JPH0680864A - Thermoplastic saturated norbornene-based resin composition, optical material, medical equipment material and electrical insulating material composed thereof - Google Patents
Thermoplastic saturated norbornene-based resin composition, optical material, medical equipment material and electrical insulating material composed thereofInfo
- Publication number
- JPH0680864A JPH0680864A JP25737292A JP25737292A JPH0680864A JP H0680864 A JPH0680864 A JP H0680864A JP 25737292 A JP25737292 A JP 25737292A JP 25737292 A JP25737292 A JP 25737292A JP H0680864 A JPH0680864 A JP H0680864A
- Authority
- JP
- Japan
- Prior art keywords
- norbornene
- fluorophosphonite
- thermoplastic saturated
- saturated norbornene
- based resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、耐候性に優れた熱可塑
性飽和ノルボルネン系樹脂組成物、それから成る光学材
料、医療用器材、及び電気絶縁材料に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic saturated norbornene resin composition having excellent weather resistance, an optical material comprising the same, a medical device, and an electric insulating material.
【０００２】[0002]
【従来の技術】従来から光学材料に用いられる樹脂とし
てポリメチルメタクリレート（ＰＭＭＡ）やポリカーボ
ネート（ＰＣ）が知られている。しかし、ＰＭＭＡは透
明性に優れているが、耐熱性、耐湿性などの点で問題が
あり、また、ＰＣは耐熱性、耐湿性はＰＭＭＡよりも優
れているが、複屈折が大きいなどの問題があり、透明
性、耐熱性、耐湿性、低複屈折性などの全てに優れた光
学材料が求められていた。2. Description of the Related Art Polymethyl methacrylate (PMMA) and polycarbonate (PC) have been conventionally known as resins used for optical materials. However, PMMA is excellent in transparency, but has problems in heat resistance and humidity resistance. In addition, PC is superior in heat resistance and humidity resistance to PMMA, but has a large birefringence. Therefore, an optical material excellent in transparency, heat resistance, moisture resistance, low birefringence, etc. has been demanded.
【０００３】近時、熱可塑性飽和ノルボルネン系樹脂は
透明性、耐熱性、耐湿性、低複屈折性に優れた光学材料
として注目されている。Recently, thermoplastic saturated norbornene resins have attracted attention as optical materials excellent in transparency, heat resistance, moisture resistance and low birefringence.
【０００４】熱可塑性飽和ノルボルネン系樹脂を光学材
料として、実際に使用するために、通常、種々の添加剤
を添加して熱可塑性飽和ノルボルネン系樹脂組成物とし
て用いる。例えば、熱安定性を得るため、有機ホスファ
イト系酸化防止剤を添加する（特開平２−２６９７６０
号、特開平２−２７６８４２号）、耐候性を向上させる
ために、ヒンダードアミン系耐光安定剤や紫外線吸収剤
を添加する（特開平４−１５４８６２号）などして用い
られている。In order to actually use the thermoplastic saturated norbornene-based resin as an optical material, various additives are usually added and used as the thermoplastic saturated norbornene-based resin composition. For example, in order to obtain thermal stability, an organic phosphite-based antioxidant is added (JP-A-2-269760).
JP-A-2-276842), and a hindered amine light stabilizer and an ultraviolet absorber are added to improve weather resistance (JP-A-4-1544862).
【０００５】しかし、有機ホスファイト系酸化防止剤は
加水分解しやすいため、保存が困難であり、有機ホスフ
ァイト系酸化防止剤を添加した熱可塑性飽和ノルボルネ
ン系樹脂のペレットや成形品の表面で加水分解して、耐
湿性を低下させるという問題があった。また、熱可塑性
飽和ノルボルネン系樹脂に紫外線吸収剤を添加すると、
耐候性は向上するが、樹脂に黄色の着色が認められ、使
用上、問題となる。However, since the organic phosphite antioxidant is easily hydrolyzed, it is difficult to store it, and the surface of the pellet or the molded article of the thermoplastic saturated norbornene resin containing the organic phosphite antioxidant is hydrolyzed. There is a problem that it decomposes to reduce the moisture resistance. Moreover, when an ultraviolet absorber is added to the thermoplastic saturated norbornene-based resin,
Although the weather resistance is improved, yellow coloring is recognized in the resin, which causes a problem in use.
【０００６】一般に、耐候性を向上させるため、熱可塑
性飽和ノルボルネン系樹脂にヒンダードアミン系耐光安
定剤を添加することが多いが、耐候性が不十分であった
り、酸化防止剤や紫外線吸収剤と併用すると白濁しやす
いなどの問題があった。Generally, in order to improve weather resistance, a hindered amine light stabilizer is often added to a thermoplastic saturated norbornene resin, but the weather resistance is insufficient, or it is used in combination with an antioxidant or an ultraviolet absorber. Then, there was a problem that it became cloudy.
【０００７】[0007]
【発明が解決しようとする課題】本発明者らは、熱可塑
性飽和ノルボルネン系樹脂の耐候性の向上を目的に鋭意
研究の結果、熱可塑性飽和ノルボルネン系樹脂にフルオ
ロホスフォナイト系酸化防止剤を添加すれば、耐候性が
向上することを見いだし、本発明を完成させるに到っ
た。DISCLOSURE OF INVENTION Problems to be Solved by the Invention As a result of intensive research aimed at improving the weather resistance of a thermoplastic saturated norbornene resin, the present inventors have found that a fluorophosphonite antioxidant is added to a thermoplastic saturated norbornene resin. We have found that the addition of these elements improves the weather resistance, and have completed the present invention.
【０００８】[0008]
【課題を解決するための手段】かくして本発明によれ
ば、熱可塑性飽和ノルボルネン系樹脂１００重量部に対
して、フルオロホスフォナイト系酸化防止剤０．０１〜
５重量部を添加してなる熱可塑性飽和ノルボルネン系樹
脂組成物が提供される。Thus, according to the present invention, 0.01 to 100 parts by weight of the fluorosaturated thermoplastic norbornene-based resin is added with 0.01 to 100 parts by weight of the fluorophosphonite-based antioxidant.
A thermoplastic saturated norbornene-based resin composition obtained by adding 5 parts by weight is provided.
【０００９】（熱可塑性飽和ノルボルネン系樹脂）本発
明で用いる熱可塑性飽和ノルボルネン系樹脂は、特開平
３−１４８８２号や特開平３−１２２１３７号、特開平
４−６３８０７号などで公知の樹脂であり、具体的に
は、ノルボルネン系単量体の開環重合体水素添加物、ノ
ルボルネン系単量体の付加型重合体、ノルボルネン系単
量体とオレフィンの付加型重合体、これらの重合体の変
性物などが挙げられる。(Thermoplastic Saturated Norbornene Resin) The thermoplastic saturated norbornene resin used in the present invention is a resin known in JP-A-3-14882, JP-A-3-122137 and JP-A-4-63807. , Specifically, ring-opening polymer hydrogenated products of norbornene-based monomers, addition-type polymers of norbornene-based monomers, addition-type polymers of norbornene-based monomers and olefins, modification of these polymers The thing etc. are mentioned.
【００１０】ノルボルネン系単量体も、上記公報や特開
平２−２２７４２４号、特開平２−２７６８４２号など
で公知の単量体であって、例えば、ノルボルネン、その
アルキル、アルキリデン、芳香族置換誘導体およびこれ
ら置換または非置換のオレフィンのハロゲン、水酸基、
エステル基、アルコキシ基、シアノ基、アミド基、イミ
ド基、シリル基等の極性基置換体、例えば、２−ノルボ
ルネン、５−メチル−２−ノルボルネン、５，５−ジメ
チル−２−ノルボルネン、５−エチル−２−ノルボルネ
ン、５−ブチル−２−ノルボルネン、５−エチリデン−
２−ノルボルネン、５−メトキシカルボニル−２−ノル
ボルネン、５−シアノ−２−ノルボルネン、５−メチル
−５−メトキシカルボニル−２−ノルボルネン、５−フ
ェニル−２−ノルボルネン、５−フェニル−５−メチル
−２−ノルボルネン、５−ヘキシル−２−ノルボルネ
ン、５−オクチル−２−ノルボルネン、５−オクタデシ
ル−２−ノルボルネン等；ノルボルネンに一つ以上のシ
クロペンタジエンが付加した単量体、その上記と同様の
誘導体や置換体、例えば、１，４：５，８−ジメタノ−
１，２，３，４，４ａ，５，８，８ａ−２，３−シクロ
ペンタジエノナフタレン、６−メチル−１，４：５，８
−ジメタノ−１，４，４ａ，５，６，７，８，８ａ−オ
クタヒドロナフタレン、１，４：５，１０：６，９−ト
リメタノ−１，２，３，４，４ａ，５，５ａ，６，９，
９ａ，１０，１０ａ−ドデカヒドロ−２，３−シクロペ
ンタジエノアントラセン等；シクロペンタジエンの多量
体である多環構造の単量体、その上記と同様の誘導体や
置換体、例えば、ジシクロペンタジエン、２，３−ジヒ
ドロジシクロペンタジエン等；シクロペンタジエンとテ
トラヒドロインデン等との付加物、その上記と同様の誘
導体や置換体、例えば、１，４−メタノ−１，４，４
ａ，４ｂ，５，８，８ａ，９ａ−オクタヒドロフルオレ
ン、５，８−メタノ−１，２，３，４，４ａ，５，８，
８ａ−オクタヒドロ−２，３−シクロペンタジエノナフ
タレン等；等が挙げられる。The norbornene-based monomer is also a monomer known in the above publications, JP-A-2-227424 and JP-A-2-276842, and examples thereof include norbornene, its alkyl, alkylidene, and aromatic substituted derivatives. And halogens, hydroxyl groups of these substituted or unsubstituted olefins,
Polar group substituents such as ester group, alkoxy group, cyano group, amide group, imide group and silyl group, for example, 2-norbornene, 5-methyl-2-norbornene, 5,5-dimethyl-2-norbornene, 5- Ethyl-2-norbornene, 5-butyl-2-norbornene, 5-ethylidene-
2-norbornene, 5-methoxycarbonyl-2-norbornene, 5-cyano-2-norbornene, 5-methyl-5-methoxycarbonyl-2-norbornene, 5-phenyl-2-norbornene, 5-phenyl-5-methyl- 2-norbornene, 5-hexyl-2-norbornene, 5-octyl-2-norbornene, 5-octadecyl-2-norbornene and the like; a monomer in which one or more cyclopentadiene is added to norbornene, a derivative similar to the above Or a substitution product, for example, 1,4: 5,8-dimethano-
1,2,3,4,4a, 5,8,8a-2,3-cyclopentadienonaphthalene, 6-methyl-1,4: 5,8
-Dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, 1,4: 5,10: 6,9-trimethano-1,2,3,4,4a, 5,5a , 6, 9,
9a, 10,10a-dodecahydro-2,3-cyclopentadienoanthracene, etc .; a polycyclic monomer which is a multimer of cyclopentadiene, a derivative or substituent similar to the above, for example, dicyclopentadiene, 2,3-dihydrodicyclopentadiene and the like; addition products of cyclopentadiene and tetrahydroindene and the like, derivatives and substitution products similar to the above, for example, 1,4-methano-1,4,4
a, 4b, 5,8,8a, 9a-octahydrofluorene, 5,8-methano-1,2,3,4,4a, 5,8,
8a-octahydro-2,3-cyclopentadienonaphthalene and the like; and the like.
【００１１】ノルボルネン系単量体の重合は公知の方法
でよく、必要に応じて、他の共重合可能な単量体と共重
合したり、水素添加することにより熱可塑性飽和ノルボ
ルネン系樹脂である熱可塑性ノルボルネン系重合体水素
添加物とすることができる。また、重合体や重合体水素
添加物を特開平３−９５２３５号などで公知の方法によ
り、α，β−不飽和カルボン酸および／またはその誘導
体、スチレン系炭化水素、オレフィン系不飽和結合およ
び加水分解可能な基を持つ有機ケイ素化合物、不飽和エ
ポキシ単量体を用いて変性させてもよい。The norbornene-based monomer may be polymerized by a known method. If necessary, the norbornene-based monomer may be copolymerized with another copolymerizable monomer or may be hydrogenated to obtain a thermoplastic saturated norbornene-based resin. It can be a thermoplastic norbornene-based polymer hydrogenated product. Further, a polymer or a polymer hydrogenated product is subjected to a method known in JP-A-3-95235 or the like to obtain an α, β-unsaturated carboxylic acid and / or a derivative thereof, a styrene-based hydrocarbon, an olefin-based unsaturated bond and a hydrolyzed product. It may be modified by using an organosilicon compound having a decomposable group or an unsaturated epoxy monomer.
【００１２】分子量はシクロヘキサンを溶媒とするＧＰ
Ｃ（ゲル・パーミエション・クロマトグラフィー）分析
により測定した数平均分子量で１〜２０万が適当であ
る。また、水素添加する場合、耐候性を向上させるため
に、水素添加率は９０％以上、好ましくは９５％以上、
より好ましくは９９％以上である。The molecular weight is GP using cyclohexane as a solvent.
The number average molecular weight measured by C (gel permeation chromatography) analysis is suitably from 1 to 200,000. When hydrogenated, the hydrogenation rate is 90% or more, preferably 95% or more, in order to improve weather resistance.
More preferably, it is 99% or more.
【００１３】（フルオロホスフォナイト系酸化防止剤）
本発明で熱可塑性飽和ノルボルネン系樹脂組成物に添加
するフルオロホスフォナイト系酸化防止剤は、一般式(Fluorophosphonite antioxidant)
In the present invention, the fluorophosphonite-based antioxidant added to the thermoplastic saturated norbornene-based resin composition has the general formula
【化１】 で表される酸化防止剤である。式中のＲ1、Ｒ2は、同一
または異なる炭化水素基または置換炭化水素基であり、
直鎖構造のもの、分岐構造を有するもの、または環構造
を有するものでもよく、例えば、プロピル基、ブチル
基、ペンチル基などの脂肪族基； シクロヘキシル基、
シクロオクチル基などの脂環族基； フェニル基、ｔ−
ブチルフェニル基、プロピルフェニル基などの芳香族
基； これらの構造の一部が置換されたものが挙げら
れ、環構造を有するものが好ましく、特に芳香族基が好
ましい。また、Ｒ1、Ｒ2の二つの芳香族基が、アルキレ
ン基などを介して環を形成している場合に、特に熱可塑
性飽和ノルボルネン系樹脂組成物に耐候性を付与するの
で好ましい。フルオロホスフォナイト系酸化防止剤とし
て、具体的には、ジフェニルフルオロホスフォナイト、
フェニル（２−ブチルフェニル）フルオロホスフォナイ
ト、ジ−２−プロピルフェニルフルオロホスフォナイ
ト、ジ−２，４−ジ−ｔ−ブチルフェニルフルオロホス
フォナイト、２，２’−エチリデンビス（ブチルフェニ
ル）フルオロホスフォナイト、２，２’−プロピリデン
ビス（４−プロピルフェニル）フルオロホスフォナイ
ト、２，２’−エチリデンビス（４−ｔ−ブチルフェニ
ル）フルオロホスフォナイト、２，２’−エチリデンビ
ス（４，６−ジ−ｔ−ブチルフェニル）フルオロホスフ
ォナイト、２，２’−エチリデン−フェニル（４，６−
ジ−ｔ−ブチルフェニル）フルオロホスフォナイト、
２，２’−プロピリデンビス（４，６−ジ−ｔ−ブチル
フェニル）フルオロホスフォナイトが挙げられ、２，
２’−エチリデンビス（４，６−ジ−ｔ−ブチルフェニ
ル）フルオロホスフォナイトが市販されている。[Chemical 1] It is an antioxidant represented by. R 1 and R 2 in the formula are the same or different hydrocarbon groups or substituted hydrocarbon groups,
It may have a linear structure, a branched structure, or a cyclic structure, and examples thereof include an aliphatic group such as a propyl group, a butyl group, a pentyl group; a cyclohexyl group,
Alicyclic group such as cyclooctyl group; phenyl group, t-
Aromatic groups such as butylphenyl group and propylphenyl group; those in which a part of these structures are substituted are preferable, those having a ring structure are preferable, and aromatic groups are particularly preferable. Further, when two aromatic groups of R 1 and R 2 form a ring via an alkylene group or the like, it is preferable because it imparts weather resistance to the thermoplastic saturated norbornene-based resin composition. As the fluorophosphonite-based antioxidant, specifically, diphenylfluorophosphonite,
Phenyl (2-butylphenyl) fluorophosphonite, di-2-propylphenylfluorophosphonite, di-2,4-di-t-butylphenylfluorophosphonite, 2,2'-ethylidenebis (butylphenyl) ) Fluorophosphonite, 2,2'-propylidenebis (4-propylphenyl) fluorophosphonite, 2,2'-ethylidenebis (4-t-butylphenyl) fluorophosphonite, 2,2'-ethylidenebis (4,6-di-t-butylphenyl) fluorophosphonite, 2,2′-ethylidene-phenyl (4,6-
Di-t-butylphenyl) fluorophosphonite,
2,2'-propylidene bis (4,6-di-t-butylphenyl) fluorophosphonite,
2'-Ethylidene bis (4,6-di-t-butylphenyl) fluorophosphonite is commercially available.
【００１４】（熱可塑性飽和ノルボルネン系樹脂組成
物）本発明の熱可塑性飽和ノルボルネン系樹脂組成物
は、熱可塑性飽和ノルボルネン系樹脂１００重量部に対
して、フルオロホスフォナイト系酸化防止剤０．０１〜
５重量部、好ましくは０．０２〜１重量部、より好まし
くは０．０３〜０．５重量部添加してなる。フルオロホ
スフォナイト系酸化防止剤の添加量が多すぎると、シル
バーストリークが発生しやすく、少なすぎると、耐候性
が不十分となる。(Thermoplastic Saturated Norbornene Resin Composition) The thermoplastic saturated norbornene resin composition of the present invention comprises 0.01 parts by weight of fluorophosphonite antioxidant per 100 parts by weight of the thermoplastic saturated norbornene resin. ~
5 parts by weight, preferably 0.02 to 1 part by weight, more preferably 0.03 to 0.5 part by weight. If the addition amount of the fluorophosphonite-based antioxidant is too large, silver streak is likely to occur, and if it is too small, the weather resistance becomes insufficient.
【００１５】（添加物）さらに、本発明の熱可塑性飽和
ノルボルネン系樹脂組成物には、所望により、フェノー
ル系や有機ホスファイト系などの酸化防止剤； アミン
系などの帯電防止剤； 脂肪族アルコールのエステル、
多価アルコールの部分エステル及び部分エーテルなどの
滑剤； ベンゾフェノン系、ベンゾトリアゾール系など
の紫外線吸収剤； ヒンダードアミン系などの耐光安定
剤； などの各種添加剤を添加してもよく、また、本発
明の目的を損なわない範囲で、他の樹脂などを混合して
用いることもできる。本発明の熱可塑性飽和ノルボルネ
ン系樹脂組成物においては、酸化防止剤とヒンダードア
ミン系耐光安定剤などを併用しても白濁しにくい。透明
性を必要としない成形品であれば、強度等を改良するこ
とを目的として、各種のフィラーを用いることもでき
る。(Additives) Further, in the thermoplastic saturated norbornene-based resin composition of the present invention, if desired, an antioxidant such as phenol-based or organic phosphite-based; an antistatic agent such as amine-based; aliphatic alcohol The ester of
Various additives such as lubricants such as partial esters and partial ethers of polyhydric alcohols; UV absorbers such as benzophenone-based and benzotriazole-based; light-resistant stabilizers such as hindered amine-based; and the like of the present invention may also be added. Other resins may be mixed and used as long as the purpose is not impaired. In the thermoplastic saturated norbornene-based resin composition of the present invention, even if an antioxidant and a hindered amine-based light stabilizer are used in combination, clouding is unlikely to occur. As long as the molded product does not require transparency, various fillers can be used for the purpose of improving strength and the like.
【００１６】本発明の熱可塑性飽和ノルボルネン系樹脂
組成物を成形する方法は、特に限定されない。射出成
形、溶融押し出し、熱プレス、溶剤キャスト、延伸な
ど、熱可塑性樹脂の一般の成形方法を用いることがで
き、光学材料として光学レンズ、光ディスク、光ファイ
バー、光学シート、光学フィルム等をはじめ、電子部品
材料として電子部品等の封止材などの電気絶縁材料等
を、機械部品材料として自動車部品等を、医療器材用材
料として薬品ビンやシリンジ等を成形することができ
る。The method for molding the thermoplastic saturated norbornene resin composition of the present invention is not particularly limited. General thermoplastic resin molding methods such as injection molding, melt extrusion, heat pressing, solvent casting, and stretching can be used, and optical parts such as optical lenses, optical disks, optical fibers, optical sheets, optical films, and electronic parts can be used as optical materials. Electrically insulating materials such as sealing materials for electronic parts, etc. can be molded as materials, automobile parts, etc. can be molded as machine parts materials, and chemical bottles, syringes, etc. can be molded as materials for medical equipment.
【００１７】[0017]
【発明の効果】本発明の熱可塑性飽和ノルボルネン系樹
脂組成物は、熱可塑性飽和ノルボルネン系樹脂からなる
ので、耐熱性、耐湿性、透明性、耐薬品性、電気絶縁性
などに優れ、さらに、耐候性に優れる。Since the thermoplastic saturated norbornene-based resin composition of the present invention is composed of the thermoplastic saturated norbornene-based resin, it is excellent in heat resistance, moisture resistance, transparency, chemical resistance, electrical insulation and the like. Excellent weather resistance.
【００１８】[0018]
【実施例】以下に実施例、及び比較例を挙げて本発明を
さらに具体的に説明する。EXAMPLES The present invention will be described more specifically with reference to Examples and Comparative Examples below.
【００１９】実施例１ ＺＥＯＮＥＸ ２８０（熱可塑性飽和ノルボルネン系樹
脂、日本ゼオン株式会社製、Ｔｇ１４０℃、数平均分子
量約２８０００）１００重量部にフルオロホスフォナイ
ト系酸化防止剤（２，２’−エチリデンビス（４，６−
ジ−ｔ−ブチルフェニル）フルオロホスフォナイト（Ｅ
ｔｈｙｌ Ｃｏｒｐｏｒａｔｉｏｎ製、Ｅｔｈａｎｏｘ
３９８）０．２重量部を添加して、二軸押し出し機を
用いて、２００℃で混練してペレットとした。Example 1 100 parts by weight of ZEONEX 280 (thermoplastic saturated norbornene resin, manufactured by Nippon Zeon Co., Ltd., Tg 140 ° C., number average molecular weight of about 28,000) was added to 100 parts by weight of a fluorophosphonite antioxidant (2,2′-ethylidene). Screw (4,6-
Di-t-butylphenyl) fluorophosphonite (E
Ethanolx, manufactured by tyl Corporation
398) 0.2 part by weight was added, and the mixture was kneaded at 200 ° C. using a twin-screw extruder to obtain pellets.
【００２０】このペレットを用いて、シリンダー温度２
７０℃、金型温度７０℃で射出成形し、厚さ３ｍｍのプ
レートを作製した。Using this pellet, a cylinder temperature of 2
Injection molding was performed at 70 ° C. and a mold temperature of 70 ° C. to prepare a plate having a thickness of 3 mm.
【００２１】このプレートを、紫外線フェードメータ
（スガイ試験機製、ＦＡＬ−３型）を用いて、ブラック
パネル温度６３℃でプレートに紫外線を２４０時間照射
し、紫外線照射前と２４０時間照射の４００ｎｍの光線
透過率を、紫外可視分光光度計で測定した。紫外線照射
前の光線透過率は８８．８％で、紫外線照射後の光線透
過率は８５．７％であった。The plate was irradiated with ultraviolet rays for 240 hours at a black panel temperature of 63 ° C. by using an ultraviolet fade meter (Fal-3 type manufactured by Sugai Tester Co., Ltd.). The transmittance was measured with an ultraviolet-visible spectrophotometer. The light transmittance before irradiation with ultraviolet rays was 88.8%, and the light transmittance after irradiation with ultraviolet rays was 85.7%.
【００２２】比較例１ ＺＥＯＮＥＸ ２８０にフルオロホスフォナイト系酸化
防止剤を添加しないこと以外は実施例１と同様にして、
プレートを作製し、２４０時間の紫外線照射を行った。COMPARATIVE EXAMPLE 1 ZEONEX 280 was prepared in the same manner as in Example 1 except that no fluorophosphonite antioxidant was added.
A plate was prepared and irradiated with ultraviolet rays for 240 hours.
【００２３】紫外線照射前の光線透過率は８９．０％、
紫外線照射後の光線透過率は７９．０％であった。The light transmittance before ultraviolet irradiation is 89.0%,
The light transmittance after irradiation with ultraviolet rays was 79.0%.
【００２４】実施例２ ＺＥＯＮＥＸ ２８０ １００重量部にフルオロホスフ
ォナイト系酸化防止剤（２，２’−エチリデンビス
（４，６−ジ−ｔ−ブチルフェニル）フルオロホスフォ
ナイト）０．２重量部、ヒンダードアミン系耐光安定剤
（テトラキス（２，２，６，６−テトラメチル−４−ピ
ペリジル）−１，２，３，４−ブタンテトラカルボキシ
レート、旭電化工業製、アデカスタブＬＡ−５２、分子
量８４７）０．２重量部、紫外線吸収剤（２−（２’−
ヒドロキシ−５’−ｔ−オクチルフェニル）ベンゾトリ
アゾール、シプロ化成製，シーソーブ７０９）０．０５
重量部、オクタデシル−３−（３，５−ジ−ｔ−ブチル
−４−ヒドロキシフェニル）プロピオネート、日本チバ
ガイギー製、ＩＲＧＡＮＯＸ１０７６）０．１重量部を
添加して、二軸押し出し機を用いて、２００℃で混練し
てペレットとした。Example 2 100 parts by weight of ZEONEX 280 and 0.2 part by weight of a fluorophosphonite-based antioxidant (2,2'-ethylidene bis (4,6-di-t-butylphenyl) fluorophosphonite). , Hindered amine light stabilizer (tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, manufactured by Asahi Denka Co., Ltd., ADEKA STAB LA-52, molecular weight 847 ) 0.2 parts by weight, ultraviolet absorber (2- (2'-
Hydroxy-5'-t-octylphenyl) benzotriazole, manufactured by Cypro Kasei, Seesorb 709) 0.05
Parts by weight, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 0.1 part by weight of IRGANOX 1076, manufactured by Nippon Ciba-Geigy, were added, and a twin-screw extruder was used. The mixture was kneaded at 0 ° C to obtain pellets.
【００２５】このペレットを用いて、シリンダー温度２
７０℃、金型温度７０℃で射出成形し、厚さ３ｍｍのプ
レートを作製した。Using this pellet, a cylinder temperature of 2
Injection molding was performed at 70 ° C. and a mold temperature of 70 ° C. to prepare a plate having a thickness of 3 mm.
【００２６】このプレートを、紫外線フェードメータを
用いて、ブラックパネル温度６３℃でプレートに紫外線
を２４０時間照射し、紫外線照射前と２４０時間照射の
４００ｎｍの光線透過率を、紫外可視分光光度計で測定
した。紫外線照射前の光線透過率は８６．８％で、紫外
線照射後の光線透過率は８６．０％であった。The plate was irradiated with ultraviolet rays for 240 hours at a black panel temperature of 63 ° C. using an ultraviolet fade meter, and the light transmittance of 400 nm before and 240 hours of irradiation with ultraviolet rays was measured by an ultraviolet-visible spectrophotometer. It was measured. The light transmittance before ultraviolet irradiation was 86.8%, and the light transmittance after ultraviolet irradiation was 86.0%.
【００２７】比較例２ ＺＥＯＮＥＸ ２８０にフルオロホスフォナイト系酸化
防止剤を添加しないこと以外は実施例２と同様にして、
プレートを作製し、２４０時間の紫外線照射を行った。Comparative Example 2 ZEONEX 280 was prepared in the same manner as in Example 2 except that no fluorophosphonite antioxidant was added.
A plate was prepared and irradiated with ultraviolet rays for 240 hours.
【００２８】紫外線照射前の光線透過率は８６．８％で
あったが、紫外線照射後は白濁した。The light transmittance before irradiation with ultraviolet rays was 86.8%, but it became cloudy after irradiation with ultraviolet rays.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 夏梅 伊男 神奈川県川崎市川崎区夜光１−２−１ 日 本ゼオン株式会社研究開発センター内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Ima Natsume 1-2-1 Yokou, Kawasaki-ku, Kawasaki-shi, Kanagawa Nihon Zeon Co., Ltd. Research and Development Center
Claims (5)
重量部に対して、フルオロホスフォナイト系酸化防止剤
０．０１〜５重量部を添加してなる熱可塑性飽和ノルボ
ルネン系樹脂組成物。1. A thermoplastic saturated norbornene resin 100.
A thermoplastic saturated norbornene-based resin composition obtained by adding 0.01 to 5 parts by weight of a fluorophosphonite-based antioxidant to parts by weight.
２，２’−エチリデンビス（４，６−ジ−ｔ−ブチルフ
ェニル）フルオロホスフォナイトである請求項１記載の
熱可塑性飽和ノルボルネン系樹脂組成物。2. The thermoplastic saturated norbornene-based resin according to claim 1, wherein the fluorophosphonite-based antioxidant is 2,2′-ethylidene bis (4,6-di-t-butylphenyl) fluorophosphonite. Composition.
ノルボルネン系樹脂組成物からなる光学材料。3. An optical material comprising the thermoplastic saturated norbornene-based resin composition according to claim 1 or 2.
ノルボルネン系樹脂組成物からなる医療用器材。4. A medical device comprising the thermoplastic saturated norbornene-based resin composition according to claim 1 or 2.
ノルボルネン系樹脂組成物からなる電気絶縁材料。5. An electrical insulating material comprising the thermoplastic saturated norbornene resin composition according to claim 1 or 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25737292A JP3243854B2 (en) | 1992-09-01 | 1992-09-01 | Thermoplastic saturated norbornene-based resin composition, optical material, medical equipment and electrical insulating material comprising the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25737292A JP3243854B2 (en) | 1992-09-01 | 1992-09-01 | Thermoplastic saturated norbornene-based resin composition, optical material, medical equipment and electrical insulating material comprising the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0680864A true JPH0680864A (en) | 1994-03-22 |
| JP3243854B2 JP3243854B2 (en) | 2002-01-07 |
Family
ID=17305477
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25737292A Expired - Fee Related JP3243854B2 (en) | 1992-09-01 | 1992-09-01 | Thermoplastic saturated norbornene-based resin composition, optical material, medical equipment and electrical insulating material comprising the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3243854B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999038918A1 (en) * | 1998-02-01 | 1999-08-05 | Nippon Zeon Co., Ltd. | Thermoplastic cycloolefin resin composition and molded object |
| US6030255A (en) * | 1995-01-31 | 2000-02-29 | Nippon Zeon Co., Ltd. | Insulator and high frequency connector |
| JP2005112809A (en) * | 2003-10-09 | 2005-04-28 | Asahi Denka Kogyo Kk | Polyvalent hindered amine compound suitable for optical material, its production method, norbornene-based resin composition, and light guide plate |
| JP2006169542A (en) * | 2006-03-10 | 2006-06-29 | Jsr Corp | Molding for light diffusion |
| KR20150093206A (en) | 2012-12-07 | 2015-08-17 | 다이요 홀딩스 가부시키가이샤 | Crosslinkable resin composition, cured product and method for producing same |
-
1992
- 1992-09-01 JP JP25737292A patent/JP3243854B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6030255A (en) * | 1995-01-31 | 2000-02-29 | Nippon Zeon Co., Ltd. | Insulator and high frequency connector |
| WO1999038918A1 (en) * | 1998-02-01 | 1999-08-05 | Nippon Zeon Co., Ltd. | Thermoplastic cycloolefin resin composition and molded object |
| JP2005112809A (en) * | 2003-10-09 | 2005-04-28 | Asahi Denka Kogyo Kk | Polyvalent hindered amine compound suitable for optical material, its production method, norbornene-based resin composition, and light guide plate |
| JP2006169542A (en) * | 2006-03-10 | 2006-06-29 | Jsr Corp | Molding for light diffusion |
| KR20150093206A (en) | 2012-12-07 | 2015-08-17 | 다이요 홀딩스 가부시키가이샤 | Crosslinkable resin composition, cured product and method for producing same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3243854B2 (en) | 2002-01-07 |
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