JPH0724911A - Syndyotactic polystyrene film - Google Patents
Syndyotactic polystyrene filmInfo
- Publication number
- JPH0724911A JPH0724911A JP5169293A JP16929393A JPH0724911A JP H0724911 A JPH0724911 A JP H0724911A JP 5169293 A JP5169293 A JP 5169293A JP 16929393 A JP16929393 A JP 16929393A JP H0724911 A JPH0724911 A JP H0724911A
- Authority
- JP
- Japan
- Prior art keywords
- film
- stretching
- less
- flatness
- heat
- 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
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、包装材料、工業用材
料、磁気テープ、コンデンサなどに用いる際、平面性、
印刷性、耐熱性、耐擦傷性、耐磨耗性に優れた、シンジ
オタクチック構造を有するスチレン系樹脂からなるフィ
ルムに関する。INDUSTRIAL APPLICABILITY The present invention is applied to packaging materials, industrial materials, magnetic tapes, capacitors, etc.
The present invention relates to a film made of a styrene resin having a syndiotactic structure, which is excellent in printability, heat resistance, scratch resistance, and abrasion resistance.
【０００２】[0002]
【従来の技術】近年、シンジオタクチック構造を有する
スチレン系重合体が開発され（特開昭62−104818号公
報）、またこれらを用いた延伸フィルムの開発も行われ
ている（特開平１−110122号、同１−168709号、同１−
182346号、同２−279731号、同３−74437 号、同３−10
9453号、同３−99828 号、同３−124427号、同３−1316
44号など）これらのシンジオタクチックポリスチレン系
フィルムは機械的特性、透明性、耐薬品性、誘電損失や
誘電率などの電気的特性が優れているため、各種工業
用、包装用フィルムに展開されることが期待されてい
る。しかしこれまでのシンジオタクチックポリスチレン
系フィルムは、平面性、印刷性、耐熱性、耐磨耗性の点
で満足のいくものではなかったため、非常に限られた用
途展開しか行われなかった。2. Description of the Related Art In recent years, styrene polymers having a syndiotactic structure have been developed (JP-A-62-104818), and a stretched film using them has also been developed (JP-A-1- 110122, 1-168709, 1-
182346, 2-279731, 3-74437, 3-10
9453, 3-99828, 3-124427, 3-1316
These syndiotactic polystyrene films have excellent mechanical properties, transparency, chemical resistance, and electrical properties such as dielectric loss and permittivity, so they have been developed into various industrial and packaging films. Is expected to However, the conventional syndiotactic polystyrene films have not been satisfactory in terms of flatness, printability, heat resistance, and abrasion resistance, so that they have been applied to very limited applications.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、前期の欠
点、即ち、平面性、印刷性、耐熱性、耐擦傷性、耐磨耗
性に優れかつ機械的、電気的特性、透明性、耐薬品性の
満足する基材を提供せんとするものである。DISCLOSURE OF THE INVENTION The present invention has the above-mentioned drawbacks, namely, excellent flatness, printability, heat resistance, scratch resistance, and abrasion resistance and mechanical, electrical characteristics, transparency, and resistance to abrasion. It is intended to provide a base material having satisfactory chemical properties.
【０００４】[0004]
【課題を解決するための手段】すなわちこれらを解決す
るための手段としての本発明の主旨は、主としてシンジ
オタクチック構造を有するポリスチレン系重合体におい
て少なくとも１軸方向に延伸され、フィルムの厚み方向
の屈折率Nzが1.623 以下でありかつ150 ℃の熱収縮率が
3%以下であることを特徴とするフィルムに関する。本発
明におけるシンジオタクチック構造を有するポリスチレ
ンとは、立体規則性がシンジオタクチック構造すなわ
ち、炭素−炭素結合から形成された主鎖に対して側鎖で
あるフェニル基や置換フェニル基が交互に反対方向に位
置する立体構造を持つものである。That is, the gist of the present invention as a means for solving these is to stretch at least uniaxially in a polystyrene polymer mainly having a syndiotactic structure, The refractive index Nz is less than 1.623 and the thermal shrinkage at 150 ℃ is
It relates to a film characterized by being 3% or less. The polystyrene having a syndiotactic structure in the present invention means that stereoregularity has a syndiotactic structure, that is, a phenyl group or a substituted phenyl group, which is a side chain, is alternately opposite to a main chain formed from carbon-carbon bonds. It has a three-dimensional structure located in the direction.
【０００５】本発明におけるスチレン重合体は、分子量
については特に制限はないが、重量平均分子量が１万以
上300 万以下が望ましい（特開平３−124427号公報）。
本発明の基材には制電密着性、易滑性、延伸性、加工適
性などを向上させるためや、粗面化、不透明化、空洞
化、軽量化などの理由により、他の樹脂、無機粒子、耐
候剤、蛍光剤、紫外線吸収剤、酸化防止剤、可塑剤、相
溶化剤、着色剤、帯電防止剤などを添加してもよい。こ
れらは特開平３−124427号公報はじめこれまでに開示さ
れている方法により、シンジオタクチックポリスチレン
系フィルムのもつ特徴を著しく落とさない範囲で、ポリ
スチレン基材のフィルムのみならずポリエステル、ポリ
オレフィン、ポリアミド、ポリアクリルなどの熱可塑性
樹脂フィルムに用いられた技術を用いることができる。
またこれらの添加剤はシンジオタクチックポリスチレン
系フィルムのもつ特徴を著しく落とさない範囲で添加す
る方法は限定されない。よって、重合時添加でも、重合
後にマスターバッチとして予備混練しても、また溶融押
しだし時に直接投入しても構わない。こうして得た重合
体混合物は、以下に例示する方法で延伸フィルムを得る
が、後で述べる特性を満足するものであればここに示さ
れた方法に限定されるものではない。まずシンジオタク
チック構造ポリスチレンを主とする重合体混合物を好ま
しくは３時間以上100 〜150 ℃で乾燥し、290 〜350 ℃
で溶融押しだしし、エアーナイフ法、水冷法、静電密着
法などにより樹脂を冷却して、未延伸シートを得る。こ
こで用いる押出機は、特に限定されるものではなく、1
軸押出機、２軸押出機でも、またベントあり、なしいず
れも、またタンデム型でもシングルでも構わない。The molecular weight of the styrene polymer in the present invention is not particularly limited, but the weight average molecular weight is preferably 10,000 or more and 3,000,000 or less (JP-A-3-124427).
In order to improve antistatic adhesion, slipperiness, stretchability, processability, etc., and for the reasons of roughening, opacifying, hollowing, and weight reduction, the base material of the present invention may be made of other resin, inorganic material. Particles, weathering agents, fluorescent agents, ultraviolet absorbers, antioxidants, plasticizers, compatibilizers, colorants, antistatic agents and the like may be added. These are disclosed in Japanese Patent Application Laid-Open No. 3-124427, and by the methods disclosed up to now, within the range in which the characteristics of the syndiotactic polystyrene-based film are not significantly impaired, not only polystyrene-based films but also polyesters, polyolefins, polyamides, The technique used for the thermoplastic resin film such as polyacrylic can be used.
The method of adding these additives is not limited as long as the characteristics of the syndiotactic polystyrene film are not significantly impaired. Therefore, it may be added at the time of polymerization, preliminarily kneaded as a masterbatch after polymerization, or added directly at the time of melt extrusion. The polymer mixture thus obtained can be used to obtain a stretched film by the method illustrated below, but the method is not limited to the method shown here as long as it satisfies the properties described below. First, a polymer mixture mainly composed of syndiotactic polystyrene is dried at 100 to 150 ° C for preferably 3 hours or more, and then 290 to 350 ° C.
Is melt-extruded and the resin is cooled by an air knife method, a water cooling method, an electrostatic adhesion method or the like to obtain an unstretched sheet. The extruder used here is not particularly limited, and 1
Either a twin-screw extruder or a twin-screw extruder, with or without vents, tandem type or single type may be used.
【０００６】得られた未延伸シートは少なくとも１軸に
延伸する。その方法は速度差をもったロール間での延伸
（ロール延伸）やクリップに把持して拡げることによる
延伸（テンター延伸）や空気圧によって拡げることによ
る延伸（インフレーション延伸）などいずれでも構わな
い。しかし、機械的特性などから考えると、最初に縦方
向（フィルムの長手方向）に延伸し、次に横方向に延
伸、あるいは、横方向−縦方向の順番で延伸する逐次２
軸延伸が好ましい。この縦、横方向の順に延伸する逐次
二軸延伸を例にとって具体的に説明するが、後のフィル
ムの特性を満足するものであれば以下の方法に限定され
るものではない。The unstretched sheet obtained is stretched at least uniaxially. The method may be any of stretching between rolls having a speed difference (roll stretching), stretching by gripping and spreading by a clip (tenter stretching), stretching by expanding by air pressure (inflation stretching). However, considering the mechanical properties, etc., it is first stretched in the machine direction (longitudinal direction of the film) and then in the transverse direction, or in the order of transverse direction-machine direction.
Axial stretching is preferred. The sequential biaxial stretching in which the machine direction and the transverse direction are sequentially carried out will be specifically described as an example, but the method is not limited to the following method as long as the characteristics of the film to be obtained later are satisfied.
【０００７】まず縦延伸はロール延伸により行う。この
時の延伸倍率は1.2 〜5.0 倍、延伸温度は100 〜140 ℃
の範囲で実施することが望ましい。延伸倍率が1.2 倍未
満であると機械的強度が不足し、また5.0 倍を越えると
後の横延伸が困難になり平面性に優れたフィルムが得ら
れない。延伸温度が90℃未満であるとシートが軟化せず
延伸が困難であり、140 ℃を越えると結晶化度が高くな
りすぎ後の横延伸が困難になる。延伸時のシートの加熱
方法は、ロールによる加熱、赤外線による加熱、その他
の方法、これらの併用でも構わない。また予熱、延伸ロ
ールの任意の場所にガイドロールまたはニップロールを
用いてもよい。また縦延伸は２回以上続けて行うことが
後に述べる特性を満足するためにも好ましい。この場
合、１回目の延伸を延伸温度が115 〜140 ℃の範囲で1.
1 〜1.4 倍延伸し、２回目以降の延伸倍率は全段の合計
倍率が1.2 〜5.0 倍となるように、延伸温度は100 〜13
5 ℃の範囲で実施するのが望ましい。全段の合計延伸倍
率が1.2 倍未満であると機械的強度が不足し、また5.0
倍を越えると横延伸時破断が生じやすくなる。１回目の
延伸温度が115 ℃未満であると延伸応力が高くなり配向
が進み、Nzを1.623 以下とすることが困難になる。ま
た、140 ℃を越えると結晶化度が高くなり過ぎ破断が生
じやすくなり２回目の延伸が困難となる。２回目の延伸
は延伸温度が100℃未満であるとシートが軟化せず延伸
が困難であり、135 ℃を越えると結晶化度が高くなりす
ぎ破断が生じやすくなる。続く横延伸においてはテンタ
ー延伸が望ましい。さらに横延伸終了後に縦または横方
向に１回以上再延伸することによりその方向の機械的強
度を高くすることも可能である。また先に横延伸をした
後に縦延伸をする方法（たとえば特開昭64−5819号、特
開平１−188322号公報など）やフィルムの端部と中央部
の物性差をなくすための方法（たとえば特開平３−1582
25号公報など）を用いることもできる。First, the longitudinal stretching is performed by roll stretching. At this time, the draw ratio is 1.2 to 5.0 times, and the draw temperature is 100 to 140 ° C.
It is desirable to carry out in the range of. If the stretching ratio is less than 1.2 times, the mechanical strength will be insufficient, and if it exceeds 5.0 times, lateral stretching afterwards will be difficult and a film having excellent flatness cannot be obtained. If the stretching temperature is less than 90 ° C, the sheet will not be softened and stretching will be difficult, and if it exceeds 140 ° C, the crystallinity will be too high and lateral stretching afterwards will be difficult. The heating method of the sheet during stretching may be heating with a roll, heating with an infrared ray, other methods, or a combination thereof. Further, a guide roll or a nip roll may be used at any place of the preheating and stretching rolls. Further, it is preferable to carry out the longitudinal stretching twice or more in succession in order to satisfy the characteristics described later. In this case, the first stretching is performed at a stretching temperature of 115 to 140 ° C. for 1.
The stretching temperature is 100 to 13 so that the total stretching ratio of all stages is 1.2 to 5.0 times.
It is desirable to perform it within the range of 5 ° C. If the total draw ratio of all stages is less than 1.2 times, the mechanical strength will be insufficient and
If it exceeds twice, breakage easily occurs during transverse stretching. If the first drawing temperature is less than 115 ° C, the drawing stress becomes high and the orientation proceeds, making it difficult to set Nz to 1.623 or less. On the other hand, if the temperature exceeds 140 ° C., the degree of crystallinity becomes so high that breakage is likely to occur, making the second stretching difficult. In the second stretching, if the stretching temperature is less than 100 ° C., the sheet is not softened and it is difficult to stretch, and if it exceeds 135 ° C., the crystallinity becomes too high and breakage easily occurs. In the subsequent transverse stretching, tenter stretching is desirable. Further, it is possible to increase the mechanical strength in the direction by re-stretching once or more in the longitudinal or transverse direction after the completion of the transverse stretching. Further, a method of first performing transverse stretching and then longitudinal stretching (for example, JP-A-64-5819 and JP-A-1-188322) or a method for eliminating the difference in physical properties between the end portion and the central portion of the film (for example, JP-A-3-1582
No. 25, etc.) can also be used.
【０００８】以上の条件に加えて本発明において特に重
要となる点は、少なくとも１回は延伸温度115 〜140 ℃
の範囲で延伸速度10000%／分、好ましくは15000%／分、
さらに好ましくは20000%／分以上で延伸する工程を含む
ことである。延伸速度が10000%／分未満の場合、機械的
強度や特に平面性に優れたフィルムを得ることが困難に
なる。また、延伸温度115 ℃未満であるとフィルムの厚
み方向の屈折率Nzを1.623 以下とすることが困難にな
り、130 ℃を越えると平面性の良いフィルムを得る事が
困難となる。特にこのシンジオタクチックポリスチレン
系フィルムは延伸時にフィルムにかかる応力がポリエチ
レンテレフタレートなどに比べて低くなるため、平面性
を良好にするためには延伸時の温度、速度などの条件が
重要になる。この条件を満たせば延伸方法は特に限定さ
れるものではないが、好ましくはロール延伸法による縦
延伸時にこの条件を満たすようにし、さらに好ましくは
この縦延伸を２回以上続けて行うことが重要である。In addition to the above conditions, a particularly important point in the present invention is that the stretching temperature is 115 to 140 ° C. at least once.
In the range of 10000% / min, preferably 15000% / min,
More preferably, it includes a step of stretching at 20000% / min or more. If the stretching speed is less than 10,000% / min, it becomes difficult to obtain a film having excellent mechanical strength and particularly flatness. Further, if the stretching temperature is less than 115 ° C, it becomes difficult to set the refractive index Nz in the thickness direction of the film to 1.623 or less, and if it exceeds 130 ° C, it becomes difficult to obtain a film having good flatness. In particular, this syndiotactic polystyrene-based film has a lower stress applied to the film during stretching as compared with polyethylene terephthalate, and therefore conditions such as temperature and speed during stretching are important for achieving good flatness. The stretching method is not particularly limited as long as this condition is satisfied, but it is important that this condition is satisfied at the time of longitudinal stretching by the roll stretching method, and it is more preferable that this longitudinal stretching is performed twice or more continuously. is there.
【０００９】また本発明においては、延伸終了後に170
〜270 ℃、好ましくは220 〜270 ℃において熱処理す
る。この時縦かつ／または横方向に2%以上緩和させなが
ら熱処理させることにより、より熱収縮率の小さいもの
が得られる。このようにして得られたフィルムは厚み方
向の屈折率が1.623 以下、好ましくは1.621 以下、さら
に好ましくは1.619 以下でなくてはならない。シンジオ
タクチックポリスチレンは側鎖にベンゼン環があるた
め、分子の配向度が高くなるほどフィルムの厚み方向の
屈折率は上がる。よってNzを1.623 を越える範囲にした
場合、フィルム強度など機械的特性は向上するが裂け易
くなる場合やもろくなる場合がある。さらには耐磨耗性
が低下したりする。しかしながら、Nzを1.623 以下範囲
とすることで、側鎖の配向を押さえることができ、フィ
ルムの裂けを防ぎ、よりしなやかなフィルムとすること
が可能となる。また、該範囲にNzがある場合には、フィ
ルムの結晶化度が抑えられるために、耐磨耗性を向上さ
せることが可能となる。ただし、Nzが1.600 未満になる
と、著しく平面性が失われる場合があるため、Nzは1.60
0 以上であることが好ましい。Further, in the present invention, 170
Heat treatment is performed at ˜270 ° C., preferably 220˜270 ° C. At this time, heat treatment is performed while relaxing 2% or more in the longitudinal direction and / or the transverse direction, so that a material having a smaller heat shrinkage rate can be obtained. The film thus obtained must have a refractive index in the thickness direction of 1.623 or less, preferably 1.621 or less, more preferably 1.619 or less. Since syndiotactic polystyrene has a benzene ring in its side chain, the higher the degree of molecular orientation, the higher the refractive index in the thickness direction of the film. Therefore, when Nz is in the range of more than 1.623, mechanical properties such as film strength are improved, but tearing may be easy or brittle. Furthermore, the abrasion resistance may be reduced. However, by setting Nz in the range of 1.623 or less, the orientation of side chains can be suppressed, the film can be prevented from tearing, and a more flexible film can be obtained. Further, when Nz is in the range, the crystallinity of the film is suppressed, so that the abrasion resistance can be improved. However, when Nz is less than 1.600, the flatness may be significantly lost, so Nz is 1.60.
It is preferably 0 or more.
【００１０】また熱収縮率は3%、好ましくは2%、さらに
は1%以下であることが好ましい。3%以上では、乾熱転
写、OHP 、グラビア印刷などで印刷のピッチずれやコピ
ー機、転写機内でつまりが生じ、好ましくない。このよ
うにして得られたフィルムは平面性、印刷性、耐熱性に
優れかつ機械的、電気的特性、透明性、耐薬品性の満足
するため、工業用、包装用、磁気テープ、コンデンサ用
テープ、金属化用フィルムなどあらゆる用途に展開でき
る。特にこれらの用途に展開するためにこれまでに開示
されているポリエステル、ポリオレフィンその他のフィ
ルムの知見を応用することにより、本発明のシンジオタ
クチックポリスチレン系フィルムの特徴をあわせて持
つ、きわめて付加価値の高いフィルムが得られることが
わかった。たとえば工業用においては、制電性フィルム
（たとえば特公昭64−10136 号公報）、紫外線吸収フィ
ルム（たとえば特開昭59−98109 号、同60−54865 号公
報）、高透明フィルム（たとえば特開昭60−85925 号公
報）、粗面化フィルム（たとえば特公昭49−49180 号、
同54−44031 号公報）、空洞含有フィルム（たとえば特
開昭49−134755号公報）、白色フィルム（たとえば特開
昭62−241928号公報）、透明導電性フィルム（たとえば
特開平２−63736 号公報）など、包装用においては熱接
着性フィルム（たとえば特公昭52−30028 号公報）、熱
収縮性フィルム（たとえば特公昭57−31975 号公報）、
易切断性フィルム（たとえば特公昭55−19167 号公
報）、易印刷性フィルム（たとえば特開昭63−286346号
公報）、防曇性フィルム（たとえば特公平１−14252 号
公報）、金属蒸着フィルム（たとえば特公昭62−54671
号公報）、ひねり包装フィルム（たとえば特公昭56−52
748 号公報）など、磁気テープ用（たとえば特開昭61−
112629号、同61−170518号、同62−196121号公報）、コ
ンデンサ用（たとえば特公平１−28493 号、同２−3985
5号公報など）などの技術が応用できる。The heat shrinkage is preferably 3%, preferably 2%, and more preferably 1% or less. When it is 3% or more, it is not preferable because the pitch shift of printing occurs in dry heat transfer, OHP, gravure printing, and the like, and clogging occurs in the copying machine and the transfer machine. The film thus obtained has excellent flatness, printability, heat resistance, and satisfies mechanical, electrical characteristics, transparency, and chemical resistance. Therefore, it is used for industrial, packaging, magnetic tape, and capacitor tape. It can be applied to various applications such as metallizing films. In particular, by applying the knowledge of polyester, polyolefin and other films disclosed so far in order to expand to these applications, the characteristics of the syndiotactic polystyrene film of the present invention are also combined, which is extremely added value. It was found that a high film was obtained. For industrial use, for example, an antistatic film (for example, Japanese Patent Publication No. 64-10136), an ultraviolet absorbing film (for example, Japanese Patent Publication Nos. 59-98109 and 60-54865), and a highly transparent film (for example, Japanese Patent Publication No. 60-85925), a roughened film (for example, Japanese Examined Patent Publication No. 49-49180),
54-44031), void-containing film (for example, JP-A-49-134755), white film (for example, JP-A-62-241928), transparent conductive film (for example, JP-A-2-63736). ) And the like, for packaging, a heat-adhesive film (for example, JP-B-52-30028), a heat-shrinkable film (for example, JP-B-57-31975),
Easy-cutting film (for example, JP-B-55-19167), easy-printing film (for example, JP-A-63-286346), anti-fog film (for example, JP-B-1-14252), metal-deposited film (for example For example, Japanese Patent Publication Sho 62-54671
No.), twist wrapping film (for example, Japanese Patent Publication No. 56-52)
748) and the like for magnetic tape (for example, Japanese Patent Laid-Open No. 61-
No. 112629, No. 61-170518, No. 62-196121), for capacitors (for example, Japanese Patent Publication No. 1-28493, No. 2-3985)
Technology such as No. 5) can be applied.
【００１１】さらにフィルム表面に塗布層を設けること
によって、インキやコーティング剤などの濡れ性や接着
性が改良される（たとえば特開昭60−19522 号公報）。
該塗布層を構成する化合物としては、ポリエステル系樹
脂、ポリウレタン樹脂、ポリエステルウレタン樹脂、ア
クリル系樹脂などの接着性を向上させる手段として開示
させている化合物が適用可能である。また塗布層を設け
る方法としては、グラビアコート方式、キスコート方
式、ディップ方式、スプレイコート方式、カーテンコー
ト方式、エアナイフコート方式、ブレードコート方式、
リバースロールコート方式など通常用いられている方法
が適用できる。塗布する段階としては、配向処理を行う
前の混合重合体物表面にあらかじめ塗布する方法、１軸
方向に配向した空洞含有フィルム表面に塗布し、それを
更に直角方向に配向させる方法、配向処理の終了した空
洞含有フィルム表面に塗布する方法などのいずれの方法
も可能である。本発明においては、必要に応じて表層と
中心層を積層したいわゆる複合フィルムとしても構わな
い。その方法は特に限定されるものではない。しかし生
産性を考慮すると、表層と中心層の原料は別々の押出機
から押出し、１つのダイスに導き未延伸シートを得た
後、少なくとも1 軸に延伸する、いわゆる共押出法によ
る積層が最も好ましい。これらはこれまで例示した添加
物などを表層かつ／または中心層に添加してもよい。ま
た表層と中心層の添加剤の量かつ／または種類をそれぞ
れ変えることによりフィルムの特性を変えることも可能
である。Further, by providing a coating layer on the film surface, the wettability and adhesiveness of ink, coating agent, etc. are improved (for example, JP-A-60-19522).
As the compound constituting the coating layer, the compounds disclosed as means for improving the adhesiveness of polyester resins, polyurethane resins, polyester urethane resins, acrylic resins, etc. can be applied. Further, as a method for providing a coating layer, a gravure coating method, a kiss coating method, a dip method, a spray coating method, a curtain coating method, an air knife coating method, a blade coating method,
A commonly used method such as a reverse roll coating method can be applied. As the step of applying, a method of previously applying to the surface of the mixed polymer before the orientation treatment, a method of applying to the surface of the uniaxially oriented cavity-containing film and further orienting it in the orthogonal direction, Any method such as coating on the surface of the finished void-containing film is possible. In the present invention, a so-called composite film in which a surface layer and a central layer are laminated may be used if necessary. The method is not particularly limited. However, considering productivity, it is most preferable to use the so-called co-extrusion method in which the raw materials for the surface layer and the central layer are extruded from separate extruders, introduced into one die to obtain an unstretched sheet, and then stretched at least uniaxially. . These may be added to the surface layer and / or the central layer with the additives exemplified above. It is also possible to change the characteristics of the film by changing the amounts and / or types of additives in the surface layer and the central layer.
【００１２】[0012]
【作用】本発明において、主としてシンジオタクチック
構造を持つポリスチレンを用いるのは、平面性、印刷
性、耐熱性、耐擦傷性、耐磨耗性に優れかつ機械的、電
気的特性、透明性、耐薬品性の満足する基材を提供せん
とするためである。本発明において、該重合体を少なく
とも一軸に配向させるのは、機械的強度や平面性、耐熱
性を良好にするためである。特に本発明において、フィ
ルムの厚み方向の屈折率Nzを1.623 以下にするのは平面
性、機械的強度を保ったまま耐磨耗性を向上させるため
である。熱収縮率を3%以下にするのは耐熱性を良好にす
るためである。かくして得られたシンジオタクチック構
造ポリスチレンフィルムは工業用、包装用、磁気テープ
用、コンデンサ用などに要求される電気的特性、透明性
や機械的強度に優れ、かつ、平面性、印刷性、耐熱性、
耐擦傷性、耐摩耗性などに優れるものとなった。In the present invention, polystyrene having a syndiotactic structure is mainly used because it is excellent in flatness, printability, heat resistance, scratch resistance and abrasion resistance and mechanical, electrical characteristics, transparency, This is to provide a base material having satisfactory chemical resistance. In the present invention, the polymer is oriented at least uniaxially in order to improve mechanical strength, flatness and heat resistance. Particularly in the present invention, the reason why the refractive index Nz in the thickness direction of the film is set to 1.623 or less is to improve abrasion resistance while maintaining flatness and mechanical strength. The reason why the heat shrinkage rate is 3% or less is to improve heat resistance. The syndiotactic polystyrene film thus obtained has excellent electrical properties, transparency and mechanical strength required for industrial use, packaging, magnetic tape, capacitors, etc., and has flatness, printability, and heat resistance. sex,
It has excellent scratch resistance and abrasion resistance.
【００１３】[0013]
【実施例】次に本発明の実施例および比較例を示す。本
発明に用いる測定・評価方法を以下に示す。 １）フィルムの屈折率Nz （株）アタゴ製アッベ屈折計4Tを用いて、接眼レンズに
偏光板を取り付け、偏光板の向きおよびフィルムの向き
を測定方向に合わせて屈折率を測定した。中間液として
α−ブロモナフタレンを用いた。EXAMPLES Examples and comparative examples of the present invention will be described below. The measurement / evaluation methods used in the present invention are shown below. 1) Refractive index of film Nz Using an Abbe refractometer 4T manufactured by Atago Co., Ltd., a polarizing plate was attached to an eyepiece lens, and the refractive index was measured by aligning the polarizing plate direction and the film direction with the measuring direction. Α-Bromonaphthalene was used as an intermediate liquid.
【００１４】２）熱収縮率 フィルムを幅10mm、長さ250mm とり、200mm 間隔で印を
つけ5gの一定張力下で固定し印の間隔Ａを測る。続い
て、無荷重で30分間、150 ℃雰囲気中のオーブン中につ
るし熱処理した後、5gの一定張力下で固定し、印の間隔
Ｂを求め、以下の式により熱収縮率とした。 （Ａ−Ｂ）／Ａ×100 （％）2) Heat Shrinkage A film having a width of 10 mm and a length of 250 mm is marked at intervals of 200 mm, fixed under a constant tension of 5 g, and the distance A between the marks is measured. Subsequently, the sample was hung in an oven in an atmosphere of 150 ° C. for 30 minutes under no load, heat-treated, and then fixed under a constant tension of 5 g, the mark spacing B was determined, and the heat shrinkage rate was calculated by the following formula. (A-B) / A x 100 (%)
【００１５】３）初期弾性率 フィルムを幅10mm、長さ間隔40mmにおいて引っ張り試験
機（島津製作所製オートグラフ）に取付け、100mm ／分
の速度で引っ張り、立ち上がりの伸びに対する強度をkg
／mm2 単位で求めた。3) Initial elastic modulus The film was mounted on a tensile tester (Autograph manufactured by Shimadzu Corp.) with a width of 10 mm and a length interval of 40 mm, and the film was pulled at a speed of 100 mm / min and the strength against extension at start-up was kg.
It was calculated in units of / mm 2 .
【００１６】４）光線透過率 ＪＩＳ−Ｋ6714に準じ、ポイック積分球式H.T.R メータ
ー（日本精密光学社製）を用い、フィルムの光線透過率
を測定した。4) Light transmittance According to JIS-K6714, the light transmittance of the film was measured using a Poic integrating sphere type HTR meter (manufactured by Nippon Seimitsu Optical Co., Ltd.).
【００１７】５）ヘイズ ＪＩＳ−Ｋ6714に準じ、ポイック積分球式H.T.R メータ
ー（日本精密光学社製）を用い、フィルムのヘイズを測
定した。5) Haze According to JIS-K6714, the haze of the film was measured using a Poic integrating sphere type HTR meter (manufactured by Nippon Seimitsu Optical Co., Ltd.).
【００１８】６）表面粗さ ＪＩＳ−Ｂ0601−1982に準じ、サーフコム300 Ａ型表面
粗さ計（東京精密製）を用い、中心線平均厚さ、最大粗
さを測定した。6) Surface Roughness According to JIS-B0601-1982, the center line average thickness and the maximum roughness were measured using a Surfcom 300 A type surface roughness meter (manufactured by Tokyo Seimitsu Co., Ltd.).
【００１９】７）絶縁破壊電圧 JIS C-2318に準じて行なった。10KV直流絶縁破壊電圧試
験機を用い、23℃相対湿度50％の雰囲気下に於て、100V
/secの昇圧速度で、フィルムが破壊し短絡したときの電
圧を読み取った。7) Dielectric breakdown voltage It was performed according to JIS C-2318. Using a 10KV DC breakdown voltage tester, 100V in an atmosphere of 23 ° C and 50% relative humidity
The voltage when the film was broken and short-circuited was read at a boosting speed of / sec.
【００２０】８）寿命特性 コンデンサーの両端子間に300Vの直流電圧を印加し、15
0 ℃で2000時間以内に100 個中短絡せずにコンデンサー
としての機能を有する素子の残存率を測定した。8) Life characteristics Apply a DC voltage of 300 V between both terminals of the capacitor,
Within 2000 hours at 0 ° C., the residual rate of the element having a function as a capacitor was measured without short-circuiting among 100 pieces.
【００２１】９）フィルムの加工性 フィルムを細幅にスリットしたテープ状ロールを金属ガ
イドロールにこすりつけて高速、長時間走行させると
き、一定の供給張力に対してガイドロール擦過後のテー
プ張力の大小およびガイドロール表面に発生する白粉量
の多少をそれぞれ５段階に評価し次のランク付けで表
す。 （イ）耐擦傷性 １級・・・擦り傷多い ２級・・・擦り傷かなり多い ３級・・・擦り傷ややあり ４級・・・擦り傷ほとんどなし ５級・・・擦り傷なし （ロ）耐摩耗性 １級・・・白粉発生非常に多い ２級・・・白粉発生多い ３級・・・白粉発生ややあり ４級・・・白粉発生ほとんどなし ５級・・・白粉発生なし9) Film processability When a tape-shaped roll having a narrow slit in the film is rubbed against a metal guide roll and run at high speed for a long time, the tape tension after rubbing the guide roll against a constant supply tension is large or small. Also, the amount of white powder generated on the surface of the guide roll is evaluated on a scale of 5 and expressed by the following ranking. (A) Scratch resistance 1st grade: Many scratches 2nd grade: Scratches are fairly large 3rd grade: Slightly scratched 4th grade: Almost no scratches 5th grade: No scratches (b) Abrasion resistance 1st grade: White powder is generated very much 2nd grade: White powder is generated 3rd grade: White powder is slightly generated 4th grade: White powder is hardly generated 5th grade: White powder is not generated
【００２２】10）電磁変換特性 得られたフィルムを磁気塗工し、0.5 インチ幅のビデオ
テープを得た後、S/Nの測定には、（株）シバソク製Ｔ
Ｇ−７／１形ＮＴＳＣ−ＴＶ試験信号発生器および925
Ｄ／１形ＮＴＳＣカラーテレビノイズ測定器を用い、標
準テープに対するクロマS/N を３段階に評価し、次のラ
ンク付けで表す。 １級・・・−1dB 以下 ２級・・・−1dB 〜＋1dB ３級・・・＋1dB 以上10) Electromagnetic conversion characteristics After the obtained film was magnetically coated to obtain a 0.5-inch wide video tape, the S / N was measured by T-manufactured by Shibasoku Co., Ltd.
G-7 / 1 NTSC-TV Test Signal Generator and 925
Using a D / 1 type NTSC color television noise measuring instrument, the chroma S / N for the standard tape is evaluated in 3 levels, and the following ranking is given. Class 1 ・ ・ ・ -1dB or less Class 2 ・ ・ ・ -1dB to + 1dB Class 3 ・ ・ ・ + 1dB or more
【００２３】実施例１ 重量平均分子量28万の主としてシンジオタクチック構造
をとるポリスチレンに平均粒径0.8 μm のシリカを2000
ppm 添加したものをスクリュー径44mmの２軸押出機で31
0 ℃でT-ダイより押し出した。この溶融押し出ししたシ
ートを静電印荷法により40℃の冷却ロールに密着させ、
冷却固化させることにより120 μm の実質的に非晶質で
無配向のシートを得た。このシートをロール周速度を変
えることにより約95℃で予熱した後すぐに縦方向にロー
ル温度約130 ℃で1.4 倍に延伸し続けてロール温度約12
0 ℃で縦方向に2.15倍延伸した。この時の延伸速度は約
30,000%/分であった。続いてテンターで120 ℃で予熱し
た後すぐに横方向に140 ℃で3.3 倍延伸し、次に3%縦、
横方向にリラックスさせながら260 ℃で10秒間熱処理し
たところ12μm の透明性に優れたフィルムが得られた。
得られたフィルムをグラビア印刷したところ、印刷のヌ
ケやゆがみ、ピッチずれなどは起こらず良好なものであ
った。Example 1 To polystyrene having a weight average molecular weight of 280,000 and having a predominantly syndiotactic structure, silica having an average particle diameter of 0.8 μm was added to 2000.
What added ppm was 31 with a twin screw extruder with a screw diameter of 44 mm.
Extruded from T-die at 0 ° C. This melt-extruded sheet was brought into close contact with a 40 ° C cooling roll by the electrostatic printing method,
By cooling and solidifying, a substantially amorphous and non-oriented sheet of 120 μm was obtained. This sheet was preheated at about 95 ° C by changing the peripheral speed of the roll, and immediately after that, it was continuously stretched 1.4 times in the machine direction at a roll temperature of about 130 ° C to a roll temperature of about 12 ° C.
It was stretched 2.15 times in the machine direction at 0 ° C. The stretching speed at this time is about
It was 30,000% / min. Then, after preheating with a tenter at 120 ° C, it was immediately stretched 3.3 times in the transverse direction at 140 ° C, then 3% lengthwise,
When heat-treated at 260 ° C for 10 seconds while relaxing in the lateral direction, a film with excellent transparency of 12 µm was obtained.
When the obtained film was gravure-printed, it was good without printing blanks, distortions, and pitch deviations.
【００２４】比較例１ 実施例１において縦延伸の１回目をロール温度100 ℃で
行なった以外はまったく同様の方法において、２軸延伸
フィルムを得、グラビア印刷を行った。Nzが1.623 を超
えるため耐擦傷性に劣り、印刷後フィルム上に筋上の傷
がついた。Comparative Example 1 A biaxially stretched film was obtained and gravure printing was carried out in the same manner as in Example 1 except that the first longitudinal stretching was performed at a roll temperature of 100 ° C. Since Nz exceeds 1.623, the scratch resistance was poor, and streaks were scratched on the film after printing.
【００２５】比較例２ 実施例１において熱処理の温度を170 ℃に変更した以外
はまったく同様の方法において２軸延伸フィルムを得、
グラビア印刷を行った。熱収縮率が大きいため特に印刷
のピッチずれが起こってしまい印刷性が不良であった。Comparative Example 2 A biaxially stretched film was obtained in the same manner as in Example 1 except that the heat treatment temperature was changed to 170 ° C.
Gravure printing was performed. Since the thermal contraction rate is large, the pitch deviation of the printing particularly occurs and the printability is poor.
【００２６】実施例２ 実施例１において最終フィルムの厚みが188 μm になる
ようにした以外はまったく同様の方法において透明性に
優れた２軸延伸フィルムを得た。このフィルムを５×5m
の大きさに切り、平面なガラス板の上に広げたところ、
フィルム全体をガラス板に密着させることができる平面
性に優れたフィルムとなった。またこのフィルムをＡ４
版の大きさに切り、OHP コピーをしたところ耐熱性に優
れるため、複写機の中に詰まることなくコピーできた。
シンジオタクチックポリスチレンは、たとえばポリエチ
レンテレフタレートに比べ延伸応力が低くなるが、条件
を最適化することにより平面性を良好にできることがわ
かった。Example 2 A biaxially stretched film having excellent transparency was obtained in the same manner as in Example 1 except that the final film had a thickness of 188 μm. This film is 5x5m
When cut into a size and spread on a flat glass plate,
The film has excellent flatness so that the entire film can be brought into close contact with the glass plate. This film is A4
When cut into a plate size and OHP copied, the heat resistance was excellent, so it was possible to copy without clogging the copier.
It has been found that syndiotactic polystyrene has a lower stretching stress than that of polyethylene terephthalate, for example, but that the flatness can be improved by optimizing the conditions.
【００２７】比較例３ 比較例１において最終フィルムの厚みが188 μm になる
ようにした以外はまったく同様の方法において２軸延伸
フィルムを得た。このフィルムを実施例２と同様の試験
をしたところ、平面性は良好であったが、厚み方向のNz
が1.623 以上ためにOHP コピーではフィルム送りが不良
であり、複写機内部のローラーによってフィルムに傷が
ついた。Comparative Example 3 A biaxially stretched film was obtained in the same manner as in Comparative Example 1, except that the final film had a thickness of 188 μm. When this film was tested in the same manner as in Example 2, the flatness was good, but the Nz in the thickness direction was
However, the film feed was not good in the OHP copy because the value was 1.623 or more, and the film was scratched by the roller inside the copier.
【００２８】比較例４ 比較例２において最終フィルムの厚みが188 μm になる
ようにした以外はまったく同様の方法において２軸延伸
フィルムを得た。このフィルムを実施例２と同様の試験
をしたところ、熱処理温度が低いために熱収縮率が高く
平面性にも劣るため、OHP コピーの際に複写機内の高温
の部分でつまりが生じた。Comparative Example 4 A biaxially stretched film was obtained in the same manner as in Comparative Example 2, except that the final film had a thickness of 188 μm. When this film was tested in the same manner as in Example 2, the heat treatment temperature was low, so that the heat shrinkage rate was high and the flatness was inferior. Therefore, clogging occurred at a high temperature portion in the copying machine during OHP copying.
【００２９】実施例３ 実施例１において、添加物として平均粒径0.5 μm のシ
リコン粒子を2000ppm使用し、最終フィルムの厚みが３
μm になるようにした以外はまったく同様の方法におい
て２軸延伸フィルムを得た。このフィルムの絶縁破壊電
圧は約440v／μm であった。このフィルムにアルミニウ
ムを真空中で蒸着してコンデンサを作り、寿命特性を調
べたところ、95％であった。また厚みムラが少ないため
場所による絶縁破壊電圧の差がほとんどなかった。Example 3 In Example 1, 2000 ppm of silicon particles having an average particle size of 0.5 μm were used as an additive, and the final film had a thickness of 3 μm.
A biaxially stretched film was obtained in exactly the same manner except that the thickness was adjusted to μm. The dielectric breakdown voltage of this film was about 440 v / μm. Aluminum was vapor-deposited on this film in vacuum to make a capacitor, and its life characteristics were examined, and it was 95%. Moreover, since there was little thickness unevenness, there was almost no difference in dielectric breakdown voltage depending on the location.
【００３０】比較例５ 実施例３において１段目の縦延伸の際にロール温度約10
5 ℃で延伸した以外はまったく同様の方法において2軸
延伸フィルムを得た。このフィルムはNzが1.623以上で
あったために、アルミニウムを真空中で蒸着する際に分
子鎖方向である横方向にさけてしまった。Comparative Example 5 In Example 3, the roll temperature was about 10 during the first longitudinal stretching.
A biaxially stretched film was obtained in exactly the same manner except that it was stretched at 5 ° C. Since Nz of this film was 1.623 or more, it was avoided in the lateral direction which is the molecular chain direction when aluminum was vapor-deposited in vacuum.
【００３１】実施例４ 実施例１において、添加物として炭酸カルシウムを2500
ppm 使用し、最終フィルムの厚みが９μm になるように
した以外はまったく同様の方法において２軸延伸フィル
ムを得た。このフィルムは滑り性、耐擦傷性、耐摩耗性
が良好であった。またニッケル−コバルトで磁性層をフ
ィルム上に設け電磁変換特性を調べたところ良好であっ
た。Example 4 In Example 1, 2500 calcium carbonate was added as an additive.
A biaxially stretched film was obtained in exactly the same manner except that ppm was used and the final film thickness was set to 9 μm. This film had good slipperiness, scratch resistance, and abrasion resistance. Further, when a magnetic layer was provided on the film with nickel-cobalt and the electromagnetic conversion characteristics were examined, it was satisfactory.
【００３２】比較例６ 比較例１において、添加物として炭酸カルシウムを2500
ppm 使用し、最終フィルムの厚みが９μm になるように
した以外はまったく同様の方法において２軸延伸フィル
ムを得た。得られたフィルムを実施例４と同様の試験を
した結果、Nzが1.623 以上であるため、フィルムの加工
性試験中にフィルムに傷が入るとともに、白粉が発生し
た。COMPARATIVE EXAMPLE 6 In Comparative Example 1, 2,500 calcium carbonate was added as an additive.
A biaxially stretched film was obtained in exactly the same manner except that ppm was used and the final film thickness was set to 9 μm. The obtained film was tested in the same manner as in Example 4. As a result, Nz was 1.623 or more, so that the film was scratched during the workability test of the film and white powder was generated.
【００３３】[0033]
【発明の効果】本発明のシンジオタクチック構造ポリス
チレンフィルムは工業用、包装用、磁気テープ用、コン
デンサ用などに要求される電気的特性、透明性や機械的
強度に優れ、かつ、延伸条件の最適化により平面性、印
刷性、耐熱性、耐擦傷性、耐摩耗性などに優れるものと
なった。INDUSTRIAL APPLICABILITY The syndiotactic polystyrene film of the present invention has excellent electrical properties, transparency and mechanical strength required for industrial use, packaging, magnetic tapes, capacitors, etc. By optimizing, it has become excellent in flatness, printability, heat resistance, scratch resistance, wear resistance, etc.
【００３４】[0034]
【表１】 [Table 1]
【００３５】[0035]
【表２】 [Table 2]
【００３６】[0036]
【表３】 [Table 3]
【００３７】[0037]
【表４】 [Table 4]
Claims (1)
るポリスチレン系重合体における少なくとも1 軸方向に
延伸された、フィルムの厚み方向の屈折率Nzが1.623 以
下でありかつ150 ℃の熱収縮率が3%以下であることを特
徴とするフィルム。1. A polystyrene polymer mainly composed of a syndiotactic structure, which is stretched in at least one axis direction and has a refractive index Nz in the thickness direction of the film of 1.623 or less and a heat shrinkage ratio of 150 ° C. of 3% or less. A film characterized by being.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5169293A JPH0724911A (en) | 1993-07-08 | 1993-07-08 | Syndyotactic polystyrene film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5169293A JPH0724911A (en) | 1993-07-08 | 1993-07-08 | Syndyotactic polystyrene film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0724911A true JPH0724911A (en) | 1995-01-27 |
Family
ID=15883837
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5169293A Pending JPH0724911A (en) | 1993-07-08 | 1993-07-08 | Syndyotactic polystyrene film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0724911A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0732468A (en) * | 1993-07-16 | 1995-02-03 | Toyobo Co Ltd | Thermal shrinkable polystyrene film |
| EP0745473A3 (en) * | 1995-05-29 | 1998-03-25 | Toyo Boseki Kabushiki Kaisha | Oriented film including polystyrene polymer having syndiotactic configuration |
| JP2006152209A (en) * | 2004-12-01 | 2006-06-15 | Shin Etsu Polymer Co Ltd | Resin sheet and packaging material for electronic parts |
| WO2008156210A1 (en) * | 2007-06-21 | 2008-12-24 | Teijin Limited | Insulating film |
| JP2009096921A (en) * | 2007-10-18 | 2009-05-07 | Teijin Ltd | Highly insulating film |
| US7544414B2 (en) | 2002-05-17 | 2009-06-09 | Toyo Boseki Kabushiki Kaisha | Oriented syndiotactic polystyrene-base film |
| JP2009235321A (en) * | 2008-03-28 | 2009-10-15 | Teijin Ltd | High insulation film |
| JP2011088387A (en) * | 2009-10-23 | 2011-05-06 | Idemitsu Kosan Co Ltd | Laminate for manufacturing flexible printed board |
| US7939174B2 (en) | 2001-04-26 | 2011-05-10 | Toyo Boseki Kabushiki Kaisha | Heat-shrinkable polyester film roll and a process for producing the same |
| JP2018001626A (en) * | 2016-07-04 | 2018-01-11 | 倉敷紡績株式会社 | Release film and resin molded article manufacturing method |
| CN113276377A (en) * | 2021-05-26 | 2021-08-20 | 广东工业大学 | Preparation method of high-strength high-toughness polystyrene film |
Citations (41)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6377905A (en) * | 1986-09-22 | 1988-04-08 | Idemitsu Kosan Co Ltd | Styrene polymer molding |
| JPH01110122A (en) * | 1987-10-23 | 1989-04-26 | Asahi Chem Ind Co Ltd | Production of syndiotactic polystyrenic film |
| JPH01168709A (en) * | 1987-12-25 | 1989-07-04 | Asahi Chem Ind Co Ltd | Syndiotactic polystyrene film |
| JPH01182346A (en) * | 1988-01-14 | 1989-07-20 | Idemitsu Kosan Co Ltd | Molded body of styrene based resin and production thereof |
| JPH01316246A (en) * | 1987-12-04 | 1989-12-21 | Idemitsu Kosan Co Ltd | Styrene resin oriented molded product and its manufacture |
| JPH0267328A (en) * | 1988-08-31 | 1990-03-07 | Idemitsu Kosan Co Ltd | Raw material for food packaging |
| JPH02162083A (en) * | 1988-12-16 | 1990-06-21 | Idemitsu Petrochem Co Ltd | Ink ribbon |
| JPH02279731A (en) * | 1989-04-21 | 1990-11-15 | Asahi Chem Ind Co Ltd | Transparent syndiotactic polystyrene film |
| JPH0370746A (en) * | 1989-08-11 | 1991-03-26 | Idemitsu Kosan Co Ltd | Film having smoothness |
| JPH0374437A (en) * | 1989-08-14 | 1991-03-29 | Idemitsu Kosan Co Ltd | Readily slippery film |
| JPH0386706A (en) * | 1989-08-31 | 1991-04-11 | Idemitsu Kosan Co Ltd | Magnetic recording medium |
| JPH0395723A (en) * | 1989-09-08 | 1991-04-22 | Idemitsu Kosan Co Ltd | Magnetic card |
| JPH0399828A (en) * | 1989-09-14 | 1991-04-25 | Idemitsu Kosan Co Ltd | Preparation of styrenic polymer film |
| JPH03109454A (en) * | 1989-09-22 | 1991-05-09 | Idemitsu Kosan Co Ltd | Magnetic disk |
| JPH03114728A (en) * | 1989-09-29 | 1991-05-15 | Idemitsu Kosan Co Ltd | Manufacture of rolled article |
| JPH03124750A (en) * | 1989-10-09 | 1991-05-28 | Idemitsu Kosan Co Ltd | Electrical insulating film and capacitor |
| JPH03124427A (en) * | 1989-10-09 | 1991-05-28 | Idemitsu Kosan Co Ltd | Manufacture of styrene polymer film |
| JPH03131644A (en) * | 1989-10-18 | 1991-06-05 | Idemitsu Kosan Co Ltd | Production of styrene-based polymer film |
| JPH03149206A (en) * | 1989-11-06 | 1991-06-25 | Idemitsu Kosan Co Ltd | Production of oriented film or sheet |
| JPH04103757A (en) * | 1990-08-24 | 1992-04-06 | Idemitsu Kosan Co Ltd | Film for package |
| JPH04305429A (en) * | 1991-04-02 | 1992-10-28 | Idemitsu Kosan Co Ltd | Twist-wrapping film |
| WO1993003211A1 (en) * | 1991-07-29 | 1993-02-18 | Montecatini Tecnologie S.P.A. | SEMICRYSTALLINE MANUFACTURED ARTICLES MADE OF SYNDIOTACTIC POLY-P-METHYLSTYRENE (s-PpMS) |
| JPH05104617A (en) * | 1991-10-15 | 1993-04-27 | Idemitsu Kosan Co Ltd | Transparent molded body and manufacture thereof |
| JPH05338089A (en) * | 1992-06-12 | 1993-12-21 | Idemitsu Petrochem Co Ltd | Laminate and packaging bag |
| JPH0691750A (en) * | 1992-09-11 | 1994-04-05 | Toyobo Co Ltd | Syndiotactic polystyrene biaxially drawn film |
| JPH06100711A (en) * | 1992-09-21 | 1994-04-12 | Toyobo Co Ltd | Syndiotactic polystyrenic biaxially oriented film |
| JPH0699485A (en) * | 1992-09-21 | 1994-04-12 | Toyobo Co Ltd | Syndiotactic polystyrenic biaxially stretched film |
| JPH06107812A (en) * | 1992-09-28 | 1994-04-19 | Toyobo Co Ltd | Biaxially oriented syndiotactic polystyrene film |
| JPH06107813A (en) * | 1992-09-28 | 1994-04-19 | Toyobo Co Ltd | Biaxially oriented syndiotactic polystyrene film |
| JPH06106616A (en) * | 1992-09-28 | 1994-04-19 | Toyobo Co Ltd | Syndiotactic polystyrenr biaxially oriented film |
| JPH06114924A (en) * | 1992-10-02 | 1994-04-26 | Toyobo Co Ltd | Syndiotactic polystyrene biaxially oriented film |
| JPH06114925A (en) * | 1992-10-02 | 1994-04-26 | Toyobo Co Ltd | Syndiotactic polystyrene series biaxially oriented film |
| JP2546222B2 (en) * | 1992-01-29 | 1996-10-23 | 東洋紡績株式会社 | Syndiotactic polystyrene film |
| JP2637337B2 (en) * | 1992-08-24 | 1997-08-06 | 東洋紡績株式会社 | Syndiotactic polystyrene biaxially stretched film |
| JP2713337B2 (en) * | 1992-08-10 | 1998-02-16 | 東洋紡績株式会社 | Syndiotactic polystyrene stretched film |
| JP2713338B2 (en) * | 1992-08-10 | 1998-02-16 | 東洋紡績株式会社 | Syndiotactic polystyrene film |
| JP3191995B2 (en) * | 1992-08-10 | 2001-07-23 | 東洋紡績株式会社 | Polystyrene-based biaxially stretched film |
| JP3270135B2 (en) * | 1992-09-04 | 2002-04-02 | 東洋紡績株式会社 | Syndiotactic polystyrene biaxially stretched film for condenser |
| JP3287419B2 (en) * | 1992-08-24 | 2002-06-04 | 東洋紡績株式会社 | Syndiotactic polystyrene biaxially stretched film |
| JP3287417B2 (en) * | 1992-08-10 | 2002-06-04 | 東洋紡績株式会社 | Syndiotactic polystyrene biaxially stretched film |
| JP3287418B2 (en) * | 1992-08-24 | 2002-06-04 | 東洋紡績株式会社 | Syndiotactic polystyrene biaxially stretched film |
-
1993
- 1993-07-08 JP JP5169293A patent/JPH0724911A/en active Pending
Patent Citations (41)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6377905A (en) * | 1986-09-22 | 1988-04-08 | Idemitsu Kosan Co Ltd | Styrene polymer molding |
| JPH01110122A (en) * | 1987-10-23 | 1989-04-26 | Asahi Chem Ind Co Ltd | Production of syndiotactic polystyrenic film |
| JPH01316246A (en) * | 1987-12-04 | 1989-12-21 | Idemitsu Kosan Co Ltd | Styrene resin oriented molded product and its manufacture |
| JPH01168709A (en) * | 1987-12-25 | 1989-07-04 | Asahi Chem Ind Co Ltd | Syndiotactic polystyrene film |
| JPH01182346A (en) * | 1988-01-14 | 1989-07-20 | Idemitsu Kosan Co Ltd | Molded body of styrene based resin and production thereof |
| JPH0267328A (en) * | 1988-08-31 | 1990-03-07 | Idemitsu Kosan Co Ltd | Raw material for food packaging |
| JPH02162083A (en) * | 1988-12-16 | 1990-06-21 | Idemitsu Petrochem Co Ltd | Ink ribbon |
| JPH02279731A (en) * | 1989-04-21 | 1990-11-15 | Asahi Chem Ind Co Ltd | Transparent syndiotactic polystyrene film |
| JPH0370746A (en) * | 1989-08-11 | 1991-03-26 | Idemitsu Kosan Co Ltd | Film having smoothness |
| JPH0374437A (en) * | 1989-08-14 | 1991-03-29 | Idemitsu Kosan Co Ltd | Readily slippery film |
| JPH0386706A (en) * | 1989-08-31 | 1991-04-11 | Idemitsu Kosan Co Ltd | Magnetic recording medium |
| JPH0395723A (en) * | 1989-09-08 | 1991-04-22 | Idemitsu Kosan Co Ltd | Magnetic card |
| JPH0399828A (en) * | 1989-09-14 | 1991-04-25 | Idemitsu Kosan Co Ltd | Preparation of styrenic polymer film |
| JPH03109454A (en) * | 1989-09-22 | 1991-05-09 | Idemitsu Kosan Co Ltd | Magnetic disk |
| JPH03114728A (en) * | 1989-09-29 | 1991-05-15 | Idemitsu Kosan Co Ltd | Manufacture of rolled article |
| JPH03124750A (en) * | 1989-10-09 | 1991-05-28 | Idemitsu Kosan Co Ltd | Electrical insulating film and capacitor |
| JPH03124427A (en) * | 1989-10-09 | 1991-05-28 | Idemitsu Kosan Co Ltd | Manufacture of styrene polymer film |
| JPH03131644A (en) * | 1989-10-18 | 1991-06-05 | Idemitsu Kosan Co Ltd | Production of styrene-based polymer film |
| JPH03149206A (en) * | 1989-11-06 | 1991-06-25 | Idemitsu Kosan Co Ltd | Production of oriented film or sheet |
| JPH04103757A (en) * | 1990-08-24 | 1992-04-06 | Idemitsu Kosan Co Ltd | Film for package |
| JPH04305429A (en) * | 1991-04-02 | 1992-10-28 | Idemitsu Kosan Co Ltd | Twist-wrapping film |
| WO1993003211A1 (en) * | 1991-07-29 | 1993-02-18 | Montecatini Tecnologie S.P.A. | SEMICRYSTALLINE MANUFACTURED ARTICLES MADE OF SYNDIOTACTIC POLY-P-METHYLSTYRENE (s-PpMS) |
| JPH05104617A (en) * | 1991-10-15 | 1993-04-27 | Idemitsu Kosan Co Ltd | Transparent molded body and manufacture thereof |
| JP2546222B2 (en) * | 1992-01-29 | 1996-10-23 | 東洋紡績株式会社 | Syndiotactic polystyrene film |
| JPH05338089A (en) * | 1992-06-12 | 1993-12-21 | Idemitsu Petrochem Co Ltd | Laminate and packaging bag |
| JP3191995B2 (en) * | 1992-08-10 | 2001-07-23 | 東洋紡績株式会社 | Polystyrene-based biaxially stretched film |
| JP3287417B2 (en) * | 1992-08-10 | 2002-06-04 | 東洋紡績株式会社 | Syndiotactic polystyrene biaxially stretched film |
| JP2713337B2 (en) * | 1992-08-10 | 1998-02-16 | 東洋紡績株式会社 | Syndiotactic polystyrene stretched film |
| JP2713338B2 (en) * | 1992-08-10 | 1998-02-16 | 東洋紡績株式会社 | Syndiotactic polystyrene film |
| JP3287418B2 (en) * | 1992-08-24 | 2002-06-04 | 東洋紡績株式会社 | Syndiotactic polystyrene biaxially stretched film |
| JP3287419B2 (en) * | 1992-08-24 | 2002-06-04 | 東洋紡績株式会社 | Syndiotactic polystyrene biaxially stretched film |
| JP2637337B2 (en) * | 1992-08-24 | 1997-08-06 | 東洋紡績株式会社 | Syndiotactic polystyrene biaxially stretched film |
| JP3270135B2 (en) * | 1992-09-04 | 2002-04-02 | 東洋紡績株式会社 | Syndiotactic polystyrene biaxially stretched film for condenser |
| JPH0691750A (en) * | 1992-09-11 | 1994-04-05 | Toyobo Co Ltd | Syndiotactic polystyrene biaxially drawn film |
| JPH0699485A (en) * | 1992-09-21 | 1994-04-12 | Toyobo Co Ltd | Syndiotactic polystyrenic biaxially stretched film |
| JPH06100711A (en) * | 1992-09-21 | 1994-04-12 | Toyobo Co Ltd | Syndiotactic polystyrenic biaxially oriented film |
| JPH06106616A (en) * | 1992-09-28 | 1994-04-19 | Toyobo Co Ltd | Syndiotactic polystyrenr biaxially oriented film |
| JPH06107813A (en) * | 1992-09-28 | 1994-04-19 | Toyobo Co Ltd | Biaxially oriented syndiotactic polystyrene film |
| JPH06107812A (en) * | 1992-09-28 | 1994-04-19 | Toyobo Co Ltd | Biaxially oriented syndiotactic polystyrene film |
| JPH06114925A (en) * | 1992-10-02 | 1994-04-26 | Toyobo Co Ltd | Syndiotactic polystyrene series biaxially oriented film |
| JPH06114924A (en) * | 1992-10-02 | 1994-04-26 | Toyobo Co Ltd | Syndiotactic polystyrene biaxially oriented film |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0732468A (en) * | 1993-07-16 | 1995-02-03 | Toyobo Co Ltd | Thermal shrinkable polystyrene film |
| EP0745473A3 (en) * | 1995-05-29 | 1998-03-25 | Toyo Boseki Kabushiki Kaisha | Oriented film including polystyrene polymer having syndiotactic configuration |
| US7939174B2 (en) | 2001-04-26 | 2011-05-10 | Toyo Boseki Kabushiki Kaisha | Heat-shrinkable polyester film roll and a process for producing the same |
| US7544414B2 (en) | 2002-05-17 | 2009-06-09 | Toyo Boseki Kabushiki Kaisha | Oriented syndiotactic polystyrene-base film |
| JP2006152209A (en) * | 2004-12-01 | 2006-06-15 | Shin Etsu Polymer Co Ltd | Resin sheet and packaging material for electronic parts |
| WO2008156210A1 (en) * | 2007-06-21 | 2008-12-24 | Teijin Limited | Insulating film |
| US8859087B2 (en) | 2007-06-21 | 2014-10-14 | Teijin Limited | Insulating film |
| JP2009096921A (en) * | 2007-10-18 | 2009-05-07 | Teijin Ltd | Highly insulating film |
| JP2009235321A (en) * | 2008-03-28 | 2009-10-15 | Teijin Ltd | High insulation film |
| JP2011088387A (en) * | 2009-10-23 | 2011-05-06 | Idemitsu Kosan Co Ltd | Laminate for manufacturing flexible printed board |
| JP2018001626A (en) * | 2016-07-04 | 2018-01-11 | 倉敷紡績株式会社 | Release film and resin molded article manufacturing method |
| CN113276377A (en) * | 2021-05-26 | 2021-08-20 | 广东工业大学 | Preparation method of high-strength high-toughness polystyrene film |
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