JP2019131658A - Fluorine-containing cyclic olefin copolymer and molded body - Google Patents

Abstract

To provide a fluorine-containing cyclic olefin copolymer excellent in moldability and capable of providing a molded body having high refractive index, high Abbe number and high heat resistance.SOLUTION: The fluorine-containing cyclic olefin copolymer has a constitutional unit (A) derived from α-olefin having 2 to 10 carbon atoms, a constitutional unit (B) derived from a fluorine-containing cyclic olefin represented by a specific chemical formula, and a constitutional unit (C) derived from cyclic olefin represented by the specific chemical formula, at a specific ratio of constitutional units (A), (B) and (C), and has glass transition temperature (Tg) measured by a differential scanning calorimeter (DSC) of 100°C to 180°C.SELECTED DRAWING: None

Description

  The present invention relates to a fluorine-containing cyclic olefin copolymer and a molded body.

A cyclic olefin polymer is used for the optical lens. Cyclic olefin polymers used for such molded articles as optical lenses are required to have properties such as high transparency, excellent dimensional stability, and excellent heat resistance.
Further, the optical lens is required to have a high Abbe number and a high refractive index characteristic in order to realize a reduction in size and thickness while maintaining a clear visual field.

  Examples of the technology relating to the cyclic olefin polymer used in such an optical lens include those described in Patent Document 1 (Japanese Patent Laid-Open No. 2010-145959) and Patent Document 2 (Japanese Patent Laid-Open No. 2007-177046). Can be mentioned.

  In Patent Document 1, the refractive index nD at a wavelength of 589 nm is 1.37 or more, the Abbe number νD satisfies νD ≧ 63 and νD ≧ 430−250 × nD, the glass transition temperature is 100 ° C. or higher, A resin composition for optical materials containing a fluorine-containing ring structure-containing polymer having a repeating unit is described.

  Patent Document 2 describes an optical component material containing a fluorine-containing cyclic olefin polymer having a refractive index of 1.48 or less with respect to D-line wavelength light and having at least a specific repeating structural unit.

JP 2010-145959 A JP 2007-177046 A

According to the study by the present inventors, it has been clarified that the cyclic olefin polymer specifically disclosed in Patent Document 1 has room for improvement in moldability. Further, according to the study by the present inventors, it has been clarified that the cyclic olefin polymer specifically disclosed in Patent Document 2 has a low glass transition temperature and there is room for improvement in heat resistance.
That is, the conventional cyclic olefin polymer has room for improvement in terms of improving moldability while having a high refractive index, a high Abbe number, and a high heat resistance.

  The present invention has been made in view of the above circumstances, and provides a fluorine-containing cyclic olefin-based copolymer that is excellent in moldability and capable of obtaining a molded article having a high refractive index, a high Abbe number, and high heat resistance. It is to provide.

  The present inventors diligently studied to solve the above problems. As a result, a fluorine-containing cyclic olefin copolymer containing a specific unit of a structural unit derived from an α-olefin, a structural unit derived from a fluorine-containing cyclic olefin, and a structural unit derived from a cyclic olefin is molded. The present invention has been completed by finding that it is possible to realize a molded article having excellent properties, high refractive index, high Abbe number and high heat resistance.

  That is, according to the present invention, the following fluorine-containing cyclic olefin copolymer and molded article are provided.

（上記一般式（１）中、Ｒ^１〜Ｒ^４はそれぞれ独立に水素原子、フッ素原子、置換または無置換のアルキル基、フッ素原子を含有するアルキル基、フッ素原子を含有するアルコキシ基、フッ素原子を含有するエーテル結合含有アルキル基、あるいは、−ＣＯＯＲ^５または−ＯＣＯＲ^５で表される置換基を表し、Ｒ^１〜Ｒ^４のうちの少なくとも２つが互いに結合して環構造を形成していてもよい。Ｒ^５は置換または無置換のアルキル基、あるいは、フッ素原子を含有するアルキル基である。Ｒ^１〜Ｒ^４中に少なくとも１つのフッ素原子を含む。ｍは０または１を表す。）

（上記一般式（２）中、Ｒ^６〜Ｒ^９はそれぞれ独立に水素原子、置換または無置換のアルキル基、あるいは、−ＣＯＯＲ^１０または−ＯＣＯＲ^１０で表される置換基を表し、Ｒ^６〜Ｒ^９のうちの少なくとも２つが互いに結合して環構造を形成していてもよい。Ｒ^１０は置換または無置換のアルキル基である。ｎは０または１を表す。）
［２］
上記［１］に記載のフッ素含有環状オレフィン系共重合体において、
上記一般式（１）においてｍが１であるフッ素含有環状オレフィン系共重合体。
［３］
上記［１］または［２］に記載のフッ素含有環状オレフィン系共重合体において、
上記α−オレフィンがエチレンを含むフッ素含有環状オレフィン系共重合体。
［４］
上記［１］乃至［３］のいずれか一つに記載のフッ素含有環状オレフィン系共重合体において、
上記一般式（１）においてｍが１であり、Ｒ^１〜Ｒ^４のうちの少なくとも３つがフッ素原子であるフッ素含有環状オレフィン系共重合体。
［５］
上記［１］乃至［４］のいずれか一つに記載のフッ素含有環状オレフィン系共重合体において、
上記フッ素含有環状オレフィン系共重合体からなる厚さ１．０ｍｍの射出成形シートを作製したとき、当該射出成形シートのアッベ数（ν）が５０以上であるフッ素含有環状オレフィン系共重合体。
［６］
上記［１］乃至［５］のいずれか一つに記載のフッ素含有環状オレフィン系共重合体において、
上記フッ素含有環状オレフィン系共重合体からなる厚さ１．０ｍｍの射出成形シートを作製したとき、ＡＳＴＭ Ｄ５４２に準じて測定される上記射出成形シートの波長５８９ｎｍにおける屈折率（ｎｄ）が１．３７以上であるフッ素含有環状オレフィン系共重合体。
［７］
上記［１］乃至［６］のいずれか一つに記載のフッ素含有環状オレフィン系共重合体を含む成形体。
［８］
光学レンズである上記［７］に記載の成形体。 [1]
A structural unit (A) derived from an α-olefin having 2 to 10 carbon atoms;
A structural unit (B) derived from a fluorine-containing cyclic olefin represented by the following general formula (1);
A structural unit (C) derived from a cyclic olefin represented by the following general formula (2);
A fluorine-containing cyclic olefin copolymer having
When the total content of the structural unit (A), the structural unit (B) and the structural unit (C) in the fluorine-containing cyclic olefin copolymer is 100 mol%,
The content of the structural unit (A) in the fluorine-containing cyclic olefin copolymer is 40 mol% or more and 80 mol% or less,
The content of the structural unit (B) in the fluorine-containing cyclic olefin copolymer is 20 mol% or more and 40 mol% or less,
The content of the structural unit (C) in the fluorine-containing cyclic olefin copolymer is 0 mol% or more and 20 mol% or less,
A fluorine-containing cyclic olefin copolymer having a glass transition temperature (Tg) of 100 to 180 ° C. measured by a differential scanning calorimeter (DSC).

(In the general formula (1), R ^{1 to} R ⁴ are each independently a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group, an alkyl group containing a fluorine atom, an alkoxy group containing a fluorine atom, or a fluorine atom. Represents an ether group-containing alkyl group containing or a substituent represented by —COOR ⁵ or —OCOR ⁵ , and at least two of R ^{1 to} R ⁴ may be bonded to each other to form a ring structure. R ⁵ is a substituted or unsubstituted alkyl group or an alkyl group containing a fluorine atom, and at least one fluorine atom is contained in R ^{1 to} R ⁴ , m represents 0 or 1)

(In the general formula ^(2), R 6 ~R ⁹ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituent represented by -COOR ¹⁰ or -OCOR ^{10, R} 6 ~ At least two of R ⁹ may be bonded to each other to form a ring structure, R ¹⁰ is a substituted or unsubstituted alkyl group, and n represents 0 or 1.)
[2]
In the fluorine-containing cyclic olefin copolymer according to the above [1],
A fluorine-containing cyclic olefin copolymer in which m is 1 in the general formula (1).
[3]
In the fluorine-containing cyclic olefin copolymer according to the above [1] or [2],
A fluorine-containing cyclic olefin copolymer in which the α-olefin contains ethylene.
[4]
In the fluorine-containing cyclic olefin copolymer according to any one of [1] to [3] above,
A fluorine-containing cyclic olefin copolymer in which m is 1 in the general formula (1) and at least three of R ^{1 to} R ⁴ are fluorine atoms.
[5]
In the fluorine-containing cyclic olefin copolymer according to any one of the above [1] to [4],
A fluorine-containing cyclic olefin copolymer having an Abbe number (ν) of 50 or more when the injection-molded sheet having a thickness of 1.0 mm made of the fluorine-containing cyclic olefin copolymer is prepared.
[6]
In the fluorine-containing cyclic olefin copolymer according to any one of [1] to [5] above,
When an injection-molded sheet having a thickness of 1.0 mm made of the fluorine-containing cyclic olefin copolymer is produced, the refractive index (nd) at a wavelength of 589 nm of the injection-molded sheet measured in accordance with ASTM D542 is 1.37. The fluorine-containing cyclic olefin copolymer as described above.
[7]
The molded object containing the fluorine-containing cyclic olefin type copolymer as described in any one of said [1] thru | or [6].
[8]
The molded article according to [7], which is an optical lens.

  ADVANTAGE OF THE INVENTION According to this invention, while being excellent in a moldability, the fluorine-containing cyclic olefin type copolymer which can obtain the molded object which has a high refractive index, a high Abbe number, and high heat resistance can be provided.

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

[Fluorine-containing cyclic olefin copolymer]
First, the fluorine-containing cyclic olefin copolymer (P) according to this embodiment will be described.
The fluorine-containing cyclic olefin copolymer (P) according to this embodiment is represented by a structural unit (A) derived from an α-olefin having 2 to 10 carbon atoms and the following general formula (1). It has a structural unit (B) derived from a fluorine-containing cyclic olefin and a structural unit (C) derived from a cyclic olefin represented by the following general formula (2).
And when the total content of the structural unit (A), the structural unit (B) and the structural unit (C) in the fluorine-containing cyclic olefin copolymer is 100 mol%, the fluorine-containing cyclic olefin The content of the structural unit (A) in the copolymer is 40 mol% or more and 80 mol% or less, and the content of the structural unit (B) in the fluorine-containing cyclic olefin copolymer is 20 mol. % To 40 mol%, and the content of the structural unit (C) in the fluorine-containing cyclic olefin copolymer is 0 mol% to 20 mol%, measured by a differential scanning calorimeter (DSC) The glass transition temperature (Tg) of the fluorine-containing cyclic olefin copolymer is 100 ° C. or higher and 180 ° C. or lower.

（上記一般式（１）中、Ｒ^１〜Ｒ^４はそれぞれ独立に水素原子、フッ素原子、置換または無置換のアルキル基、フッ素原子を含有するアルキル基、フッ素原子を含有するアルコキシ基、フッ素原子を含有するエーテル結合含有アルキル基、あるいは、−ＣＯＯＲ^５または−ＯＣＯＲ^５で表される置換基を表し、Ｒ^１〜Ｒ^４のうちの少なくとも２つが互いに結合して環構造を形成していてもよい。Ｒ^５は置換または無置換のアルキル基、あるいは、フッ素原子を含有するアルキル基である。Ｒ^１〜Ｒ^４中に少なくとも１つのフッ素原子を含む。ｍは０または１を表す。）

(In the general formula (1), R ^{1 to} R ⁴ are each independently a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group, an alkyl group containing a fluorine atom, an alkoxy group containing a fluorine atom, or a fluorine atom. Represents an ether group-containing alkyl group containing or a substituent represented by —COOR ⁵ or —OCOR ⁵ , and at least two of R ^{1 to} R ⁴ may be bonded to each other to form a ring structure. R ⁵ is a substituted or unsubstituted alkyl group or an alkyl group containing a fluorine atom, and at least one fluorine atom is contained in R ^{1 to} R ⁴ , m represents 0 or 1)

（上記一般式（２）中、Ｒ^６〜Ｒ^９はそれぞれ独立に水素原子、置換または無置換のアルキル基、あるいは、−ＣＯＯＲ^１０または−ＯＣＯＲ^１０で表される置換基を表し、Ｒ^６〜Ｒ^９のうちの少なくとも２つが互いに結合して環構造を形成していてもよい。Ｒ^１０は置換または無置換のアルキル基である。ｎは０または１を表す。）

(In the general formula ^(2), R 6 ~R ⁹ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituent represented by -COOR ¹⁰ or -OCOR ^{10, R} 6 ~ At least two of R ⁹ may be bonded to each other to form a ring structure, R ¹⁰ is a substituted or unsubstituted alkyl group, and n represents 0 or 1.)

The fluorine-containing cyclic olefin-based copolymer (P) according to the present embodiment includes a structural unit (A) derived from an α-olefin having 2 to 10 carbon atoms, and a fluorine represented by the general formula (1). The structural unit (B) derived from the containing cyclic olefin and the structural unit (C) derived from the cyclic olefin represented by the general formula (2) are respectively contained in the above ratio, and the glass transition temperature is within the above range. As a result, the moldability can be improved while satisfying the high refractive index, high Abbe number and high heat resistance required for optical lenses and the like.
From the above, according to the fluorine-containing cyclic olefin copolymer (P) according to this embodiment, it is possible to obtain a molded body having excellent moldability and having a high refractive index, a high Abbe number, and high heat resistance. Become.

(Structural unit (A) derived from an α-olefin having 2 to 10 carbon atoms)
The structural unit (A) according to the present embodiment is a structural unit derived from an α-olefin having 2 to 10 carbon atoms. The α-olefin having 2 to 10 carbon atoms may be linear or branched. Examples of such α-olefins include linear α-olefins having 2 to 10 carbon atoms, such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene and 1-decene. Examples of olefins include branched α-olefins having 4 to 10 carbon atoms, such as 4-methyl-1-pentene, 3-methyl-1-pentene, and 3-methyl-1-butene. Among these, a linear α-olefin having 2 to 4 carbon atoms is preferable, and ethylene is particularly preferable. Such α-olefins may be used alone or in combination of two or more.

When the total content of the structural unit (A), the structural unit (B), and the structural unit (C) in the fluorine-containing cyclic olefin copolymer (P) according to this embodiment is 100 mol%, The content of the structural unit (A) in the fluorine-containing cyclic olefin copolymer (P) according to this embodiment is preferably 40 mol% or more and 80 mol% or less, more preferably 50 mol% or more and 78 mol%. Hereinafter, it is 60 mol% or more and 75 mol% or less more preferably.
When content of the said structural unit (A) is more than the said lower limit, while maintaining heat resistance of a molded object obtained, refractive index, and Abbe number favorable, fluorine-containing cyclic olefin type copolymer (P) The moldability can be made better. Moreover, when the content of the structural unit (A) is not more than the above upper limit value, the moldability of the fluorine-containing cyclic olefin copolymer (P), the refractive index, the Abbe number, and the transparency of the obtained molded body It is possible to further improve the heat resistance of the obtained molded product while maintaining good optical characteristics such as the above.
In the present embodiment, the content of the structural unit (A) can be measured by, for example, ¹ H-NMR or ¹³ C-NMR.

(Structural unit derived from fluorine-containing cyclic olefin (B))
The structural unit (B) according to the present embodiment is a structural unit derived from a fluorine-containing cyclic olefin represented by the general formula (1).
The substituted or unsubstituted alkyl group in ^R 1 to R ⁴ in the general formula (1) is preferably from 1 to 30 carbon atoms, more preferably from 1 to 20 carbon atoms, such as methyl group, ethyl Group, n-propyl group and the like.
Examples of the substituted alkyl group include an aralkyl group, a hydroxyalkyl group (for example, hydroxyethyl group), an alkoxyalkyl group (for example, methoxyethyl group), and the like.
The aralkyl group preferably has 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, and examples thereof include a benzyl group and a p-methoxybenzyl group.
Examples of other substituents of the substituted alkyl group include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), an alkoxy group (for example, a methoxy group, an ethoxy group), and the like.
Examples of the alkyl group containing a fluorine atom in R ^{1 to} R ⁴ include a fluorine-containing alkyl group having 1 to 30 carbon atoms, preferably a perfluoroalkyl group having 1 to 10 carbon atoms, A perfluoroalkyl group having 1 to 4 carbon atoms is more preferred.
Examples of the alkoxy group containing a fluorine atom in R ^{1 to} R ⁴ include an alkoxy group containing a fluorine atom having 1 to 30 carbon atoms, and a perfluoroalkoxy group having 1 to 10 carbon atoms. Is preferred.
Examples of the ether bond-containing alkyl group containing a fluorine atom in R ^{1 to} R ⁴ include an alkoxy group containing a fluorine atom having 1 to 30 carbon atoms. A fluoroalkoxy group is preferred.
In the above R ^{1 to} R ⁴ , —COOR ⁵ or —OCOR ⁵ is also preferable, and R ⁵ is a substituted or unsubstituted alkyl group or an alkyl group containing a fluorine atom, and an alkyl group containing a fluorine atom. More preferably. Also, of the -COOR ⁵ and -OCOR ^5, towards the -COOR ⁵ is preferred. Here, examples of the alkyl groups containing a substituted or unsubstituted alkyl group, and a fluorine atom in R ⁵ may be the same as the examples given in the above R ¹ to R ^4.

R ^{1 to} R ⁴ are preferably a fluorine atom, an alkyl group containing a fluorine atom, or an alkoxy group containing a fluorine atom, and more preferably a fluorine atom or an alkyl group containing a fluorine atom.
At least two of R ^{1 to} R ⁴ may be bonded to each other to form a ring structure. The ring structure may be monocyclic or polycyclic. For example, the case where two of R ^{1 to} R ⁴ are bonded to each other to form an alkylene group can be exemplified, and more specifically, any one of R ¹ or R ² and any of R ³ and R ⁴ And the like may be combined with each other to form an alkylene group. R ^{1 to} R ⁴ are preferably not bonded to each other to form a ring structure.
Comprising at least one fluorine atom in the ^R 1 to R ^4, preferably includes three or more fluorine atoms in the ^R 1 to R ^4, at least one trifluoromethyl in the ^R 1 to R ⁴ More preferably, it contains a group (—CF ₃ group).

M in the general formula (1) represents 0 or 1, and is preferably 1. In the general formula (1), m is 1 and at least three of R ^{1 to} R ⁴ are more preferably fluorine atoms. In the general formula (1), m is 1, three of the R ^{1 to} R ⁴ are fluorine atoms, and one of the R ^{1 to} R ⁴ is a trifluoromethyl group (—CF ₃ groups) is particularly preferable.

When the total content of the structural unit (A), the structural unit (B), and the structural unit (C) in the fluorine-containing cyclic olefin copolymer (P) according to this embodiment is 100 mol%, The content of the structural unit (B) in the fluorine-containing cyclic olefin copolymer (P) according to this embodiment is 20 mol% or more and 40 mol% or less, preferably 20 mol% or more and 35 mol% or less. Preferably they are 20 mol% or more and 33 mol% or less.
When the content of the structural unit (B) is not less than the above lower limit value, the moldability of the fluorine-containing cyclic olefin copolymer (P), the refractive index of the resulting molded body, the Abbe number, the transparency, etc. The heat resistance of the obtained molded body can be further improved while maintaining good optical characteristics. Moreover, when content of the said structural unit (B) is below the said upper limit, a fluorine-containing cyclic olefin type copolymer (P) is maintained, maintaining favorable the heat resistance of the molded object obtained, a refractive index, and an Abbe number. ) Can be made more favorable.
In the present embodiment, the content of the structural unit (B) can be measured by, for example, ¹ H-NMR or ¹³ C-NMR.

(Constitutional unit derived from cyclic olefin (C))
The structural unit (C) according to the present embodiment is a structural unit derived from a cyclic olefin represented by the general formula (2).
As a substituted or unsubstituted alkyl group in R < ⁶ > -R < ⁹ > in the said General formula (2), C1-C30 is preferable, More preferably, it is C1-C20, for example, a methyl group, ethyl, for example. Group, n-propyl group and the like.
Examples of the substituted alkyl group include an aralkyl group, a hydroxyalkyl group (for example, hydroxyethyl group), an alkoxyalkyl group (for example, methoxyethyl group), and the like.
The aralkyl group preferably has 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, and examples thereof include a benzyl group and a p-methoxybenzyl group.
Examples of other substituents of the substituted alkyl group include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), an alkoxy group (for example, a methoxy group, an ethoxy group), and the like.
In the ^R 6 to R ^9, preferably also -COOR ¹⁰ or -OCOR ^{10, R 10} is a substituted or unsubstituted alkyl group. Also, of the -COOR ¹⁰ and -OCOR ^10, towards the -COOR ¹⁰ is preferred. Here, as examples of the substituted or unsubstituted alkyl group in R ¹⁰ may be the same as the examples given in the above R ⁶ to R ^9.

R ^{6 to} R ⁹ are preferably hydrogen atoms.
At least two of R ^{6 to} R ⁹ may be bonded to each other to form a ring structure. The ring structure may be monocyclic or polycyclic. For example, the case where two of R ^{6 to} R ⁹ are bonded to each other to form an alkylene group can be exemplified. More specifically, any of R ⁶ or R ⁷ and any of R ⁸ and R ⁹ can be exemplified. A case where the heels are bonded to each other to form an alkylene group. R ^{6 to} R ⁹ are preferably not bonded to each other to form a ring structure.
In addition, at least one of R ^{6 to} R ⁹ is preferably a hydrogen atom, more preferably at least two are hydrogen atoms, more preferably at least three are hydrogen atoms, and four are hydrogen atoms. It is particularly preferred that

In the general formula (2), n represents 0 or 1 and is preferably 1. Moreover, in the said General formula (2), it is more preferable that n is 1 and at least 3 of said R < ⁶ > -R < ⁹ > is a hydrogen atom. Moreover, in the said General formula (1), it is especially preferable that n is 1 and all of said R < ⁶ > -R < ⁹ > is a hydrogen atom.

When the total content of the structural unit (A), the structural unit (B), and the structural unit (C) in the fluorine-containing cyclic olefin copolymer (P) according to this embodiment is 100 mol%, The content of the structural unit (C) in the fluorine-containing cyclic olefin copolymer (P) according to the present embodiment is 0 mol% or more and 20 mol% or less, preferably 1 mol% or more and 15 mol% or less. Preferably they are 3 mol% or more and 12 mol% or less.
When the content of the structural unit (C) is within the above range, the balance of moldability, refractive index, and Abbe number can be further improved.
In the present embodiment, the content of the structural unit (B) can be measured by, for example, ¹ H-NMR or ¹³ C-NMR.

  The copolymerization type of the fluorine-containing cyclic olefin copolymer (P) according to the present embodiment is not particularly limited, and examples thereof include a random copolymer and a block copolymer. In the present embodiment, the fluorine-containing cyclic olefin copolymer (P) according to the present embodiment from the viewpoint of obtaining a molded article having excellent optical properties such as transparency, Abbe number, refractive index and birefringence. Is preferably a random copolymer.

  In the present embodiment, one type of fluorine-containing cyclic olefin copolymer (P) may be used alone, or two or more types may be used in combination.

  Examples of the fluorine-containing cyclic olefin copolymer (P) according to this embodiment include Japanese Patent Application Laid-Open Nos. 60-168708, 61-120816, 61-115912, and Japanese Patent Application Laid-Open. Appropriate conditions are selected according to methods such as JP-A 61-115916, JP-A 61-271308, JP-A 61-272216, JP-A 62-252406, JP 62-252407, etc. Can be manufactured.

In the fluorine-containing cyclic olefin copolymer (P) according to this embodiment, when an injection-molded sheet having a thickness of 1.0 mm made of the fluorine-containing cyclic olefin copolymer (P) is produced, it conforms to ASTM D542. The refractive index (nd) at a wavelength of 589 nm of the injection molded sheet to be measured is preferably 1.37 or more, more preferably 1.39 or more, further preferably 1.42 or more, and particularly preferably 1.45 or more. Although the upper limit of the said refractive index (nd) is not specifically limited, For example, it is 1.60 or less.
When the refractive index is within the above range, the thickness can be further reduced while maintaining good optical properties of the molded product obtained using the fluorine-containing cyclic olefin copolymer (P) according to the present embodiment. .

  Further, in the fluorine-containing cyclic olefin copolymer (P) according to this embodiment, from the viewpoint of further improving the transparency of the obtained molded product, the thickness 1 made of the fluorine-containing cyclic olefin copolymer (P) is 1 When an injection molded sheet of 0.0 mm is produced, the haze of the injection molded sheet measured in accordance with JIS K7136 is preferably less than 5%.

In addition, in the fluorine-containing cyclic olefin copolymer (P) according to the present embodiment, an injection having a thickness of 1.0 mm made of the fluorine-containing cyclic olefin copolymer (P) from the viewpoint of reducing chromatic aberration of the obtained molded product. When a molded sheet is produced, the Abbe number (ν) of the injection molded sheet is preferably 50 or more, more preferably 55 or more, and still more preferably 58 or more. The upper limit of the Abbe number (ν) is not particularly limited, but is 80 or less, preferably 70 or less, for example.
The Abbe number (ν) of the injection-molded sheet can be calculated from the refractive index of the injection-molded sheet at wavelengths of 486 nm, 589 nm, and 656 nm using the following formula.
v = (nD-1) / (nF-nC)
nD: Refractive index at a wavelength of 589 nm nC: Refractive index at a wavelength of 656 nm nF: Refractive index at a wavelength of 486 nm

Further, in the cyclic olefin copolymer (P) according to this embodiment, from the viewpoint of adjusting the birefringence of the obtained molded product to a more suitable range, the thickness 1 made of the cyclic olefin copolymer (P) is 1. When an injection molded sheet of 0.0 mm is produced, the birefringence of the injection molded sheet is preferably 1 nm or more and 200 nm or less.
In this embodiment, the birefringence of the injection-molded sheet is an average value of a phase difference of 20 to 35 mm from the gate direction measured at a measurement wavelength of 650 nm using a KOBRA CCD manufactured by Oji Scientific Instruments.

  The glass transition temperature (Tg) of the fluorine-containing cyclic olefin copolymer (P) according to this embodiment, measured with a differential scanning calorimeter (DSC), is 100 ° C. or higher and 180 ° C. or lower. While maintaining good optical properties such as transparency, haze, Abbe number, birefringence and refractive index, the balance between the heat resistance of the resulting molded product and the moldability of the fluorine-containing cyclic olefin copolymer (P) is improved. From the viewpoint of improving, it is preferably 120 ° C. or higher and 190 ° C. or lower, more preferably 130 ° C. or higher and 180 ° C. or lower, and further preferably 140 ° C. or higher and 175 ° C. or lower.

  The intrinsic viscosity [η] (in 135 ° C. decalin) of the fluorine-containing cyclic olefin copolymer (P) according to this embodiment is, for example, 0.05 to 5.0 dl / g, preferably 0.2 to 4 0.0 dl / g, more preferably 0.3 to 2.0 dl / g, and particularly preferably 0.4 to 1.0 dl / g.

[Molded body]
The molded body according to the present embodiment is a molded body including the fluorine-containing cyclic olefin copolymer (P) according to the present embodiment.
Since the molded body according to the present embodiment includes the fluorine-containing cyclic olefin copolymer (P) according to the present embodiment, the molded body according to the present embodiment has an excellent balance of transparency, haze, birefringence, chemical resistance, low hygroscopicity, and the like. Furthermore, it has high refractive index, high Abbe number and high heat resistance. Therefore, it is suitable for the use of an optical lens.

  Since the molded article according to the present embodiment has excellent optical characteristics, for example, a spectacle lens, an optical device lens, an optoelectronic lens, a laser lens, a pickup lens, an in-vehicle camera lens, a portable camera lens, and a digital camera It can be suitably used as an optical lens such as a lens, an OHP lens, or a microlens array.

  Further, the content of the fluorine-containing cyclic olefin copolymer (P) in the molded product according to this embodiment further improves the performance balance of transparency, haze, birefringence, heat resistance, Abbe number and refractive index. From the viewpoint, when the entire molded body is 100% by mass, it is preferably 50% by mass or more and 100% by mass or less, more preferably 70% by mass or more and 100% by mass or less, and further preferably 80% by mass or more. It is 100 mass% or less, Most preferably, it is 90 mass% or more and 100 mass% or less.

  The molded body according to the present embodiment can be obtained by molding a resin composition containing a fluorine-containing cyclic olefin copolymer (P) into a predetermined shape. The method for obtaining a molded product by molding a resin composition containing the fluorine-containing cyclic olefin copolymer (P) is not particularly limited, and a known method can be used. Depending on the application and shape, for example, extrusion molding, injection molding, compression molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, vacuum molding, powder slush molding, calendar molding, foam molding, etc. Is applicable. 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.

  The molded body according to the present embodiment can be used in various forms such as a lens shape, a spherical shape, a rod shape, a plate shape, a columnar shape, a tubular shape, a tube shape, a fiber shape, a film shape or a sheet shape.

  If necessary, the molded product according to the present embodiment may contain known additives as optional components within a range that does not impair the good physical properties of the molded product according to the present embodiment. Examples of additives include phenolic stabilizers, higher fatty acid metal salts, antioxidants, UV absorbers, hindered amine light stabilizers, hydrochloric acid absorbers, metal deactivators, antistatic agents, antifogging agents, and lubricants. Further, a slip agent, a nucleating agent, a plasticizer, a flame retardant, a phosphorus stabilizer and the like can be blended to such an extent that the object of the present invention is not impaired, and the blending ratio is an appropriate amount.

The optical lens according to the present embodiment may be combined with an optical lens different from the optical lens to form an optical lens system.
That is, the optical lens system according to the present embodiment includes a first optical lens constituted by a molded body including the fluorine-containing cyclic olefin copolymer (P) according to the present embodiment, and the first optical lens described above. Comprises a different second optical lens.

  Although it does not specifically limit as said 2nd optical lens, For example, the optical lens comprised by at least 1 type of resin selected from polycarbonate resin and polyester resin can be used.

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.

<Production of fluorine-containing cyclic olefin copolymer>
[Production Example 1]
After flowing nitrogen as an inert gas at a flow rate of 50 Nl / hr for 60 minutes in a 500 ml glass reaction vessel equipped with a stirrer, toluene (72 ml) and a fluorine-containing tetracyclododecene derivative represented by the following formula (141 mmol, hereinafter also referred to as F6-TD) was added. Next, the solvent temperature was raised to 25 ° C. while stirring the polymerization solvent at a rotation speed of 600 rpm. After the solvent temperature reaches a predetermined temperature, nitrogen gas is supplied to the reaction vessel at a supply rate of 25 Nl / hr, ethylene is 25 Nl / hr, and hydrogen is 5 Nl / hr. After 10 minutes, PMAO (5 mmol), A toluene solution of FI catalyst (0.02 mmol) was added to a glass reaction vessel to initiate polymerization.
After 10 minutes, 5 ml of isobutyl alcohol was added to terminate the polymerization, and a polymerization solution containing a copolymer of ethylene and F6-TD was obtained. Thereafter, the polymerization solution was diluted with 200 ml of toluene, and added to a beaker having a volume of 2 L containing 4 times acetone / methanol (3/1, volume ratio) of the diluted polymerization solution and 5 ml of hydrochloric acid with stirring to precipitate the copolymer. Further, the precipitated copolymer was separated from the filtrate by filtration. When the polymer containing the obtained solvent was dried under reduced pressure at 130 ° C. for 10 hours, 2.1 g of white powdery ethylene / F6-TD copolymer was obtained.
In this way, a fluorine-containing cyclic olefin copolymer (P-1) was obtained.

[Production Example 2]
After circulating nitrogen as an inert gas at a flow rate of 50 Nl / hr for 60 minutes in a glass reaction vessel having a volume of 500 ml equipped with a stirrer, cyclohexane, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene (0.5 mmol, hereinafter also referred to as tetracyclododecene) and F6-TD (140 mmol) represented by the above formula were added. Next, the solvent temperature was raised to 25 ° C. while stirring the polymerization solvent at a rotation speed of 600 rpm. After the solvent temperature reaches a predetermined temperature, nitrogen 25Nl / hr, ethylene 25Nl / hr, and hydrogen 5Nl / hr are passed through the reaction vessel at a feed rate of 10 N. After 10 minutes, PMAO (5 mmol), FI catalyst Of toluene (0.02 mmol) was added to a glass reaction vessel to initiate polymerization.
After 10 minutes, 5 ml of isobutyl alcohol was added to terminate the polymerization, and a polymerization solution containing a copolymer of ethylene, tetracyclododecene and F6-TD was obtained. Thereafter, the polymerization solution was diluted with 200 ml of toluene, and added to a beaker having a volume of 2 L containing 4 times acetone / methanol (3/1, volume ratio) of the diluted polymerization solution and 5 ml of hydrochloric acid with stirring to precipitate the copolymer. Further, the precipitated copolymer was separated from the filtrate by filtration. When the polymer containing the obtained solvent was dried under reduced pressure at 130 ° C. for 10 hours, 2.6 g of white powdery ethylene / tetracyclododecene / F6-TD copolymer was obtained.
Thus, a fluorine-containing cyclic olefin copolymer (P-2) was obtained.

[Production Example 3]
Nitrogen was passed as an inert gas at a flow rate of 50 Nl / hr for 60 minutes in a 500 ml glass reaction vessel equipped with a stirrer, and then cyclohexane and F6-TD (70.8 mmol) represented by the following formula were added. It was. Next, the solvent temperature was raised to 25 ° C. while stirring the polymerization solvent at a rotation speed of 600 rpm. After the solvent temperature reaches a predetermined temperature, nitrogen 25Nl / hr, ethylene 25Nl / hr, and hydrogen 5Nl / hr are passed through the reaction vessel at a feed rate of 10 N. After 10 minutes, PMAO (5 mmol), FI catalyst A toluene solution (0.004 mmol) was added to a glass reaction vessel to initiate polymerization.
After 10 minutes, 5 ml of isobutyl alcohol was added to terminate the polymerization, and a polymerization solution containing a copolymer of ethylene and F6-TD was obtained. Thereafter, the polymerization solution was diluted with 200 ml of toluene, and added to a beaker having a volume of 2 L containing 4 times acetone / methanol (3/1, volume ratio) of the diluted polymerization solution and 5 ml of hydrochloric acid with stirring to precipitate the copolymer. Further, the precipitated copolymer was separated from the filtrate by filtration. When the polymer containing the obtained solvent was dried under reduced pressure at 130 ° C. for 10 hours, 2.8 g of a white powdery ethylene / F6-TD copolymer was obtained.
As described above, a fluorine-containing cyclic olefin copolymer (P-3) was obtained.

[Production Example 4]
Under a nitrogen atmosphere, 0.1 mmol of palladium bisacetylacetonate and 0.11 mmol of tricyclohexylphosphine were dissolved in 5 mL of toluene and stirred at room temperature for 10 minutes to prepare a catalyst solution. Under a nitrogen atmosphere, 20 ml of toluene and 10 mmol of F6-TD were added to a 100 ml glass eggplant flask equipped with a stirring bar. While stirring with a magnetic stirrer, the catalyst solution was added and reacted at 80 ° C. for 3 hours. The solution after the reaction was diluted with 300 ml of toluene, and slowly added with stirring to a 2 L beaker containing 1200 ml of acetone to precipitate a polymer, and the precipitated polymer was separated from the filtrate by filtration. The polymer containing the obtained solvent was dried under reduced pressure at 130 ° C. for 10 hours to obtain 2.5 g of a fine gray powdery F6-TD addition polymer.

<Examples 1-2 and Comparative Examples 1-2>
In each Example and Comparative Example, various physical properties were measured or evaluated by the following methods. The obtained results are shown in Table 1, respectively.

[Method for measuring the content of each structural unit constituting the fluorine-containing cyclic olefin copolymer]
The contents of ethylene, F6-TD and tetracyclododecene were measured by using the “ECA500 type” nuclear magnetic resonance apparatus manufactured by JEOL Ltd. under the following conditions.
Solvent: Heavy tetrachloroethane Sample concentration: 50-100 g / l-solvent
Pulse repetition time: 5.5 seconds Integration count: 6000 to 16000 times Measurement temperature: 120 ° C
The compositions of ethylene, F6-TD, and tetracyclododecene were quantified by ¹³ C-NMR spectrum measured under the above conditions.

[Glass transition temperature Tg (° C)]
The glass transition temperature Tg of the fluorine-containing cyclic olefin copolymer was measured under a N ₂ (nitrogen) atmosphere using Shimadzu Science Co., Ltd., DSC-6220. The fluorine-containing cyclic olefin copolymer is heated from room temperature to 200 ° C. at a temperature rising rate of 10 ° C./min, held for 5 minutes, and then cooled to −20 ° C. at a temperature lowering rate of 10 ° C./min for 5 minutes. Retained. And the glass transition point (Tg) of the fluorine-containing cyclic olefin copolymer was calculated | required from the endothermic curve at the time of heating up to 200 degreeC with the temperature increase rate of 10 degreeC / min. In Comparative Example 2, the temperature was raised to 400 ° C., but the glass transition point (Tg) was not detected.

[Intrinsic viscosity [η]]
A sample obtained by dissolving 0.25 to 0.30 g of a fluorine-containing cyclic olefin-based copolymer in 25 ml of decalin using a moving viscometer (manufactured by Kosei Co., Ltd., type VNR053U type) was used. The specific viscosity of the fluorine-containing cyclic olefin copolymer is measured at 135 ° C. in accordance with ASTM J1601, and the ratio of this to the concentration is extrapolated to a concentration of 0 to limit the intrinsic viscosity [η] of the fluorine-containing cyclic olefin copolymer. Asked. Comparative Example 2 was not measurable because it was insoluble in decalin.

[Formability evaluation]
The moldability of the fluorine-containing cyclic olefin-based (co) polymer synthesized in Production Examples 1 to 4 was evaluated according to the following criteria.
○: Can be molded with a micro compounder ×: Could not be molded because it did not melt

[Microcompound molding]
Example 1
The fluorine-containing cyclic olefin-based copolymer synthesized in Production Example 1 was kneaded for 5 minutes at a kneading temperature = 300 ° C. and 50 rpm using a small kneader manufactured by Xplore Instruments, and then an injection molding machine manufactured by Xplor Instruments was used. The injection molding was performed under the conditions of cylinder temperature = 300 ° C., injection pressure = 12 to 15 bar, and mold temperature 135 ° C. to produce an injection molded sheet having a thickness of 1.0 mm.

(Example 2)
The fluorine-containing cyclic olefin copolymer synthesized in Production Example 2 was used in place of the fluorine-containing cyclic olefin copolymer synthesized in Production Example 1, except that the kneading temperature was 280 ° C. and the cylinder temperature was 280 ° C. In the same manner as in Example 1, an injection molded sheet having a thickness of 1.0 mm was produced.

(Comparative Example 1)
Example 2 except that the fluorine-containing cyclic olefin copolymer synthesized in Production Example 3 was used instead of the fluorine-containing cyclic olefin copolymer synthesized in Production Example 2, and the mold temperature was changed to 80 ° C. Similarly, an injection molded sheet having a thickness of 1.0 mm was produced.

(Comparative Example 2)
An attempt was made to mold the fluorine-containing cyclic olefin addition polymer synthesized in Production Example 4, but it could not be molded because it did not melt even at 350 ° C. or higher.

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

[Abbe number (ν)]
Using an Abbe refractometer, the refractive index of wavelengths 486 nm, 589 nm, and 656 nm at 23 ° C. was measured for an injection molded sheet 30 mm × 30 mm × thickness 1.0 mm molded with a micro compounder, and further using the following formula: The Abbe number (ν) was calculated.
v = (nD-1) / (nF-nC)
nD: Refractive index at a wavelength of 589 nm nC: Refractive index at a wavelength of 656 nm nF: Refractive index at a wavelength of 486 nm

  As described above, the fluorine-containing cyclic olefin copolymers of the examples were excellent in moldability, and it was possible to obtain molded articles having a high refractive index, a high Abbe number, and high heat resistance. On the other hand, the fluorine-containing cyclic olefin copolymer of the comparative example was inferior in the balance of moldability, refractive index, Abbe number, and heat resistance.

Claims (8)

A structural unit (A) derived from an α-olefin having 2 to 10 carbon atoms;
A structural unit (B) derived from a fluorine-containing cyclic olefin represented by the following general formula (1);
A structural unit (C) derived from a cyclic olefin represented by the following general formula (2);
A fluorine-containing cyclic olefin copolymer having
When the total content of the structural unit (A), the structural unit (B) and the structural unit (C) in the fluorine-containing cyclic olefin copolymer is 100 mol%,
The content of the structural unit (A) in the fluorine-containing cyclic olefin copolymer is 40 mol% or more and 80 mol% or less,
The content of the structural unit (B) in the fluorine-containing cyclic olefin copolymer is 20 mol% or more and 40 mol% or less,
The content of the structural unit (C) in the fluorine-containing cyclic olefin copolymer is 0 mol% or more and 20 mol% or less,
A fluorine-containing cyclic olefin copolymer having a glass transition temperature (Tg) of 100 ° C. or higher and 180 ° C. or lower as measured with a differential scanning calorimeter (DSC).

(In the general formula (1), R ^{1 to} R ⁴ are each independently a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group, an alkyl group containing a fluorine atom, an alkoxy group containing a fluorine atom, or a fluorine atom. Represents an ether group-containing alkyl group containing or a substituent represented by —COOR ⁵ or —OCOR ⁵ , and at least two of R ^{1 to} R ⁴ may be bonded to each other to form a ring structure. R ⁵ is a substituted or unsubstituted alkyl group or an alkyl group containing a fluorine atom, and at least one fluorine atom is contained in R ^{1 to} R ⁴ , m represents 0 or 1)

(In the general formula ^(2), each of R 6 to R ⁹ independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituent represented by -COOR ¹⁰ or -OCOR ^{10, R} 6 ~ At least two of R ⁹ may be bonded to each other to form a ring structure, R ¹⁰ is a substituted or unsubstituted alkyl group, and n represents 0 or 1.) In the fluorine-containing cyclic olefin copolymer according to claim 1,
A fluorine-containing cyclic olefin copolymer in which m is 1 in the general formula (1). In the fluorine-containing cyclic olefin copolymer according to claim 1 or 2,
A fluorine-containing cyclic olefin copolymer in which the α-olefin contains ethylene. In the fluorine-containing cyclic olefin copolymer according to any one of claims 1 to 3,
A fluorine-containing cyclic olefin copolymer in which m is 1 in the general formula (1) and at least three of R ^{1 to} R ⁴ are fluorine atoms. In the fluorine-containing cyclic olefin copolymer according to any one of claims 1 to 4,
A fluorine-containing cyclic olefin copolymer having an Abbe number (ν) of 50 or more when the injection-molded sheet having a thickness of 1.0 mm made of the fluorine-containing cyclic olefin copolymer is prepared. In the fluorine-containing cyclic olefin copolymer according to any one of claims 1 to 5,
When an injection-molded sheet having a thickness of 1.0 mm made of the fluorine-containing cyclic olefin copolymer is prepared, the refractive index (nd) at a wavelength of 589 nm of the injection-molded sheet measured according to ASTM D542 is 1.37. The fluorine-containing cyclic olefin copolymer as described above.   The molded object containing the fluorine-containing cyclic olefin type copolymer as described in any one of Claims 1 thru | or 6.   The molded article according to claim 7, which is an optical lens.