JPH05279554A - Ring-opening norbornene polymer resin composition - Google Patents
Ring-opening norbornene polymer resin compositionInfo
- Publication number
- JPH05279554A JPH05279554A JP4103931A JP10393192A JPH05279554A JP H05279554 A JPH05279554 A JP H05279554A JP 4103931 A JP4103931 A JP 4103931A JP 10393192 A JP10393192 A JP 10393192A JP H05279554 A JPH05279554 A JP H05279554A
- Authority
- JP
- Japan
- Prior art keywords
- ring
- glass transition
- resin
- transition temperature
- norbornene
- 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.)
- Pending
Links
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- Compositions Of Macromolecular Compounds (AREA)
- Optical Record Carriers And Manufacture Thereof (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ノルボルネン系開環重
合樹脂組成物に関し、さらに詳しくは低複屈折性などに
優れたノルボルネン系開環重合樹脂組成物に関する。TECHNICAL FIELD The present invention relates to a norbornene ring-opening polymerized resin composition, and more particularly to a norbornene ring-opening polymerized resin composition excellent in low birefringence and the like.
【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熱
可塑性飽和ノルボルネン系樹脂が光学材料として注目さ
れている。しかし、技術の進歩に伴い、より低複屈折性
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, a thermoplastic saturated norbornene-based resin, which is excellent in transparency, heat resistance, moisture resistance, low birefringence, and the like, is drawing attention as an optical material. However, with the progress of technology, lower birefringence has been required.
【０００３】熱可塑性飽和ノルボルネン系樹脂の内、ノ
ルボルネン系単量体とエチレン成分の共重合体である環
状オレフィン系ランダム共重合体について、軟化温度、
またはガラス転移温度に差のある２種のものからなる組
成物が公知である（特開昭６３−２７３６５５号等）。
しかし、その組成物が低複屈折性を有しているかどうか
は知られておらず、ガラス転移温度の異なる２種のノル
ボルネン系開環重合樹脂からなる組成物も知られていな
かった。Among the thermoplastic saturated norbornene resins, the cyclic olefin random copolymer, which is a copolymer of norbornene monomer and ethylene component, has a softening temperature,
Alternatively, a composition composed of two kinds having different glass transition temperatures is known (JP-A-63-273655, etc.).
However, it is not known whether the composition has a low birefringence, and a composition comprising two kinds of norbornene ring-opening polymerized resins having different glass transition temperatures has not been known.
【０００４】[0004]
【発明が解決しようとする課題】本発明者らは、鋭意研
究の結果、ガラス転移温度差のある２種のノルボルネン
系開環重合樹脂を配合した組成物の成形品が複屈折が小
さいことを見いだし、本発明を完成するに到った。DISCLOSURE OF THE INVENTION As a result of earnest research, the present inventors have found that a molded product of a composition containing two kinds of norbornene ring-opening polymerized resins having a glass transition temperature difference has a small birefringence. They have found and completed the present invention.
【０００５】かくして本発明によれば、ガラス転移温度
９０℃以上のノルボルネン系開環重合樹脂（Ａ）１００
重量部に対して、該樹脂（Ａ）と相溶性を有し、かつ該
樹脂（Ａ）に比べて７０℃以上低いガラス転移温度を有
する開環重合樹脂（Ｂ）１〜４０重量部を配合してなる
樹脂組成物が提供される。Thus, according to the present invention, the norbornene-based ring-opening polymerized resin (A) 100 having a glass transition temperature of 90 ° C. or higher is used.
1 to 40 parts by weight of a ring-opening polymerized resin (B) having compatibility with the resin (A) and having a glass transition temperature lower than that of the resin (A) by 70 ° C. or more based on parts by weight. A resin composition obtained by the above is provided.
【０００６】（ノルボルネン系開環重合樹脂）ノルボル
ネン系開環重合樹脂は、特開平３−１２２１３７号や特
開平３−２１０５０１号などで公知の樹脂であり、ノル
ボルネン系開環（共）重合体、その水素添加物、それら
の変性物をいう。(Norbornene-based ring-opening polymerized resin) The norbornene-based ring-opening polymerized resin is a resin known in JP-A-3-122137 and JP-A-3-210501, and a norbornene-based ring-opening (co) polymer, The hydrogenated products and their modified products are referred to.
【０００７】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 and the like; a monomer in which one or more cyclopentadiene is added to norbornene, a derivative or a substitution product similar to the above, 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 that is a multimer of cyclopentadiene, a derivative or substituent similar to the above, for example, dicyclopentadiene, 2,3-dihydrodicyclopentadiene and the like; adducts 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.
【０００８】ノルボルネン系単量体の開環重合は公知の
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、水素添加してもよい。また、開環重合体
や開環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 ring-opening polymerization of the norbornene-based monomer may be carried out by a known method, and if necessary, it may be copolymerized with another copolymerizable monomer or hydrogenated. Further, the ring-opening polymer and the hydrogenated product of the ring-opening polymer are treated by a method known in JP-A-3-95235 and the like, α, β-unsaturated carboxylic acid and / or its derivative, styrene-based hydrocarbon, olefin-based It may be modified by using an organosilicon compound having a saturated bond and a hydrolyzable group, or an unsaturated epoxy monomer.
【０００９】耐光劣化性や耐候劣化性、各種薬品からの
分解や着色などの劣化を受けにくいという点からはオレ
フィン性不飽和結合を多く含まないことが好ましく、そ
のために重合後の構造単位のなかに１つ以上の炭素−炭
素不飽和結合が存在する場合には水素添加することが好
ましく、その場合、通常、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％以上にす
る。From the viewpoint of light deterioration resistance, weather resistance, and resistance to deterioration such as decomposition from various chemicals and coloration, it is preferable that a large amount of olefinic unsaturated bonds are not contained. Therefore, among the structural units after polymerization, In the case where one or more carbon-carbon unsaturated bonds are present, hydrogenation is preferable, and in that case, the hydrogenation rate is usually 90% or more, preferably 95% or more, more preferably 99% or more. To do.
【００１０】（高ガラス転移温度を有するノルボルネン
系開環重合樹脂）本発明の高ガラス転移温度を有するノ
ルボルネン系開環重合樹脂（Ａ）は、ガラス転移温度が
９０℃以上、好ましくは、１１０℃以上、より好ましく
は１３０℃以上のものである。ただし、成形の容易さか
らガラス転移温度が２００℃以下のものが好ましい。(Norbornene ring-opening polymerized resin having a high glass transition temperature) The norbornene ring-opening polymerized resin (A) having a high glass transition temperature of the present invention has a glass transition temperature of 90 ° C. or higher, preferably 110 ° C. As described above, more preferably 130 ° C. or higher. However, those having a glass transition temperature of 200 ° C. or lower are preferable from the viewpoint of ease of molding.
【００１１】高ガラス転移温度を有するノルボルネン系
開環重合樹脂（Ａ）を得るには、例えば、多環のモノマ
ーを多く用いればよい。In order to obtain the norbornene-based ring-opening polymerized resin (A) having a high glass transition temperature, for example, many polycyclic monomers may be used.
【００１２】分子量はトルエン溶媒によるＧＰＣ（ゲル
・パーミエーション・クロマトグラフィ）分析により測
定した数平均分子量で１〜２０万が適当であり、好まし
くは２〜１０万であり、この範囲よりも分子量が小さい
場合には十分な強度が得られない、割れやすいなどの不
都合があり、この範囲よりも分子量が大きいと、成形時
の流動性が悪くなり成形しにくい、樹脂の合成時に再現
性よくかつ生産性よく合成しにくいという不都合が生じ
る。The number average molecular weight measured by GPC (gel permeation chromatography) analysis with a toluene solvent is suitably from 1 to 200,000, preferably from 2 to 100,000, and the molecular weight is smaller than this range. In that case, there are inconveniences such as insufficient strength and cracking. If the molecular weight is higher than this range, the fluidity during molding will be poor and molding will be difficult. There is the inconvenience that it is difficult to synthesize well.
【００１３】（低ガラス転移温度を有するノルボルネン
系開環重合樹脂）本発明の低ガラス転移温度を有するノ
ルボルネン系開環重合樹脂（Ｂ）は、本発明の高ガラス
転移温度を有するノルボルネン系開環重合樹脂（Ａ）と
比較して、ガラス転移温度が７０℃以上、好ましくは８
０℃以上、より好ましくは９０℃以上、特に好ましくは
１００℃以上低いノルボルネン系開環重合樹脂である。
また、ガラス転移温度が−１０〜１３０℃のものが好ま
しく、０〜１００℃のものがより好ましい。(Norbornene ring-opening polymerized resin having a low glass transition temperature) The norbornene ring-opening polymerized resin (B) having a low glass transition temperature of the present invention is a norbornene ring-opening polymerized resin having a high glass transition temperature of the present invention. Compared with the polymer resin (A), it has a glass transition temperature of 70 ° C. or higher, preferably 8
A norbornene-based ring-opening polymerized resin having a temperature of 0 ° C or higher, more preferably 90 ° C or higher, and particularly preferably 100 ° C or higher.
The glass transition temperature is preferably -10 to 130 ° C, more preferably 0 to 100 ° C.
【００１４】また、本発明の低ガラス転移温度を有する
ノルボルネン系開環重合樹脂（Ｂ）は、本発明の高ガラ
ス転移温度を有するノルボルネン系開環重合樹脂（Ａ）
と相溶するものである。ノルボルネン系開環重合樹脂同
士は、通常、相溶するが、例えば、四環体以上のノルボ
ルネン系モノマーの開環重合樹脂と二環体であるノルボ
ルネンの開環重合樹脂のように、主たるモノマーの環数
が２つ以上差があるノルボルネン系開環重合樹脂は、相
溶しにくく、量比によっては溶融した状態で分離するこ
とがある。分子量に大きな差がある場合で、主として極
性基を有しているモノマーからなる開環重合樹脂と主と
して極性基を有さないモノマーからなる開環重合体も相
溶しにくい。そこで、本発明においては、高ガラス転移
温度を有するノルボルネン系開環重合樹脂（Ａ）に応じ
て、それに配合する低ガラス転移温度を有するノルボル
ネン系開環重合樹脂（Ｂ）を何にするか、どれだけ配合
するかを検討して、決定する必要がある。一般に、極性
を持たず、環数の同じ、または一つ違うノルボルネン系
モノマーのホモ開環重合樹脂同士が相溶しやすく、好ま
しい。ガラス転移温度に差を持たせるためには、特に環
数が一つ違う高ガラス転移温度を有するノルボルネン系
開環重合樹脂（Ａ）と低ガラス転移温度を有するノルボ
ルネン系開環重合樹脂（Ｂ）の組み合せが好ましい。The norbornene ring-opening polymerized resin (B) having a low glass transition temperature of the present invention is a norbornene ring-opening polymerized resin (A) having a high glass transition temperature of the present invention.
It is compatible with. Norbornene-based ring-opening polymer resins are usually compatible with each other, but, for example, a ring-opening polymerized resin of a norbornene-based monomer having a tetracyclic structure or more and a norbornene ring-opening polymerized resin that is a bicyclic compound are used. Norbornene-based ring-opening polymerized resins having a difference in the number of rings of 2 or more are difficult to be compatible with each other and may be separated in a molten state depending on the amount ratio. When there is a large difference in molecular weight, a ring-opening polymer resin mainly composed of a monomer having a polar group and a ring-opening polymer mainly composed of a monomer not having a polar group are not easily compatible with each other. Therefore, in the present invention, depending on the norbornene-based ring-opening polymerized resin (A) having a high glass transition temperature, what is the norbornene-based ring-opening polymerized resin (B) having a low glass transition temperature to be blended with it, It is necessary to consider and decide how much to mix. In general, homo-ring-opening polymerization resins of norbornene-based monomers having no polarity and the same or different ring number are easily compatible with each other, which is preferable. In order to make the glass transition temperatures different, a norbornene ring-opening polymerized resin (A) having a high glass transition temperature and a norbornene ring-opening polymerized resin (B) having a low glass transition temperature, each having one different ring number. Is preferred.
【００１５】なお、非相溶であることを確認するには、
両者を目的の量比で配合し、成形し、０．０５μｍ程度
の厚さにスライスし、例えば四酸化ルテニウム等で染色
し、光学顕微鏡で１００倍程度の倍率で拡大して観察す
ればよい。非相溶であれば、ドメインを形成しており、
ドメインが染色される。また、簡便な方法としては、表
面が平滑な成形品を成形して、スリット等を通した光を
一方向から当てる方法があり、非相溶であれば、光がド
メインにより散乱し、光の経路が観察できる。ただし、
この方法では、ドメインがごく小さく、可視光の波長よ
り小さければ、散乱が起こり難く、非相溶であることが
確認できない場合がある。To confirm that they are incompatible,
Both may be mixed in a desired amount ratio, molded, sliced to a thickness of about 0.05 μm, stained with, for example, ruthenium tetroxide, etc., and magnified and observed with an optical microscope at a magnification of about 100 times. If they are incompatible, they form a domain,
The domain is stained. Further, as a simple method, there is a method of molding a molded product having a smooth surface and irradiating light passing through a slit or the like from one direction. The route can be observed. However,
In this method, if the domain is very small and smaller than the wavelength of visible light, scattering may be difficult to occur and it may not be possible to confirm incompatibility.
【００１６】低ガラス転移温度を有する飽和ノルボルネ
ン系開環重合樹脂を得るには、例えば、環の少ないモノ
マー、特に２環体モノマーを多く用いればよい。To obtain a saturated norbornene ring-opening polymerized resin having a low glass transition temperature, for example, a monomer having a small number of rings, especially a bicyclic monomer may be used in large amounts.
【００１７】分子量はトルエン溶媒によるＧＰＣ（ゲル
・パーミエーション・クロマトグラフィ）分析により測
定した数平均分子量で２千〜４万、好ましくは３千〜３
万が適当である。The molecular weight is 2,000 to 40,000, preferably 3,000 to 3 as a number average molecular weight measured by GPC (gel permeation chromatography) analysis using a toluene solvent.
Anything is appropriate.
【００１８】（配合）本発明の樹脂組成物は、高ガラス
転移温度を有するノルボルネン系開環重合樹脂１００重
量部に対する低ガラス転移温度を有するノルボルネン系
開環重合樹脂の配合量は１〜４０重量部、好ましくは２
〜３０重量部、より好ましくは３〜２０重量部である。
低ガラス転移温度を有するノルボルネン系開環重合樹脂
の配合量が少なすぎると、本発明の効果が得られず、低
カラス転移温度を有するノルボルネン系開環重合樹脂の
配合量が多すぎると、開環重合樹脂の組み合せによって
は相溶しなかったり、また高温で変形しやすくなる。(Blending) The resin composition of the present invention contains 1 to 40 parts by weight of the norbornene ring-opening polymerized resin having a low glass transition temperature based on 100 parts by weight of the norbornene ring-opening polymerized resin having a high glass transition temperature. Part, preferably 2
-30 parts by weight, more preferably 3-20 parts by weight.
If the amount of the norbornene ring-opening polymerized resin having a low glass transition temperature is too small, the effect of the present invention cannot be obtained, and if the amount of the norbornene ring-opening polymerized resin having a low glass transition temperature is too large, the Depending on the combination of ring-polymerized resins, they may not be compatible with each other or may be easily deformed at high temperature.
【００１９】また、本発明の樹脂組成物は高ガラス転移
温度を有するノルボルネン系開環重合樹脂（Ａ）と低ガ
ラス転移温度を有するノルボルネン系開環重合樹脂
（Ｂ）が必須であるが、必要に応じて、樹脂（Ａ）、樹
脂（Ｂ）の混合物に相溶性を有する他の樹脂を混合して
もよい。そのような樹脂の具体例として、樹脂（Ａ）と
樹脂（Ｂ）の中間のガラス転移温度を有するノルボルネ
ン系開環重合樹脂が挙げられるが、その配合量は、樹脂
（Ａ）が樹脂組成物全体の５０重量％を下まわらない範
囲であることが好ましい。Further, the resin composition of the present invention requires a norbornene ring-opening polymerized resin (A) having a high glass transition temperature and a norbornene ring-opening polymerized resin (B) having a low glass transition temperature, but it is necessary. Depending on the above, other compatible resins may be mixed with the mixture of the resin (A) and the resin (B). A specific example of such a resin is a norbornene-based ring-opening polymerized resin having a glass transition temperature intermediate between those of the resin (A) and the resin (B). It is preferably in a range not exceeding 50% by weight of the whole.
【００２０】配合する方法は特に限定されず、一般の二
軸押し出し機等を用いてペレットにする方法のほか、例
えば、両者の良溶媒に両者を溶解し、両者の貧溶媒を多
量に加えることにより、凝固させ、濾過等により凝固し
た樹脂を回収し、十分に乾燥させることにより、粉末状
の樹脂組成物としてもよく、またはその粉末状の樹脂組
成物を押し出し機などを用いてペレットにしてもよい。The method of blending is not particularly limited, and in addition to the method of pelletizing using a general twin-screw extruder, for example, both are dissolved in a good solvent for both and a poor solvent for both is added in a large amount. By coagulating, collecting the resin coagulated by filtration, etc., and by sufficiently drying, it may be a powdered resin composition, or the powdered resin composition into pellets using an extruder or the like. Good.
【００２１】（添加剤）本発明の組成物には、所望によ
り、フェノール系やリン系などの老化防止剤；フェノー
ル系などの熱劣化防止剤；ベンゾフェノン系やヒンダー
ドアミン系などの紫外線安定剤；アミン系の帯電防止
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助剤；などの各種添
加剤を添加してもよい。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。さらに、透明性を必要としない電子部品生産用部材
に用いる場合は、色分けによる識別や耐熱性や強度等を
改良することを目的として、各種のタルクやチタン白な
どの鉱物系やその他のフィラー、有機系または無機系の
顔料などを用いることもできる。(Additives) In the composition of the present invention, if desired, an antioxidant such as a phenol type or a phosphorus type; a heat deterioration inhibitor such as a phenol type; an ultraviolet stabilizer such as a benzophenone type or a hindered amine type; an amine Various additives such as a system antistatic agent; an auxiliary agent such as an ester of an aliphatic alcohol, a partial ester and a partial ether of a polyhydric alcohol; and the like may be added. Further, other resins and the like can be mixed and used as long as the object of the present invention is not impaired. Furthermore, when used for a member for electronic component production that does not require transparency, various minerals such as talc and titanium white and other fillers for the purpose of improving identification and heat resistance and strength by color coding, It is also possible to use an organic or inorganic pigment.
【００２２】（樹脂組成物）本発明の樹脂組成物は、耐
薬品性、誘電特性、剛性は、ノルボルネン系開環重合樹
脂と実質的に同じである。また、本発明の樹脂組成物は
高ガラス転移温度を有するノルボルネン系開環重合樹脂
を少なくとも５０重量％含有しているので、耐熱性に優
れている。(Resin Composition) The resin composition of the present invention has substantially the same chemical resistance, dielectric properties and rigidity as the norbornene ring-opening polymerized resin. Further, the resin composition of the present invention contains at least 50% by weight of a norbornene-based ring-opening polymerized resin having a high glass transition temperature, and therefore has excellent heat resistance.
【００２３】樹脂組成物の成形方法は特に限定されな
い。目的に応じて、射出成形法、ブロー成形法、インジ
ェクションブロー成形法、回転成形法、真空成形法、押
出成形法、カレンダー成形法、溶液流延法などが可能で
ある。The method for molding the resin composition is not particularly limited. Depending on the purpose, an injection molding method, a blow molding method, an injection blow molding method, a rotational molding method, a vacuum molding method, an extrusion molding method, a calender molding method, a solution casting method and the like are possible.
【００２４】本発明の樹脂組成物から成る成形品、特に
樹脂を溶融して成形した成形品においては複屈折が小さ
く、光ディスク基板などを成形することが可能であり、
本発明の樹脂組成物は光学材料として優れた性質を有し
ている。A molded article made of the resin composition of the present invention, especially a molded article obtained by melting a resin, has a small birefringence and can be molded into an optical disk substrate or the like.
The resin composition of the present invention has excellent properties as an optical material.
【００２５】[0025]
【実施例】以下に参考例、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。なお、数平均分子量
はトルエン溶媒によるＧＰＣ分析により、水素添加率は
1Ｈ−ＮＭＲにより、ガラス転移温度はＤＳＣ法によ
り、レタデーション値は波長６３０ｎｍのダブルパス法
により直径１３０ｍｍ、厚さ１．２ｍｍのディスクの中
心から半径２５〜６０ｍｍの範囲のものを測定し、光線
透過率は波長８３０ｎｍについて測定した。EXAMPLES The present invention will be described more specifically below with reference to reference examples, examples and comparative examples. The number average molecular weight was determined by GPC analysis using a toluene solvent.
By 1 H-NMR, the glass transition temperature was measured by the DSC method, and the retardation value was measured by the double-pass method with a wavelength of 630 nm in the range of a radius of 25 to 60 mm from the center of a disk having a diameter of 130 mm and a thickness of 1.2 mm, and the light transmission. The ratio was measured at a wavelength of 830 nm.
【００２６】実施例１ ８−メチル−テトラシクロ〔４．４．０．１2,5．１
7,10〕−３−ドデセンの開環重合体水素添加物（数平均
分子量２８，０００、水素添加率９９．５％、ガラス転
移温度１５２℃、以下、ポリマーＡという）９０重量部
と、５−エチル−ビシクロ〔２．２．１〕−２−ヘプテ
ン８０重量％と８−メチル−テトラシクロ〔４．４．
０．１2,5．１7,10〕−３−ドデセン２０重量％の開環
共重合体水素添加物（数平均分子量２０，０００、水素
添加率９９．５重量％、ガラス転移温度２５℃、以下、
ポリマーＢという）１０重量部を、二軸押し出し機（東
芝機械社製、ＴＥＭ−３５）を用いて１８０℃で混練
し、ペレットにした。Example 1 8-Methyl-tetracyclo [4.4.0.1 2,5 . 1
7,10 ] -3-dodecene ring-opening polymer hydrogenated product (number average molecular weight 28,000, hydrogenation rate 99.5%, glass transition temperature 152 ° C., hereinafter referred to as polymer A) 90 parts by weight and 5 80% by weight of -ethyl-bicyclo [2.2.1] -2-heptene and 8-methyl-tetracyclo [4.4.
0.1 2,5 . 1 7,10 ] -3-dodecene 20% by weight of a ring-opening copolymer hydrogenated product (number average molecular weight 20,000, hydrogenation rate 99.5% by weight, glass transition temperature 25 ° C., or less,
10 parts by weight of polymer B) was kneaded at 180 ° C. using a twin-screw extruder (manufactured by Toshiba Machine Co., Ltd., TEM-35) to form pellets.
【００２７】このペレットを射出成形機（住友重機械工
業株式会社製、ＤＩＳＫ−５ ＭIII）により、樹脂温
度３３０℃、金型温度１１０℃で射出成形を行い、直径
１３０ｍｍ、厚さ１．２ｍｍの光ディスク基板を成形し
た。The pellets were injection-molded with an injection molding machine (DISK-5 MIII, manufactured by Sumitomo Heavy Industries, Ltd.) at a resin temperature of 330 ° C. and a mold temperature of 110 ° C. to have a diameter of 130 mm and a thickness of 1.2 mm. An optical disk substrate was molded.
【００２８】この光ディスク基板の光線透過率は９２
％、レタデーション値は１０ｎｍ以下であった。The light transmittance of this optical disk substrate is 92.
%, And the retardation value was 10 nm or less.
【００２９】実施例２ ポリマーＡ９５重量部と、ポリマーＢ５重量部を、９０
０重量部のトルエンに溶解し、攪拌している２０００重
量部のイソプロピルアルコール中に添加し、凝固した樹
脂粉末を濾過により回収し、真空乾燥機を用いて、２ｍ
ｍＨｇ、１００℃で４８時間乾燥した後、押出機でペレ
ット化した。Example 2 95 parts by weight of polymer A and 5 parts by weight of polymer B were added to 90 parts by weight.
It is dissolved in 0 part by weight of toluene and added to 2000 parts by weight of isopropyl alcohol which is being stirred, and the solidified resin powder is collected by filtration, and is dried for 2 m by using a vacuum dryer.
It was dried at mHg and 100 ° C. for 48 hours, and then pelletized by an extruder.
【００３０】このペレットを用いて実施例１と同様に成
形して光ディスク基板を得た。The pellets were molded in the same manner as in Example 1 to obtain an optical disk substrate.
【００３１】この光ディスク基板の光線透過率は９３
％、レタデーション値は１５ｎｍ以下であった。The light transmittance of this optical disk substrate is 93.
%, And the retardation value was 15 nm or less.
【００３２】実施例３ ポリマーＡ９０重量部とポリマーＢ１０重量部の代わり
に、ポリマーＡ８０重量部とトリシクロ〔４．３．０．
１2,5〕−３，７−デカジエン５０重量％と５−エチル
−ビシクロ〔２．２．１〕−２−ヘプテン５０重量％の
開環共重合体水素添加物（数平均分子量２２，０００、
水素添加率９９．５重量％、ガラス転移温度４５℃）２
０重量部を用いる以外は実施例１と同様にペレット化、
成形して光ディスク基板を得た。Example 3 Instead of 90 parts by weight of polymer A and 10 parts by weight of polymer B, 80 parts by weight of polymer A and tricyclo [4.3.0.
1 2,5 ] -3,7-decadiene 50 wt% and 5-ethyl-bicyclo [2.2.1] -2-heptene 50 wt% ring-opening copolymer hydrogenated product (number average molecular weight 22,000) ,
Hydrogenation rate 99.5% by weight, glass transition temperature 45 ° C) 2
Pelletization as in Example 1 except using 0 parts by weight,
An optical disk substrate was obtained by molding.
【００３３】この光ディスク基板の光線透過率は９１
％、レタデーション値は１２ｎｍであった。The light transmittance of this optical disk substrate is 91.
% And the retardation value was 12 nm.
【００３４】比較例１ ポリマーＡ９０重量部とポリマーＢ１０重量部の代わり
にポリマーＡのみを用いる以外は実施例１と同様にペレ
ット化し、成形し、光ディスク基板を得た。Comparative Example 1 An optical disk substrate was obtained by pelletizing and molding in the same manner as in Example 1 except that only Polymer A was used instead of Polymer A 90 parts by weight and Polymer B 10 parts by weight.
【００３５】この光ディスク基板の光線透過率は９３
％、レタデーション値は２２ｎｍ以下であった。The light transmittance of this optical disk substrate is 93.
%, And the retardation value was 22 nm or less.
【００３６】比較例２ ポリマーＢの代わりに５−エチル−ビシクロ〔２．２．
１〕−２−ヘプテンの開環重合体水素添加物（数平均分
子量１９，０００、水素添加率９９．５％、ガラス転移
温度２℃）を用いる以外は実施例１と同様にペレット化
し、成形し、光ディスク基板を得た。Comparative Example 2 Instead of the polymer B, 5-ethyl-bicyclo [2.2.
1] -2-Heptene ring-opening polymer Hydrogenated product (number average molecular weight 19,000, hydrogenation rate 99.5%, glass transition temperature 2 ° C.) was pelletized and molded in the same manner as in Example 1. Then, an optical disk substrate was obtained.
【００３７】この光ディスク基板の光線透過率は７０
％、レタデーション値は２０ｎｍ以下であった。The light transmittance of this optical disk substrate is 70.
%, And the retardation value was 20 nm or less.
【００３８】なお、この光ディスク基板を光学顕微鏡で
観察したところ、樹脂の相分離が認められ、スリットを
通した光束を当てると強い光線の散乱が見られ、２種の
開環重合体水素添加物が非相溶であることが判った。When this optical disk substrate was observed with an optical microscope, phase separation of the resin was observed, strong light scattering was observed when the light flux passing through the slit was applied, and two types of hydrogenated ring-opening polymer hydrogenated products were observed. Were found to be incompatible.
【００３９】比較例３ ５−エチル−ビシクロ〔２，２，１〕−２−ヘプテン１
０重量％と８−メチル−テトラシクロ〔４．４．０．１
2,5．１7,10〕−３−ドデセン９０重量％の開環共重合
体水素添加物（数平均分子量２９，０００、水素添加率
９９．５％、ガラス転移温度１３７℃）を用いる以外は
実施例１と同様にペレット化し、成形し、光ディスク基
板を得た。Comparative Example 3 5-Ethyl-bicyclo [2,2,1] -2-heptene 1
0% by weight and 8-methyl-tetracyclo [4.4.0.1
2,5 . Example 1 except that a hydrogenated product of a ring-opening copolymer containing 90% by weight of 1,7,10 ] -3-dodecene (number average molecular weight of 29,000, hydrogenation rate of 99.5%, glass transition temperature of 137 ° C.) was used. Pelletization and molding were carried out in the same manner as in 1. to obtain an optical disk substrate.
【００４０】この光ディスク基板の光線透過率は９２
％、レタデーション値は２２ｎｍ以下であった。The light transmittance of this optical disk substrate is 92.
%, And the retardation value was 22 nm or less.
【００４１】比較例４ ポリマーＡ９０重量部とポリマーＢ１０重量部の代わり
にポリマーＡ８０重量部とトリシクロ〔４．３．０．１
2,5〕−３，７−デカジエンの開環重合体水素添加物
（数平均分子量２１，０００、水素添加率９９．５％、
ガラス転移温度９０℃）２０重量部を用いる以外は実施
例１と同様にペレット化し、成形し、光ディスク基板を
得た。Comparative Example 4 Instead of 90 parts by weight of Polymer A and 10 parts by weight of Polymer B, 80 parts by weight of Polymer A and tricyclo [4.3.0.1] were used.
2,5 ] -3,7-decadiene ring-opening polymer hydrogenated product (number average molecular weight 21,000, hydrogenation rate 99.5%,
An optical disk substrate was obtained by pelletizing and molding in the same manner as in Example 1 except that 20 parts by weight of glass transition temperature 90 ° C.) was used.
【００４２】この光ディスク基板の光線透過率は９０
％、レタデーション値は２０ｎｍ以下であった。The light transmittance of this optical disk substrate is 90.
%, And the retardation value was 20 nm or less.
【００４３】[0043]
【発明の効果】本発明の熱可塑性飽和ノルボルネン系樹
脂組成物の成形品は、レタデーション値が小さい。The molded article of the thermoplastic saturated norbornene resin composition of the present invention has a small retardation value.
───────────────────────────────────────────────────── 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 (1)
ン系開環重合樹脂（Ａ）１００重量部に対して、該樹脂
（Ａ）と相溶性を有し、かつ該樹脂（Ａ）に比べて７０
℃以上低いガラス転移温度を有するノルボルネン系開環
重合樹脂（Ｂ）１〜４０重量部を配合してなる樹脂組成
物。1. A resin which is compatible with 100 parts by weight of a norbornene-based ring-opening polymerized resin (A) having a glass transition temperature of 90 ° C. or higher and which is 70% more than the resin (A).
A resin composition comprising 1 to 40 parts by weight of a norbornene-based ring-opening polymerized resin (B) having a glass transition temperature lower than 0 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4103931A JPH05279554A (en) | 1992-03-31 | 1992-03-31 | Ring-opening norbornene polymer resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4103931A JPH05279554A (en) | 1992-03-31 | 1992-03-31 | Ring-opening norbornene polymer resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05279554A true JPH05279554A (en) | 1993-10-26 |
Family
ID=14367184
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4103931A Pending JPH05279554A (en) | 1992-03-31 | 1992-03-31 | Ring-opening norbornene polymer resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05279554A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002028966A1 (en) * | 2000-10-02 | 2002-04-11 | Sekisui Chemical Co., Ltd. | Melt-moldable thermoplastic norbornene resin composition and molded article and optical film both comprising the same |
| US7008569B2 (en) | 2001-04-27 | 2006-03-07 | Jsr Corporation | Thermoplastic norbornene resin based optical film |
| US7015276B2 (en) | 2000-10-02 | 2006-03-21 | Sekisui Chemical Co., Ltd. | Melt-moldable thermoplastic norbornene resin composition and molded article and optical film both comprising the same |
| WO2009066511A1 (en) * | 2007-11-21 | 2009-05-28 | Zeon Corporation | Polymer composition and use thereof |
| JP2010241851A (en) * | 2009-03-31 | 2010-10-28 | Nippon Zeon Co Ltd | Curable resin composition and insulating film for circuit board |
| US8809457B2 (en) | 2011-09-30 | 2014-08-19 | Tokyo Ohka Kogyo Co., Ltd. | Adhesive composition, adhesive film, and method for treating substrate |
| US8980997B2 (en) | 2010-06-15 | 2015-03-17 | Tokyo Ohka Kogyo Co., Ltd. | Adhesive composition |
| US9115297B2 (en) | 2010-09-30 | 2015-08-25 | Tokyo Ohka Kogyo Co., Ltd. | Adhesive composition |
-
1992
- 1992-03-31 JP JP4103931A patent/JPH05279554A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002028966A1 (en) * | 2000-10-02 | 2002-04-11 | Sekisui Chemical Co., Ltd. | Melt-moldable thermoplastic norbornene resin composition and molded article and optical film both comprising the same |
| US7015276B2 (en) | 2000-10-02 | 2006-03-21 | Sekisui Chemical Co., Ltd. | Melt-moldable thermoplastic norbornene resin composition and molded article and optical film both comprising the same |
| KR100790793B1 (en) * | 2000-10-02 | 2008-01-02 | 세끼쑤이 케미컬 가부시기가이샤 | Melt-moldable, thermoplastic norbornene-based resin composition, and molded article or optical film using the same |
| US7008569B2 (en) | 2001-04-27 | 2006-03-07 | Jsr Corporation | Thermoplastic norbornene resin based optical film |
| JP4609593B2 (en) * | 2007-11-21 | 2011-01-12 | 日本ゼオン株式会社 | Polymer composition and use thereof |
| WO2009066511A1 (en) * | 2007-11-21 | 2009-05-28 | Zeon Corporation | Polymer composition and use thereof |
| JP2011026614A (en) * | 2007-11-21 | 2011-02-10 | Nippon Zeon Co Ltd | Polymer composition and use thereof |
| JPWO2009066511A1 (en) * | 2007-11-21 | 2011-04-07 | 日本ゼオン株式会社 | Polymer composition and use thereof |
| US8277914B2 (en) | 2007-11-21 | 2012-10-02 | Zeon Corporation | Polymer composition and use thereof |
| JP2010241851A (en) * | 2009-03-31 | 2010-10-28 | Nippon Zeon Co Ltd | Curable resin composition and insulating film for circuit board |
| US8980997B2 (en) | 2010-06-15 | 2015-03-17 | Tokyo Ohka Kogyo Co., Ltd. | Adhesive composition |
| US9115297B2 (en) | 2010-09-30 | 2015-08-25 | Tokyo Ohka Kogyo Co., Ltd. | Adhesive composition |
| US8809457B2 (en) | 2011-09-30 | 2014-08-19 | Tokyo Ohka Kogyo Co., Ltd. | Adhesive composition, adhesive film, and method for treating substrate |
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