic olefin copolymer (A) having a glass transition temperature of 150 ° C. or higher and 180 ° C. or lower.
[2]
In the optical component described in [1],
When the optical component is heat-treated at 130 ° C. for 1000 hours,
An optical component in which the difference ΔPV between the surface shape variation PV value of the optical component after the heat treatment and the surface shape variation PV value of the optical component before the heat treatment is 1.00 μm or less.
[3]
The optical component according to [1] or [2], which is an fθ lens, an imaging lens, a sensor lens, a prism, or a light guide plate.
[4]
The optical component according to any one of [1] to [3], which is an in-vehicle camera lens or a camera lens for a mobile device.
[5]
In the optical component according to any one of [1] to [4],
An optical component in which the cyclic olefin-based copolymer (A) contains a copolymer (A1) of ethylene or α-olefin and a cyclic olefin.
[6]
In the optical component described in [5],
The above copolymer (A1)
The repeating unit (a) derived from at least one olefin represented by the following general formula (I) and
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). The repeating unit (b) of origin and
Optical parts with.

(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.)

(In the above 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 may be a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkyl halide group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or 6 carbon atoms. It is an aromatic hydrocarbon group of ~ 20, and R ⁷⁵ ~ R ⁷⁸ may be bonded to each other to form a monocyclic ring or a 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, and R ^{81 to} R ⁹⁹ may be the same or different from each other. A hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms or an aliphatic hydrocarbon group having 3 to 15 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or an alkoxy group. Yes, 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 directly or have an alkylene group having 1 to 3 carbon atoms. They may be bonded via each other, 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 or different from each other, and represent a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and f is 1 ≦ f ≦ 18. .)
[7]
In the optical component described in [6],
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- An optical component containing a repeating unit derived from at least one compound selected from dodecene.
[8]
In the optical component according to [6] or [7],
An optical component in which the olefin-derived repeating unit (a) in the copolymer (A1) contains a repeating unit derived from ethylene.

According to the present invention, it is possible to provide an optical component having excellent long-term reliability of optical performance in a high temperature environment.

It is sectional drawing which shows typically the structure of the optical component produced in an Example. It is the top view which showed typically the structure of the optical component produced in an Example.

Hereinafter, the present invention will be described based on the embodiments. In the present embodiment, "A to B" indicating the numerical range represent A or more and B or less unless otherwise specified.

[Optical parts]
First, the optical components according to this embodiment will be described. The optical component according to the present embodiment includes a cyclic olefin copolymer (A) having a glass transition temperature of 150 ° C. or higher and 180 ° C. or lower.

As a result of studies, the present inventors have found that when an optical component containing a cyclic olefin copolymer is exposed to a high temperature environment for a long time, the lens shape changes and the optical performance deteriorates. ..
The present inventors have diligently studied to solve the above problems. As a result, the optical component containing the cyclic olefin copolymer (A) having a glass transition temperature of 150 ° C. or higher and 180 ° C. or lower is less likely to change the shape of the lens even when exposed to a high temperature environment for a long time, and has a long-term optical performance. It was found to be highly reliable.

That is, according to the present embodiment, it is possible to realize an optical component having excellent long-term reliability of optical performance in a high temperature environment.

The glass transition temperature of the cyclic olefin copolymer (A) according to the present embodiment is 150 ° C. or higher and 180 ° C. or lower, more preferably 150 ° C. or higher and 175 ° C. or lower, and 152 ° C. or higher and 170 ° C. or lower. Is particularly preferable.
The glass transition temperature of the cyclic olefin copolymer (A) according to the present embodiment can be controlled, for example, by the type and amount of the repeating unit contained in the cyclic olefin copolymer (A) and the production conditions.

The glass transition point (Tg) of the cyclic olefin copolymer (A) according to the present embodiment can be measured using, for example, a differential scanning calorimeter (DSC). For example, using an RDC220 manufactured by SII Nanotechnology, the temperature is raised from room temperature to 200 ° C. at a heating rate of 10 ° C./min in a nitrogen atmosphere, then held for 5 minutes, and then held at a heating rate of 10 ° C./min to 30 ° C. The glass transition point can be measured when the temperature is lowered, held for 5 minutes, and then raised to 200 ° C. at a heating rate of 10 ° C./min.

In the optical component according to the present embodiment, when the optical component is heat-treated at 130 ° C. for 1000 hours, the surface shape variation PV value of the optical component after the heat treatment and the surface shape of the optical component before the heat treatment The ΔPV, which is the difference from the fluctuating PV value, is preferably 1.00 μm or less, more preferably 0.80 μm or less, still more preferably 0.60 μm or less, and particularly preferably 0.50 μm or less. Since ΔPV is preferably smaller, the lower limit is not particularly limited, but is, for example, 0.01 μm or more.
It can be said that an optical component having a smaller change in PV value, ΔPV, has a smaller change in shape such as heat shrinkage in a high temperature environment, and deterioration of optical performance is suppressed.
Here, the PV value indicates the difference between the point having the largest shape error from the design value of the molding mold (Peek) and the point having the smallest shape error from the design value of the molding mold (Valley), and ΔPV is , The change of PV value before and after the thermal test is shown. The PV value and ΔPV can be measured by measuring the shape of the lens surface with a three-dimensional measuring device, and specifically, can be evaluated by the method described in Examples.
The optical components according to the present embodiment are in both directions of the resin flow direction (MD direction) and the direction perpendicular to the resin flow (TD direction) on both sides of the lens, that is, on the mold fixing side and the mold movable side. It is particularly preferable that the ΔPV calculated based on the shape measurement is within the above numerical range.
ΔPV is more specifically contained in the cyclic olefin copolymer (A) by controlling the glass transition temperature of the cyclic olefin copolymer (A) constituting the optical component according to the present embodiment. Adjust by highly controlling the type and amount of the repeating unit, the type and amount of the additive other than the cyclic olefin copolymer (A) constituting the optical component, and the manufacturing method of the optical component. Is possible.

Further, in the optical component according to the present embodiment, when the optical component is heat-treated at 105 ° C. for 1000 hours, the surface shape variation PV value of the optical component after the heat treatment and the surface shape variation PV value of the optical component before the heat treatment and the optical component before the heat treatment The ΔPV, which is the difference from the surface shape variation PV value, is preferably 0.50 μm or less, more preferably 0.40 μm or less, and further preferably 0.30 μm or less.
Further, in the optical component according to the present embodiment, when the optical component is heat-treated at 125 ° C. for 1000 hours, the surface shape variation PV value of the optical component after the heat treatment and the surface shape variation PV value of the optical component and the optical component before the heat treatment are obtained. The ΔPV, which is the difference from the surface shape variation PV value, is preferably 0.50 μm or less, more preferably 0.45 μm or less, and further preferably 0.40 μm or less.

The lower limit of the content of the cyclic olefin copolymer (A) in the optical component according to the present embodiment is preferably 70% by mass or more, more preferably 80% by mass, when the entire optical component is 100% by mass. As mentioned above, it is more preferably 90% by mass or more, and particularly preferably 95% by mass or more. When the content of the cyclic olefin copolymer (A) in the optical component according to the present embodiment is at least the above lower limit value, the optical performance can be further improved.
The upper limit of the content of the cyclic olefin copolymer (A) in the optical component according to the present embodiment is not particularly limited, but is, for example, 100% by mass or less.

Since the optical component according to the present embodiment contains the cyclic olefin copolymer (A), 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 accuracy. The optical component is a component used in an optical system device or the like, and specific examples thereof include a sensor lens, a pickup lens, a projector lens, a prism, an fθ lens, an image pickup lens, a light guide plate, and the like, and relates to the present embodiment. From the viewpoint of effect, it can be suitably used for an fθ lens, an imaging lens, a sensor lens, a prism or a light guide plate.
The shape of the lens is a convex lens with spherical surfaces on both sides, a concave lens with spherical surfaces on both sides, a lens with spherical and convex shapes on one side and an aspherical shape on the other side, and a lens with a spherical shape and concave shape on one side and an aspherical shape on the other side. Examples thereof include a lens, a diffractive lens, a Frenel type lens, a wafer lens, a wafer lens array, and a laminate of a wafer lens array. However, for example, since it is not easily deformed even after undergoing a heat resistance test at 130 ° C. × 1000 hr under harsh conditions, it can be used as the above-mentioned conventional optical component, as well as an in-vehicle camera lens and a portable device. It can be particularly preferably used for optical components such as camera lenses for (mobile phones, smartphones, tablets, etc.) that require heat resistance. Examples of in-vehicle camera lenses and camera lenses for portable devices include view camera lenses, sensing camera lenses, light convergence lenses for head-up displays, light diffusion lenses for head-up displays, personal computer cameras, and mobile phone cameras. , Cameras for smartphones, cameras for tablet terminals, cameras for mobile devices, digital cameras, lenses in various optical devices such as cameras for medical devices, and the like. The in-vehicle camera may capture a visible image, an infrared image, or both, and in the case of a visible image, it may be a black-and-white image. It may be a color image. Further, examples of applications other than the above include automobile interior panels, automobile lamp lenses, automobile inner lenses, automobile lens protective covers, automobile light guides, and the like. The optical component according to this embodiment can be suitably used particularly for in-vehicle use.

Hereinafter, each component will be specifically described.

(Cyclic olefin copolymer (A))
The cyclic olefin copolymer (A) according to the present embodiment is a copolymer having a repeating unit derived from the cyclic olefin as an essential constituent unit.
Examples of the cyclic olefin copolymer (A) include a copolymer (A1) of ethylene or α-olefin and a cyclic olefin.

The cyclic olefin compound constituting the copolymer (A1) according to the present embodiment is not particularly limited, and examples thereof include the cyclic olefin monomers described in paragraphs 0037 to 0063 of International Publication No. 2006/0118261.

The copolymer (A1) according to the present embodiment is described below from the viewpoint of further improving heat resistance and improving moldability while maintaining a good balance of transparency and refractive index performance of the obtained optical component. A repeating unit (a) derived from at least one olefin 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. It is preferable to have a repeating unit (b) derived from at least one cyclic olefin 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 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, 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 hydrogen atom, halogen atom, alkyl group having 1 to 20 carbon atoms, alkyl halide group having 1 to 20 carbon atoms, and the like. 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 be bonded to 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 above 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 from each other, and are an aliphatic hydrocarbon group or carbon 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. It is an aromatic hydrocarbon group or alkoxy group having 6 to 20 atoms, and a carbon atom to which R ⁸⁹ and R ⁹⁰ are bonded and 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. 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 the above general formula (IV), R ¹⁰⁰ and R ¹⁰¹ may be the same or different from each other, 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 copolymerization raw materials of the copolymer (A1) according to the present embodiment, is addition-copolymerized to form a 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光学部品を得る観点から、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系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８０モル％以下、特に好ましくは５０モル％以上７０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 above 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, and 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 preferable, and ethylene is particularly preferable, from the viewpoint of obtaining an optical component 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 total amount of the structural units constituting the cyclic olefin copolymer according to the present embodiment is 100 mol%, the proportion of the repeating unit (a) derived from the olefin is preferably 5 mol% or more and 95 mol% or less. It is preferably 20 mol% or more and 90 mol% or less, more preferably 40 mol% or more and 80 mol% or less, and particularly preferably 50 mol% or more and 70 mol% or less.
The proportion of the repeating unit (a) derived from olefin can be measured by ¹³ C-NMR.

The cyclic olefin monomer (b), which is one of the copolymerization raw materials of the copolymer (A1) according to the present embodiment, is addition-copolymerized and 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. 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, 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 hydrogen atom, halogen atom, alkyl group having 1 to 20 carbon atoms, alkyl halide group having 1 to 20 carbon atoms, and the like. 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 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 or different from each other, and are an aliphatic hydrocarbon group or carbon 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. It is an aromatic hydrocarbon group or alkoxy group having 6 to 20 atoms, and a carbon atom to which R ⁸⁹ and R ⁹⁰ are bonded and 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. 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 the above general formula (IVa), R ¹⁰⁰ and R ¹⁰¹ may be the same or different from each other, and represent 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) described above and the cyclic olefin monomer (b) represented by the general formula (IIa), (IIIa) or (IVa) as the copolymerization component, a cyclic olefin system is used. Since the solubility of the copolymer (A) in the solvent is further improved, the moldability is improved and the yield of the product is improved.

For 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. 2006/0118261 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 Pentadecadien 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 -Heneikosen derivative, octacyclo-5-docosene derivative, nonacyclo-5-pentacosene derivative, nonacyclo-6-hexacosene derivative, cyclopentadiene-acenaftylene adduct, 1,4-methano-1,4,4a, 9a-tetrahydrofluorene derivative, Examples thereof include 1,4-methano-1,4,4a, 5,10,10a-hexahydroanthracene derivatives and cycloalkylene derivatives having 3 to 20 carbon atoms.

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.

As the cyclic olefin monomer (b) represented by the above general formula (IIa), 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.) It is preferable to use at least one selected from tetracyclo [4.4.0.1 ^{2, 5.} It is more preferable to use 17 and ¹⁰ ] -3-dodecene. Since these cyclic olefins have a rigid ring structure, they have an advantage that the elastic modulus of the copolymer and the optical component can be easily maintained.

When the total amount of the structural units constituting the copolymer (A1) according to the present 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. It is mol% or less, more preferably 10 mol% or more and 80 mol% or less, further preferably 20 mol% or more and 60 mol% or less, and particularly preferably 30 mol% or more and 50 mol% or less.

The copolymerization type of the copolymer (A1) according to the present embodiment is not particularly limited, and examples thereof include random copolymers and block copolymers. In the present embodiment, the copolymer (A1) according to the present embodiment is a random copolymer from the viewpoint of being excellent in optical properties such as transparency, refractive index and birefringence, and being able to obtain highly accurate optical components. It is preferable to use a polymer.

Examples of the copolymer (A1) according to the present embodiment include ethylene and tetracyclo [4.4.0.1 ^2,5 . It is preferably at least one selected from a random copolymer of ^17,10 ] -3-dodecene and a random copolymer of ethylene and bicyclo [2.2.1] -2-heptene, preferably with ethylene. Tetracyclo [4.4.0.1 ^2,5 . A random copolymer with ^17,10 ] -3-dodecene is more preferred.

In the present embodiment, one type of the cyclic olefin copolymer (A) may be used alone, or two or more types may be used in combination.
The lower limit of the content of the copolymer (A1) contained in the cyclic olefin copolymer (A) according to the present embodiment is the cyclic olefin copolymer (A) contained in the optical component according to the present embodiment. When it is 100% by mass, it is preferably 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 content of the copolymer (A1) in the cyclic olefin copolymer (A) according to the present embodiment is at least the above lower limit value, the optical performance can be further improved.
The upper limit of the content of the copolymer (A1) contained in the cyclic olefin copolymer (A) according to the present embodiment is not particularly limited, but the cyclic olefin copolymer contained in the optical component according to the present embodiment is not particularly limited. When (A) is 100% by mass, it is 100% by mass or less.

Examples of the copolymer (A1) according to the present embodiment include JP-A-60-168708, JP-A-61-120816, JP-A-61-115912, and JP-A-61-115916. , Japanese Patent Application Laid-Open No. 61-271308, Japanese Patent Application Laid-Open No. 61-272216, Japanese Patent Application Laid-Open No. 62-252406, Japanese Patent Application Laid-Open No. 62-252407, etc. Can be done.

(Other ingredients)
In addition to the cyclic olefin copolymer (A), the optical component according to the present embodiment contains an additive known as an optional component as an optional component within a range that does not impair the good physical properties of the optical component according to the present embodiment. Can be done.
Additives include, for example, hydrophilic stabilizers, hydrophilic agents, antioxidants, secondary antioxidants, lubricants, mold release agents, antifogging agents, weather stabilizers, light stabilizers, UV absorbers, antistatic agents. , Metal inactivating agent and the like.

Among the above, it is preferable that the optical component according to the present embodiment contains a hydrophilic stabilizer. It is more preferable to include a hydrophilic stabilizer because deterioration of optical performance under high temperature and high humidity conditions can be suppressed.
The hydrophilic stabilizer is preferably a fatty acid ester of a fatty acid and a polyhydric alcohol. Fatty acid esters of fatty acids and polyhydric alcohols having one or more ether groups are more preferred.

Examples of the fatty acid ester include monoglycerin fatty acid ester, diglycerin fatty acid ester, triglycerin fatty acid ester, pentaerythritol monostearate, pentaerythritol distearate, and pentaerythritol tristearate.
A fatty acid ester of a fatty acid and a polyhydric alcohol having one or more ether groups is an ester of a fatty acid and a polyhydric alcohol having one or more ether groups. The ether group of the polyhydric alcohol does not contain the ether group in the ester group.
Examples of the polyhydric alcohol having one or more ether groups include monoglycerin, diglycerin, triglycerin, tetraglycerin, sorbitan and the like.
In the present embodiment, the fatty acid ester preferably contains a monoglycerin fatty acid ester, a diglycerin fatty acid ester, and a triglycerin fatty acid ester. A diglycerin fatty acid ester is one in which at least one of the four hydroxy groups contained in diglycerin is esterified with a fatty acid.

Fatty acids include saturated fatty acids such as butanoic acid, pentanoic acid, hexanoic acid, heptanic acid, octanoic acid, nonanoic acid, capric acid, lauric acid, myristic acid, palmitic acid and stearic acid; , Sapienoic acid, oleic acid, elaidic acid, gadrainic acid, eicosenoic acid and other monounsaturated fatty acids; Triunsaturated fatty acids such as enoic acid; tetraunsaturated fatty acids such as stearidonic acid, arachidonic acid, and eikosatetraenoic acid; and the like can be mentioned.

Diglycerin fatty acid esters include diglycerin monocaprelate, diglycerin dicaprelate, diglycerin monocaplate, diglycerin dicaplate, diglycerin monolaurate, diglycerin dilaurate, diglycerin monomillistate, and diglycerin dimylystate. , Diglycerin monopalmitate, diglycerin dipalmitate, diglycerin monostearate, diglycerin distearate, diglycerin monobehenate, diglycerin dibehenate and other diglycerin saturated fatty acid esters; diglycerin monoolate, di Diglycerin unsaturated fatty acid esters such as glycerin diolate; and the like; one or a combination of two or more selected from these can be used.
In the present embodiment, the diglycerin fatty acid ester is preferably an ester of diglycerin and a saturated or unsaturated fatty acid having 12 to 18 carbon atoms selected from the above.

From the viewpoint that the additive and the cyclic olefin copolymer are evenly and uniformly mixed, it is preferable to contain diglycerin unsaturated fatty acid ester as a main component, and among them, diglycerin monooleate may be contained as a main component. More preferred. Since the diglycerin skeleton has hydrophilicity and the fatty acid improves compatibility with the resin, transparency is maintained and moisture resistance is excellent.

The optical component according to the present embodiment may contain at least one diglycerin fatty acid ester. Preferred embodiments of the at least one diglycerin fatty acid ester include monoester alone or a combination of monoester and diester.

The triglycerin fatty acid ester is an ester of a fatty acid and triglycerin.
The triglycerin fatty acid ester according to the present embodiment is one in which at least one of the five hydroxy groups contained in triglycerin is esterified with a fatty acid.

Triglycerin fatty acid esters include triglycerin monocaprelate, triglycerin dicaprelate, triglycerin tricaprylate, triglycerin monocaplate, triglycerin dica plate, triglycerin trica plate, triglycerin monolaurate, triglycerin dilaurate, etc. Triglycerin trilaurate, triglycerin monomillistate, triglycerin dimillistate, triglycerin trimillistate, triglycerin monopalmitate, triglycerin dipalmitate, triglycerin tripalmilate, triglycerin monostearate, triglycerin Triglycerin saturated fatty acid esters such as distearate, triglycerin tristearate, triglycerin monobehenate, triglycerin dibehenate, triglycerin tribehenate; triglycerin monooleate, triglycerin dioleate, triglycerin triolate Etc., such as triglycerin unsaturated fatty acid ester; etc., and one or a combination of two or more selected from these can be used.
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 or more and 24 or less carbon atoms, and the triglycerin and a saturated or unsaturated fatty acid having 12 or more and 18 or less carbon atoms. It is more preferable to contain an ester of.

Examples of the triglycerin fatty acid ester according to the present embodiment include monoester alone, a mixture of monoester and diester, or a mixture of monoester, diester and triester.
As such a triglycerin fatty acid ester, for example, the compounds described in JP-A-2006-232714, JP-A-2002-275308, JP-A-10-165152 and the like can be used.
Examples of commercially available hydrophilic stabilizers according to the present embodiment include Rikemar DO-100 (manufactured by RIKEN Vitamin Co., Ltd.) and Exepearl PE-MS (manufactured by Kao Corporation).
In the optical component according to the present embodiment, the lower limit of the content of the hydrophilic stabilizer is preferably 0.05 part by mass or more and 0.4 part by mass or more with respect to 100 parts by mass of the optical component. Is more preferable. The upper limit of the content of the hydrophilic stabilizer is preferably 3.0 parts by mass or less, more preferably 2.5 parts by mass or less, and 1.2 parts by mass or less with respect to 100 parts by mass of the optical component. Is more preferable.

<Manufacturing method of optical parts>
Next, a method of manufacturing an optical component according to the present embodiment will be described.
The optical component according to the present embodiment can be obtained, for example, by a manufacturing method including at least the following step (1). Further, the optical component according to the present embodiment can also be obtained by a manufacturing method including the following steps (1) and (2). However, the method for manufacturing optical components according to this embodiment is not limited to the following examples.
Step (1): A step of producing a molded product (optical component) by molding a cyclic olefin resin composition containing a cyclic olefin copolymer (A) into a predetermined shape Step (2): Obtained molding A step of aging a body under specific conditions to obtain an optical component according to the present embodiment The steps (1) and (2) will be described below.

First, a molded product which is (a precursor of) an optical component according to the present embodiment is manufactured by molding a cyclic olefin resin composition containing the cyclic olefin copolymer (A) into a predetermined shape.
The method for molding the cyclic olefin resin composition to obtain a molded product 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 and the like can be applied. Is. Among these, the injection molding method is preferable from the viewpoint 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 in the range.

In the cyclic olefin resin composition according to the present embodiment, for example, the cyclic olefin copolymer (A) and other components added as necessary are mixed with a known kneading device such as an extruder and a Banbury mixer. Method of melting and kneading; a method of dissolving the cyclic olefin copolymer (A) and other components added as necessary in a common solvent and then evaporating the solvent; a cyclic olefin copolymer in a poor solvent. It can be obtained by a method of adding and precipitating a solution of the coalescence (A) and other components added as needed;

Then, the obtained molded product is, for example, (glass transition point Tg-40 of the cyclic olefin copolymer (A)) to (glass transition point Tg-5 of the cyclic olefin copolymer (A)) ° C. It is also possible to carry out the annealing treatment for 2 to 8 hours within the range of. By performing the annealing treatment, the molecules of the cyclic olefin copolymer (A) in the molded product are relaxed and the free volume is reduced. Therefore, even if the heat treatment is performed, the change in specific gravity (change in volume) is less likely to occur, and an optical component having a smaller change in shape can be obtained.
Here, if the conditions for the annealing treatment are strict, the molded product will be deformed and will not return. Therefore, it is preferable to perform the annealing treatment under the above conditions and within a range in which the molded product is not deformed. That is, when annealing, it is preferable to perform the annealing treatment at a temperature and time so that deformation of the molded product does not occur.

A coat layer such as an antireflection layer or a hard coat layer may be provided on the surface of the optical component of the present invention, if necessary. The antireflection layer may be a single layer or a multilayer, and may be an organic substance or an inorganic substance, but is preferably an inorganic substance. Specific examples thereof include oxides or fluorides such as silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, cerium oxide, tantalum oxide, magnesium oxide and magnesium fluoride. The film forming method is not particularly limited, but an antireflection layer can be formed on the surface of the optical lens by a method such as a vacuum deposition method or a sputtering method.
A water-repellent layer and other functional layers may or may not be further provided on the antireflection layer. Further, if necessary, by forming a buffer layer between the lens surface and the antireflection layer, it is possible to prevent the antireflection layer from cracking during thermal expansion.
Amorphous silica, acrylic resin, or the like can be used as the coating of the buffer layer.
The coating method is not particularly limited, and examples thereof include a method of forming a coating liquid in which a substance to be coated is dispersed or dissolved in a solvent that can be dissolved or dispersed, and applying the coating liquid by a method such as a spin coating method, or a method of vapor deposition. be able to.
The coating layer and the buffer layer may be formed before the annealing treatment or after the annealing treatment.

The present invention is not limited to the above-described embodiment, and modifications, improvements, and the like within the range in which the object of the present invention can be achieved are included in the present invention.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to the description of these Examples.

<Example>
<Preparation of resin composition A>
(Catalyst preparation)
Diluted VO a _{(OC 2} H 5) Cl ₂ with cyclohexane, vanadium concentration was prepared vanadium catalyst is 6.7 mmol / L-cyclohexane. Ethylaluminum 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)
Using a stirring polymerizer (inner diameter 500 mm, reaction volume 100 L), ethylene and tetracyclo [4.4.0.1 ^2,5 . A copolymerization reaction with 17 and ¹⁰ ] -3-dodecene was carried out. Here, ethylene was supplied into the polymerizer together with hydrogen gas. When this copolymerization reaction is carried out, the vanadium catalyst prepared by the above method is used in an amount such that the vanadium catalyst concentration with respect to cyclohexane in the polymer used as the polymerization solvent is 0.6 mmol / L. Supplied in. Further, ethyl aluminum sesquichloride, which is an organoaluminum compound, was supplied into the polymer in an amount such that Al / V = 18.0. The polymerization temperature was 8 ° C., the polymerization pressure was 1.8 kg / cm ² G, and the copolymerization reaction was continuously carried out.

(Decalcification)
25% by mass of water and pH adjuster with respect to the copolymer solution of ethylene and tetracyclo [4.4.0.1 ² , 5.1 ^7,10 ] -3-dodecene extracted from the polymerizer. Sodium hydroxide aqueous solution was added to stop the polymerization reaction. In addition, the catalyst residue present in the copolymer was removed (decalcified) from the copolymer solution. In a cyclohexane solution (polymer concentration 7.7% by mass) of a copolymer of ethylene and tetracyclo [4.4.0.1 ² , 5.1 ^7,10 ] -3-dodecene that had undergone the above decalcification treatment. The amount of pentaerythrityl-tetrax [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] added to the copolymer as a stabilizer is 0.4% by mass with respect to 100 parts by mass of the copolymer. It was added so as to form a part. Then, before entering the flash drying step, the mixture was once mixed for 1 hour using a stirring tank having an effective volume of 1.0 m ³ .

(Desolvent)
Double-pipe heater with steam 20 kg / cm ² G as heat source (the outer tube diameter 2B, Uchikan径3 / 4B, length 21m), the concentration of the copolymer in cyclohexane solution of 5 wt% The cyclohexane solution of the above-mentioned copolymer was supplied at an amount of 150 kg / h and heated to 180 ° C.
Using steam 25 kg / cm ² G as heat source double-pipe flash dryer (outer pipe diameter 2B, Uchikan径3 / 4B, length 27m) using a flash hopper (volume 200L) and said heating Ethylene and tetracyclo [4.4.0.1 ² , 5.1] in a molten state flash-dried by removing most of the unreacted monomers together with cyclohexane as a polymerization solvent from the cyclohexane solution of the above copolymer that has undergone the steps. ^7,10 ] -3-Dodecene and a random copolymer (cyclic olefin copolymer (A-1) were obtained. The glass transition temperature Tg of the cyclic olefin copolymer (A-1) was obtained by the method described later. When (° C.) was evaluated, it was 155 ° C.

(Extrusion)
Rikemar DO-100 (manufactured by RIKEN Vitamin) as a fatty acid ester was heated at 100 ° C. for 4 hours in a molten state in an amount of 0.9 parts by mass with respect to 100 parts by mass of the cyclic olefin copolymer (A-1). An underwater pelletizer that is directly charged into a twin-screw kneading extruder with a vent, kneaded with a cyclic olefin copolymer (A-1) charged from the resin charging part of the extruder, and attached to the extruder outlet. The obtained pellets were dried with hot air at a temperature of 100 ° C. for 4 hours to obtain a resin composition A-1. When the MFR of the resin composition A-1 was evaluated by the method described later, it was 11 g / 10 min.

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

[Melt flow rate (MFR)]
The measurement was carried out at 260 ° C. and a load of 2.16 kg according to ASTM D1238.

(Manufacturing of optical parts)
<Example 1>
Using an injection molding machine (SE30DUZ manufactured by Sumitomo Heavy Industries, Ltd.), the resin composition A-1 was polished into an optically planar shape under the conditions of a cylinder temperature of 275 ° C. and a mold temperature of 145 ° C. in a mold having a transfer surface. Injection molding was performed to obtain an optical component having an optical surface to which the polished surface of the mold was transferred in the shape shown in FIG.
R1 surface: diameter 6 mm, R (radius of curvature) 10 mm
R2 surface: diameter 6 mm, R 8 mm

<Comparative example 1>
Ethylene and a cyclic olefin in place of the cyclic olefin copolymer A-1 (tetracyclo ^[4.4.0.1 2,5 ^.1 7,10] -3- dodecene), a copolymer (manufactured by Mitsui Chemicals, Inc. , Product name: Apel 5015AL, MFR: 36g / 10min (260 ° C, 2.16kg load, conforms to ASTM D1238), Tg: 145 ° C) and the mold temperature during injection molding is 138 ° C. An optical component was obtained by injection molding in the same manner as in Example 1 except for the above.

[Evaluation method for optical components]
The obtained optical components were evaluated by the following methods.

<Change in lens surface shape>
(Shape measurement before heat resistance test)
First, the shape of the lens surface of the optical components of Examples and Comparative Examples before the heat resistance test was measured with an ultra-high precision coordinate measuring device UA3P (manufactured by Panasonic Corporation). The measurement was performed using a diamond stylus with a radius of curvature of 2 μm at a measurement speed of 0.1 mm / s for the R1 and R2 surfaces of the optical component, in the MD direction and TD in the range of 87% of the effective diameter (diameter 6 mm). Each direction was carried out and the PV value was determined. Here, the difference between the point with the largest shape error from the design value of the molding mold (Peek) and the point with the smallest shape error from the design value of the molding mold (Valley) is taken as the acronym and the PV value. Called.
The R1 surface is the surface on the fixed side of the mold in injection molding, and the R2 surface is the surface on the movable side of the mold in injection molding. Further, as shown in FIG. 2, the MD direction indicates the resin flow direction, and the TD direction indicates the direction perpendicular to the resin flow.

(Heat resistance test)
The optical components whose shape was measured on the lens surface were allowed to stand in an oven at a temperature of 105 ° C., 125 ° C., or 130 ° C. for 1000 hours, respectively.

(Shape measurement after heat resistance test)
After the heat resistance test, the optical component was taken out from the oven, and the shape of the lens surface was measured 24 hours later. As before the heat resistance test, using a diamond stylus with a tip curvature radius of 2 μm, the R1 and R2 surfaces of the optical component were measured at a measurement speed of 0.1 mm / s for a range of 87% of the effective diameter (diameter 6 mm). The shape of the lens surface was measured in each of the MD direction and the TD direction, and the PV value was obtained. In addition, the change in PV value (ΔPV μm) before and after the heat resistance test was evaluated. Table 1 shows the ΔPV (μm) of the obtained optical component.

As can be understood from Table 1, in the optical component containing the cyclic olefin copolymer (A) having a glass transition temperature (Tg) of 150 ° C. or higher, ΔPV even before and after the harsh heating test of 130 ° C. × 1000 hr. Is 1.00 μm or less, and it is understood that the optical component has little shape change before and after the heating test. Further, the optical component according to the present embodiment, which is not easily deformed even after such a harsh heating test, is particularly suitable for in-vehicle use and the like.

Claims (8)

An optical component containing a cyclic olefin copolymer (A) having a glass transition temperature of 150 ° C. or higher and 180 ° C. or lower. In the optical component according to claim 1,
When the optical component is heat-treated at 130 ° C. for 1000 hours,
An optical component in which the difference ΔPV between the surface shape variation PV value of the optical component after the heat treatment and the surface shape variation PV value of the optical component before the heat treatment is 1.00 μm or less. The optical component according to claim 1 or 2, which is an fθ lens, an imaging lens, a sensor lens, a prism, or a light guide plate. The optical component according to any one of claims 1 to 3, which is an in-vehicle camera lens or a camera lens for a mobile device. In the optical component according to any one of claims 1 to 4.
An optical component in which the cyclic olefin copolymer (A) contains a copolymer (A1) of ethylene or α-olefin and a cyclic olefin. In the optical component according to claim 5,
The copolymer (A1)
The repeating unit (a) derived from at least one olefin represented by the following general formula (I) and
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). The repeating unit (b) of origin and
Optical parts with.

(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 identical to each other. However, they may be different, and may be a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkyl halide group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or 6 carbon atoms. It is an aromatic hydrocarbon group of ~ 20, and R ⁷⁵ ~ R ⁷⁸ may be bonded to each other to form a monocyclic ring or a 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 or different from each other. A hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms or an aliphatic hydrocarbon group having 3 to 15 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or an alkoxy group. Yes, 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 directly or have an alkylene group having 1 to 3 carbon atoms. They may be bonded via each other, 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 general formula (IV), R ¹⁰⁰ and R ¹⁰¹ may be the same or different from each other, and represent a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and f is 1 ≦ f ≦ 18. .) In the optical component according to claim 6,
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- An optical component containing a repeating unit derived from at least one compound selected from dodecene. In the optical component according to claim 6 or 7.
An optical component in which the olefin-derived repeating unit (a) in the copolymer (A1) contains a repeating unit derived from ethylene.

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