JP3287417B2 - Syndiotactic polystyrene biaxially stretched film - Google Patents
Syndiotactic polystyrene biaxially stretched filmInfo
- Publication number
- JP3287417B2 JP3287417B2 JP21269992A JP21269992A JP3287417B2 JP 3287417 B2 JP3287417 B2 JP 3287417B2 JP 21269992 A JP21269992 A JP 21269992A JP 21269992 A JP21269992 A JP 21269992A JP 3287417 B2 JP3287417 B2 JP 3287417B2
- Authority
- JP
- Japan
- Prior art keywords
- film
- less
- biaxially stretched
- syndiotactic polystyrene
- poly
- 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.)
- Expired - Fee Related
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Description
【０００１】[0001]
【産業上の利用分野】本発明はシンジオタクチックポリ
スチレン系二軸延伸フィルム、さらに詳しく言えば透明
性及び耐熱性に優れ、且つフィルム表面の平滑性に優
れ、フィルムの厚みに関係なくハンドリング特性に優
れ、更にフィルム表面の耐摩耗性に優れたシンジオタク
チックポリスチレン系二軸延伸フィルムに関するもので
ある。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a biaxially stretched syndiotactic polystyrene film, and more particularly, to a film having excellent transparency and heat resistance, excellent surface smoothness, and excellent handling properties regardless of film thickness. The present invention relates to a syndiotactic polystyrene-based biaxially stretched film which is excellent in abrasion resistance of the film surface.
【０００２】[0002]
【従来の技術】シンジオタクチックポリスチレン系二軸
延伸フィルムは耐熱性、電気特性、透明性などに優れ、
磁気テープ用、写真・製版用、コンデンサー用、包装用
等、各種のフィルム用途に展開が期待されてる。これら
のフィルム用として用いられる場合、そのすべり性及び
耐摩耗性はフィルムの製造工程及び各用途における加工
工程の作業性の良否、更にはその製品品質の良否を左右
する大きな要因になっている。一方、フィルム表面が平
滑で、透明性が良好または薄手であること等が強く要求
されている。しかし、シンジオタクチックポリスチレン
系二軸延伸フィルムにおいては、単に表面を平滑化し、
且つ透明化または薄手化したのでは、フィルムの製造時
及び加工時のハンドリング特性の不良、及びフィルムの
走行時のガイドロール等との接触による滑り性不良によ
り、擦り傷や削れによる白紛等が発生すると言う耐摩耗
性が不良となる。また、シンジオタクチックポリスチレ
ン系二軸延伸フィルムは脆く、すべり性を得るために添
加された滑剤の周りにボイドが発生し易く、透明性の低
下が見られる。また、このボイドの発生及び、耐熱性を
良好にするために熱固定温度を高くすることにより、更
に脆さが増し、フィルムの走行時の削れが増大する。す
べり性の良好なフィルムとして、無機粒子を添加し、表
面粗さRaが特定の範囲にあり、静摩擦係数が限定された
ものが知られている（特開平3-74437号）。また、シン
ジオタクチックポリスチレン系二軸延伸フィルムを用い
た、透明性、耐熱性の優れたフィルムが知られている
（特開平1-316246、特開平1-168709、特開平2-279731)
。2. Description of the Related Art Syndiotactic polystyrene biaxially stretched films have excellent heat resistance, electrical properties, transparency, etc.
It is expected to be used in various film applications such as magnetic tapes, photographic / plate making, capacitors, and packaging. When used for these films, their slipperiness and abrasion resistance are major factors that affect the workability of the film production process and the working process in each application, and the quality of the product. On the other hand, it is strongly required that the film surface be smooth, have good transparency or be thin. However, in syndiotactic polystyrene-based biaxially stretched films, the surface is simply smoothed,
In addition, if the film is made transparent or thin, poor handling characteristics during film production and processing, and poor slipperiness due to contact with guide rolls etc. during film running, white scratches due to abrasion and scraping will occur Then, the wear resistance becomes poor. In addition, the syndiotactic polystyrene-based biaxially stretched film is brittle, and a void is easily generated around a lubricant added for obtaining slipperiness, and a decrease in transparency is observed. In addition, by increasing the heat setting temperature to generate the voids and improve the heat resistance, the brittleness further increases, and the abrasion of the film during running increases. As a film having good slip properties, there is known a film to which inorganic particles are added, the surface roughness Ra is in a specific range, and the coefficient of static friction is limited (JP-A-3-74437). Further, using a syndiotactic polystyrene-based biaxially stretched film, a film excellent in transparency and heat resistance is known (JP-A-1-316246, JP-A-1-168709, JP-A-2-79731).
.
【０００３】[0003]
【発明が解決しようとする課題】しかし、上記従来のす
べり性良好なフィルムでは、低速作業時には良好なハン
ドリング特性が得られるが、作業が高速になるとハンド
リング特性が急激に悪化するという問題があった。また
シンジオタクチックポリスチレン系二軸延伸フィルムに
おいては、特にフィルムの厚みが薄くなるとハンドリン
グ特性が悪化する傾向が大きく、上記の無機粒子を添加
し、表面粗さRaと静摩擦係数の範囲を規定したフィルム
においても同様の傾向を備えており、そのために良好な
ハンドリング特性が得られたとしても、厚みが変わると
所望のハンドリング特性が得られなくなっていた。更
に、シンジオタクチックポリスチレン系二軸延伸フィル
ムは脆く、フィルムの製造時及び加工時にロール等との
摩擦によりフィルム表面に擦り傷や白紛等が発生しやす
く、耐摩耗性不良の問題があった。また、このシンジオ
タクチックポリスチレン系二軸延伸フィルムの脆さが原
因となり、すべり性を良好にするために添加した滑剤の
周りにボイドが発生しやすくなり、その結果透明性の低
下や削れの増加などの問題を生じやすくなっていた。一
方、上記従来の、透明性、耐熱性に優れたフィルムにお
いては、透明性を向上させたためにフィルム表面が平滑
になり易く、その結果、ハンドリング特性が不良にな
る。また、シンジオタクチックポリスチレン系ポリマー
の脆さが原因となり、すべり性を良好にするために添加
した滑剤の周りに、延伸時にボイドを発生しやすくな
り、その結果透明性の低下や削れの増加などの問題を生
じやすくなっていた。更に、シンジオタクチックポリス
チレン系二軸延伸フィルムは、耐熱性を優れたものとす
るために高温で熱固定処理を行なうが、これが脆さを更
に増大させる結果となり、耐削れ性不良の原因となって
いた。However, in the above-mentioned conventional film having good slipperiness, good handling characteristics can be obtained at a low speed operation, but there is a problem that the handling characteristics rapidly deteriorate at a high speed operation. . In the case of a syndiotactic polystyrene-based biaxially stretched film, the handling characteristics tend to deteriorate particularly when the thickness of the film is reduced, and the above-mentioned inorganic particles are added, and the surface roughness Ra and the range of the static friction coefficient are defined. Has the same tendency. Therefore, even if good handling characteristics are obtained, desired handling characteristics cannot be obtained when the thickness changes. Further, the syndiotactic polystyrene-based biaxially stretched film is brittle, and abrasion, white powder, and the like are easily generated on the film surface due to friction with a roll or the like at the time of production and processing of the film, and there is a problem of poor abrasion resistance. In addition, due to the brittleness of this syndiotactic polystyrene-based biaxially stretched film, voids tend to be generated around the lubricant added to improve the slipperiness, resulting in reduced transparency and increased scraping. And other problems. On the other hand, in the above-mentioned conventional film having excellent transparency and heat resistance, the film surface is easily smoothed due to the improvement in transparency, and as a result, the handling characteristics are poor. In addition, due to the brittleness of the syndiotactic polystyrene polymer, voids are likely to be generated during stretching around the lubricant added to improve the slipperiness, resulting in reduced transparency and increased scraping. Problems were more likely to occur. Furthermore, the syndiotactic polystyrene-based biaxially stretched film is subjected to a heat setting treatment at a high temperature in order to improve heat resistance, but this results in further increase in brittleness, resulting in poor abrasion resistance. I was
【０００４】本発明は、透明性及び耐熱性に優れ、且つ
フィルム表面の平滑性に優れ、フィルムの厚みに関係な
くハンドリング特性に優れ、更にフィルム表面の耐摩耗
性の良好なシンジオタクチックポリスチレン系二軸延伸
フィルムを提供することを目的とする。The present invention relates to a syndiotactic polystyrene system having excellent transparency and heat resistance, excellent film surface smoothness, excellent handling characteristics irrespective of film thickness, and excellent film surface wear resistance. An object is to provide a biaxially stretched film.
【０００５】[0005]
【課題を解決するための手段】本発明のシンジオタクチ
ックポリスチレン系二軸延伸フィルムの表面ヘーズと内
部ヘーズ（１０μｍ当り）の和が１０％以下で、２００
℃３０分後の熱収縮率が２％以下、少なくとも片面の三
次元表面粗さＳＲａが０．０１７μｍ以上０．０５μｍ
以下、粗さの中心面における単位面積当たりの突起数Ｐ
ＣＣ値が１２００個／ｍｍ2以上であり、且つ空気抜け
速さが５００秒以下であることを特徴とする、透明性及
び耐熱性に優れ、且つフィルム表面の平滑性に優れ、フ
ィルムの厚みに関係なくハンドリング特性に優れ、更に
フィルム表面の耐磨耗性が良好なシンジオタクチックポ
リスチレン系二軸延伸フィルムを提供するものである。Means for Solving the Problems When the sum of the surface haze and the internal haze (per 10 μm) of the syndiotactic polystyrene-based biaxially stretched film of the present invention is 10% or less and 200% or less.
C. The heat shrinkage after 30 minutes is 2% or less , and the three-dimensional surface roughness SRa of at least one side is 0.017 μm or more and 0.05 μm or less.
Hereinafter, the number of protrusions P per unit area on the center plane of roughness will be described.
The CC value is 1200 / mm 2 or more, and the air bleeding speed is 500 seconds or less, excellent in transparency and heat resistance, excellent in film surface smoothness, and excellent in film thickness. Regardless, the present invention provides a syndiotactic polystyrene-based biaxially stretched film having excellent handling characteristics and excellent abrasion resistance on the film surface.
【０００６】本発明に用いられる立体規則性がシンジオ
タクチック構造であるポリスチレン系重合体は、側鎖で
あるフェニル基又は置換フェニル基が核磁気共鳴法によ
り定量されるタクテイシテイがダイアッド（構成単位が
二個）で85％以上、ペンタッド（構成単位が５個）で50
％以上のシンジオタクチック構造であることが望まし
い。The polystyrene-based polymer having a stereoregular syndiotactic structure used in the present invention has a dyad whose phenyl group or substituted phenyl group as a side chain is determined by nuclear magnetic resonance. 85% or more for 2) and 50 for pentad (5 constituent units)
% Or more of the syndiotactic structure.
【０００７】該ポリスチレン系重合体としては、ポリス
チレン、ポリ（p-、m-又はo-メチルスチレン）、ポリ
（2,4-、2,5-、3,4-又は3,5-ジメチルスチレン）、ポリ
（p-ターシャリーブチルスチレン）などのポリ（アルキ
ルスチレン）、ポリ（p-、m-又はo-クロロスチレン）、
ポリ（p-、m-又はo-ブロモスチレン）、ポリ（p-、m-又
はo-フルオロスチレン）、ポリ（o-メチル-p- フルオロ
スチレン）などのポリ（ハロゲン化スチレン）、ポリ
（p-、m-又はo-クロロメチルスチレン）などのポリ（ハ
ロゲン置換アルキルスチレン）、ポリ（p-、m-又はo-メ
トキシスチレン）、ポリ（p-、m-又はo-エトキシスチレ
ン）などのポリ（アルコキシスチレン）、ポリ（p-、m-
又はo-カルボキシメチルスチレン）などのポリ（カルボ
キシアルキルスチレン）ポリ（p-ビニルベンジルプロピ
ル）などのポリ（アルキルエーテルスチレン）、ポリ
（p-トリメチルシリルスチレン）などのポリ（アルキル
シリルスチレン）、さらにはポリ（ビニルベンジルジメ
トキシホスファイド）などが挙げられる。The polystyrene polymer includes polystyrene, poly (p-, m- or o-methylstyrene), poly (2,4-, 2,5-, 3,4- or 3,5-dimethylstyrene) ), Poly (alkylstyrene) such as poly (p-tert-butylstyrene), poly (p-, m- or o-chlorostyrene),
Poly (halogenated styrene) such as poly (p-, m- or o-bromostyrene), poly (p-, m- or o-fluorostyrene), poly (o-methyl-p-fluorostyrene), poly ( Poly (halogen-substituted alkylstyrene) such as p-, m- or o-chloromethylstyrene, poly (p-, m- or o-methoxystyrene), poly (p-, m- or o-ethoxystyrene) Poly (alkoxystyrene), poly (p-, m-
Or o-carboxymethylstyrene) such as poly (carboxyalkylstyrene) poly (alkyletherstyrene) such as poly (p-vinylbenzylpropyl), poly (alkylsilylstyrene) such as poly (p-trimethylsilylstyrene), and furthermore Poly (vinylbenzyldimethoxyphosphide) and the like.
【０００８】本発明においては、前記ポリスチレン系重
合体のなかで、特にポリスチレンが好適である。また、
本発明で用いるシンジオタクチック構造を有するポリス
チレン系重合体は、必ずしも単一化合物である必要はな
く、シンジオタクティシティが前記範囲内であればアタ
クチック構造やアイソタクチック構造のポリスチレン系
重合体との混合物や、共重合体及びそれらの混合物でも
よい。In the present invention, among the polystyrene-based polymers, polystyrene is particularly preferred. Also,
The polystyrene-based polymer having a syndiotactic structure used in the present invention is not necessarily a single compound, and a polystyrene-based polymer having an atactic or isotactic structure as long as the syndiotacticity is within the above range. Or copolymers and mixtures thereof.
【０００９】また本発明に用いるポリスチレン系重合体
は、重量平均分子量が10,000以上、更に好ましくは50,0
00以上である。重量平均分子量が10,000未満のもので
は、強伸度特性や耐熱性に優れた二軸延伸フィルムを得
ることができない。重量平均分子量の上限については、
特に限定されるものではないが、1500,000以上では延伸
張力の増加に伴う破断の発生などが生じるため余り好ま
しくない。The polystyrene polymer used in the present invention has a weight average molecular weight of 10,000 or more, more preferably 50,000 or more.
00 or more. If the weight average molecular weight is less than 10,000, a biaxially stretched film having excellent elongation characteristics and heat resistance cannot be obtained. For the upper limit of the weight average molecular weight,
Although it is not particularly limited, if it is more than 1500,000, it is not preferable because breakage occurs due to increase of the stretching tension.
【００１０】更に、本発明のシンジオタクチックポリス
チレン系二軸延伸フィルムは、公知の方法、例えば、縦
延伸及び横延伸を順に行なう逐次二軸延伸方法のほか、
横・縦・縦延伸法、縦・横・縦延伸法、縦・縦・横延伸
法などの延伸方法を採用することができ、要求される強
度や寸法安定性などの諸特性に応じて選択される。本発
明の、200 ℃における熱収縮率を5%以下にするために
は、この延伸方法の他に、延伸条件の影響が大きい。ま
た、熱固定処理、縦弛緩処理、横弛緩処理などを施すこ
とが必要である。そして、前記の三次元表面粗さSRa 、
粗さの中心面における突起数PCC 値、及び空気抜け速さ
は、フィルムの製膜条件及び滑剤粒子によって調整され
る。滑剤粒子の種類及び添加量は三次元表面粗さSRa、
粗さの中心面における突起数PCC値、及び空気抜け速さ
が所定の範囲内に入るならば特に限定されるものではな
いが、シリカ、二酸化チタン、タルク、カオリナイト等
の金属酸化物、炭酸カルシウム、リン酸カルシウム、硫
酸バリウムなどの金属の塩または有機ポリマーからなる
粒子等のシンジオタクチックポリスチレン系ポリマーに
対し不活性な粒子が例示される。そして、これらの滑剤
は、いずれか一種を単独で用いてもよく、また２種以上
を併用してもよいが、使用する滑剤の平均粒子系は0.01
μｍ以上2.0 μｍ以下、特に0.05μｍ以上1.5 μｍ以下
が好ましく、粒子径のばらつき度（標準偏差と平均粒子
径との比率）が２５％以下が好ましく、添加量はシンジ
オタクチックポリスチレン系ポリマー100 重量％に対し
0.005 重量％以上2.0 重量％以下含有することが好まし
く、特に0.1 重量％以上1.0 重量％以下が好ましい。ま
た、滑剤粒子の形状は、面積形状係数が60% 以上のもの
が１種類以上含まれていることが好ましい。この面積形
状係数は次式によって求められる。 面積形状係数＝（粒子の投影断面積／粒子に外接する円
の面積）× 100（％） 本発明に用いられるポリスチレン系重合体には必要に応
じて、公知の酸化防止剤、帯電防止剤などを適量配合し
たものを用いることができる。配合量は、ポリスチレン
系重合体100 重量％に対して、10重量％以下が望まし
い。10重量％を越えると延伸時に破断が起こり易くな
り、生産安定性が不良となる。本発明のシンジオタクチ
ックポリスチレン系二軸延伸フィルムは表面ヘーズと内
部 ヘーズ(10 μｍ当たり）の和が10％以下、好ましく
は７％以下、更に好ましくは５％以下である。表面ヘー
ズと内部へーず(10 μｍ当たり) の和が10% を越える
と、特に写真、製版用では好ましくない。Furthermore, the syndiotactic polystyrene-based biaxially stretched film of the present invention can be prepared by a known method, for example, a sequential biaxial stretching method in which longitudinal stretching and transverse stretching are performed in order.
We can adopt stretching methods such as horizontal / vertical / longitudinal stretching method, vertical / horizontal / longitudinal stretching method, vertical / longitudinal / horizontal stretching method, and select according to various properties such as required strength and dimensional stability. Is done. In order to reduce the heat shrinkage at 200 ° C. to 5% or less according to the present invention, in addition to this stretching method, the effect of stretching conditions is great. In addition, it is necessary to perform a heat setting process, a vertical relaxation process, a horizontal relaxation process, and the like. And the three-dimensional surface roughness SRa,
The PCC value of the number of protrusions on the central surface of the roughness and the air bleeding speed are adjusted by the film forming conditions and the lubricant particles. The type and amount of the lubricant particles are three-dimensional surface roughness SRa,
No particular limitation is imposed on the number of protrusions PCC value on the center surface of the roughness, and the air bleeding speed is within a predetermined range, but metal oxides such as silica, titanium dioxide, talc, and kaolinite, and carbonates Examples include particles that are inert to syndiotactic polystyrene-based polymers, such as particles of salts of metals such as calcium, calcium phosphate, barium sulfate, or organic polymers. Any one of these lubricants may be used alone, or two or more of them may be used in combination.
μm or more and 2.0 μm or less, particularly preferably 0.05 μm or more and 1.5 μm or less, and the degree of dispersion of the particle diameter (the ratio of the standard deviation to the average particle diameter) is preferably 25% or less, and the amount added is 100% by weight of the syndiotactic polystyrene-based polymer. For%
The content is preferably 0.005% by weight or more and 2.0% by weight or less, particularly preferably 0.1% by weight or more and 1.0% by weight or less. Further, the shape of the lubricant particles preferably includes one or more types having an area shape factor of 60% or more. This area shape factor is obtained by the following equation. Area shape factor = (projected cross-sectional area of particle / area of circle circumscribed to particle) × 100 (%) The polystyrene-based polymer used in the present invention may contain a known antioxidant, antistatic agent, etc., if necessary. Can be used in an appropriate amount. The compounding amount is desirably 10% by weight or less based on 100% by weight of the polystyrene-based polymer. If it exceeds 10% by weight, breakage tends to occur during stretching, and the production stability becomes poor. The sum of the surface haze and the internal haze (per 10 μm) of the biaxially stretched film of the syndiotactic polystyrene of the present invention is 10% or less, preferably 7% or less, more preferably 5% or less. If the sum of the surface haze and the internal haze (per 10 μm) exceeds 10%, it is not preferable particularly for photography and plate making.
【００１１】また、本発明のシンジオタクチックポリス
チレン系二軸延伸フィルムの２００℃３０分後の熱収縮
率は２％以下である。２００℃３０分後の熱収縮率が２
％を越えると製造時に平面性の悪化やしわの発生等によ
り、製品収率の低下が生じる。ここで、熱収縮率を下げ
るために高温にフィルムを長時間さらすと耐磨耗性が不
良になるため、縦延伸処理後に緩和処理を行うことや、
熱固定温度及び時間を一定範囲に保つこと、更に必要に
応じて熱固定処理後に横及び／叉は縦弛緩処理すること
が好ましい。ここで、縦延伸後の縦弛緩処理は延伸温度
以上、冷結晶化温度以下で、縦弛緩処理後のフィルムの
１５０℃３０分後の熱収縮率が５％以下になるように弛
緩処理し、熱固定温度は２２０℃以上、融点未満の温度
で３０秒以内、好ましくは１０秒以内で行い、横及び縦
方向の弛緩処理は熱固定処理の最高温度以下で平面性が
乱れない程度に弛緩処理することが好ましい。 The heat shrinkage of the biaxially stretched syndiotactic polystyrene film of the present invention at 200 ° C. for 30 minutes is 2% or less . The heat shrinkage after 30 minutes at 200 ° C is 2
% , The product yield is reduced due to deterioration of flatness or wrinkles during production. Here, if the film is exposed to a high temperature for a long time to reduce the heat shrinkage, the abrasion resistance becomes poor.
It is preferable to keep the heat setting temperature and time within a certain range, and further to perform a horizontal and / or longitudinal relaxation treatment after the heat setting treatment as necessary. Here, the longitudinal relaxation treatment after the longitudinal stretching is performed at a temperature not lower than the stretching temperature and not higher than the cold crystallization temperature so that the heat shrinkage of the film after the longitudinal relaxation treatment at 150 ° C. for 30 minutes becomes 5% or less, The heat setting temperature is 220 ° C. or higher and lower than the melting point within 30 seconds, preferably within 10 seconds. The horizontal and vertical relaxation processes are performed at a temperature lower than the maximum temperature of the heat setting process so that the flatness is not disturbed. Is preferred.
【００１２】本発明のシンジオタクチックポリスチレン
系二軸延伸フィルムの少なくとも片面の三次元表面粗さ
SRa は0.01μm 以上0.05μm 以下の範囲内にある事が必
要である。SRa が0.01μm 未満ではハンドリング特性及
び走行特性が不良になり0.05μm を越えると、例えば磁
気テープ用途では電磁変換特性が不良になり、写真、製
版用途では透明性が減少するため好ましくなく、フィル
ムコンデンサー用途では耐電圧特性の低下の問題を生じ
る。The three-dimensional surface roughness of at least one surface of the biaxially stretched syndiotactic polystyrene film of the present invention.
SRa must be within the range of 0.01 μm or more and 0.05 μm or less. If SRa is less than 0.01 μm, the handling characteristics and running characteristics will be poor, and if it exceeds 0.05 μm, for example, electromagnetic conversion characteristics will be poor in magnetic tape applications, and transparency will be reduced in photographic and plate making applications. In applications, there arises a problem that the withstand voltage characteristics deteriorate.
【００１３】また、粗さの中心面における単位面積当た
りの突起数PCC 値は1200個／mm2 以上であることが必要
である。PCC 値が1200個／mm2 未満では走行特性が不良
となる。PCC 値について特に上限は設けていないが、SR
a が0.05μｍ以下の場合5000個／mm2 以上とすることは
困難である。更に、本発明のシンジオタクチックポリス
チレン系二軸延伸フィルムの空気抜け速さは500 秒以下
である必要がある。更に好ましくは300 秒以下である。
即ち、空気抜け速さを500 秒以下、更に好ましくは300
秒以下にすることにより、高速作業時においても、フィ
ルムの厚みや強度とは無関係にハンドリング特性が良好
なシンジオタクチックポリスチレン系二軸延伸フィルム
が得られる。反対に、空気抜け速さが500 秒を越えた場
合、高速作業時のハンドリング特性が不良となり、例え
ばフィルムを高速でロール状に巻き取る場合にフィルム
と巻き取りロールの間に空気が取り込まれしわが生じや
すく、巻姿が不良になったり、フィルムが巻き込む空気
層の潤滑効果によってフィルムが幅方向に蛇行してロー
ルの端面の不揃いが生じたりする。Further, the PCC value of the number of projections per unit area on the central surface of the roughness needs to be 1200 / mm 2 or more. If the PCC value is less than 1200 pieces / mm 2 , the running characteristics will be poor. There is no specific upper limit for PCC value, but SR
When a is 0.05 μm or less, it is difficult to increase the number to 5000 / mm 2 or more. Furthermore, the air bleeding speed of the biaxially stretched syndiotactic polystyrene-based film of the present invention must be 500 seconds or less. More preferably, the time is 300 seconds or less.
That is, the air bleed speed is 500 seconds or less, more preferably 300 seconds.
By setting the time to seconds or less, a syndiotactic polystyrene-based biaxially stretched film having good handling characteristics can be obtained irrespective of the thickness and strength of the film even during high-speed operation. Conversely, if the air bleed speed exceeds 500 seconds, the handling characteristics during high-speed operation will be poor.For example, when winding a film at high speed, air will be trapped between the film and the take-up roll. The film is likely to be wrinkled, the winding appearance is poor, or the film is meandered in the width direction due to the lubricating effect of the air layer in which the film is wound, and the end faces of the roll are irregular.
【００１４】実施例 以下に実施例にて本発明を具体的に説明するが、本発明
はこれら実施例のみに限定されるものではない。なお、
フィルムの評価方法を以下に示す。 （１）フィルムヘーズ ＪＩＳ−Ｋ６７１４に準じ日本精密光学株式会社製ポイ
ック積分球式ＨＴＲメータＳＥＰ−Ｈ２Ｄ形により表面
ヘーズと内部ヘーズを求めた。 （２）２００℃における熱収縮率 ２００℃で３０分放置後の熱収縮率を測定した。 （３）三次元表面粗さＳＲａ フィルム表面を触針式３次元表面粗さ計（ＳＥ−３Ａ
Ｋ、株式会社小坂研究所社製）を用いて、針の半径２μ
ｍ、荷重３０ｍｇの条件下に、フィルムの長手方向にカ
ットオフ値０．２５ｍｍで、測定長１ｍｍにわたって測
定し、２μｍピッチで５００点に分割し、各点の高さを
３次元粗さ解析装置（ＳＰＡ−１１）に取り込ませた。
これと同様の操作をフィルムの幅方向について２μｍ間
隔で連続的に１５０回、即ちフィルムの幅方向０．３ｍ
ｍにわたって行ない、解析装置にデータを取り込ませ
た。次に、解析装置を用いて、ＳＲａを求めた。EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In addition,
The evaluation method of the film is shown below. (1) Film haze Surface haze and internal haze were determined using a Poic integrating sphere type HTR meter SEP-H2D manufactured by Nippon Seimitsu Optical Co., Ltd. in accordance with JIS-K6714. (2) Heat Shrinkage Rate at 200 ° C. The heat shrinkage rate after standing at 200 ° C. for 30 minutes was measured. (3) Three-dimensional surface roughness SRa The film surface is measured with a stylus type three-dimensional surface roughness meter (SE-3A).
K, manufactured by Kosaka Laboratory Co., Ltd.
m, under a load of 30mg, in the cut-off value 0.25mm in the longitudinal direction of the film, measured over a measurement length 1 mm, divided into 500 points at 2μm pitch, the height of each point three-dimensional roughness analyzer (SPA-11).
The same operation is continuously performed 150 times at intervals of 2 μm in the width direction of the film, that is, 0.3 m in the width direction of the film.
m, and the data was taken into the analyzer. Next, SRa was determined using an analyzer.
【００１５】（４）PCC 値 SRa の算出時における基準高さを有する基準面から0.00
625μｍ以上の高さをもつ突起数を1mm2当たりについて
表したもの。 （５）空気抜け速度 図１に示す測定装置を用意する。即ち、台盤１の上面に
円形の孔１a を設け、この孔1a内に直径70mmのガラス平
板２を固定してガラス平板２を固定してガラス平板２の
外周と孔壁１b との間に溝を形成し、更に上記の孔1bを
囲むリング状の溝孔1cを明け、この溝孔1cを上記ガラス
平板２の外周の溝と連通させ、溝孔1cにパイプ３を介し
て真空ポンプ４の吸引口を接続する。そして、台盤１の
上面に、ガラス平板２を覆う大きさのフィルム試料５を
重ね、その外周を粘着テープ６で台盤１状に密封状に固
定し、真空ポンプ４を駆動し、ガラス平板２の外周部に
干渉縞が出現してからガラス平板２の全面に干渉縞が広
がり、その動きが止るまでの時間（秒）を測定し、この
時間（秒）をもって空気抜け速さとする。(4) From the reference plane having the reference height when calculating the PCC value SRa, 0.00
The number of protrusions having a height of 625 μm or more per mm 2 . (5) Vent Speed The measurement device shown in FIG. 1 is prepared. That is, a circular hole 1a is provided on the upper surface of the base 1, and a glass plate 2 having a diameter of 70 mm is fixed in the hole 1a, and the glass plate 2 is fixed between the outer periphery of the glass plate 2 and the hole wall 1b. A groove is formed, and a ring-shaped groove 1c surrounding the hole 1b is formed. The groove 1c is communicated with a groove on the outer periphery of the glass plate 2, and a vacuum pump 4 is connected to the groove 1c via a pipe 3. Connect the suction port. Then, a film sample 5 having a size to cover the glass plate 2 is placed on the upper surface of the platen 1, and the outer periphery thereof is fixed in a sealed manner to the platen 1 with an adhesive tape 6, and the vacuum pump 4 is driven to drive the glass plate The time (seconds) from when the interference fringes appear on the outer peripheral portion of the glass plate 2 until the interference fringes spread over the entire surface of the glass plate 2 and the movement stops is measured, and this time (seconds) is defined as the air bleeding speed.
【００１６】（６）フィルムのハンドリング特性 広幅のスリットロールを高速でスリットし、小幅のロー
ルに巻直すに際しロール端部の巻ずれ、しわ、バルブ等
を生じないで問題のないロールが得られるかどうかを４
段階評価し、次のランク付けで評価した。 １級；問題のないスリットロールを得ることは極めて困
難 ２級；低速で問題のないスリットロールが得られる ３級；中速で問題のないスリットロールが得られる ４級；高速で問題のないスリットロールが得られる(6) Film Handling Characteristics When slitting a wide slit roll at a high speed and rewinding it into a small width roll, is it possible to obtain a roll that does not cause any problem such as unwinding of the roll end, wrinkles, and valves, etc. Please 4
It was evaluated on a scale and evaluated according to the following ranking. 1st grade: It is extremely difficult to obtain a slit roll with no problem 2nd grade: A slit roll with no problem can be obtained at low speed 3rd grade: A slit roll with no problem can be obtained at medium speed 4th grade: A slit with high speed and no problem Get the roll
【００１７】（７）フィルムの耐摩耗性 フィルムを細幅にスリットしたテープ上ロールを金属製
ガイドロールにこすり付けて走行するとき、一定の供給
張力に体してガイドロール擦過後のテープ張力の大小及
びガイドロール表面に発生する白紛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。 １級；擦り傷多い、または白紛発生非常に多い ２級；擦り傷かなり多い、または白紛発生多い ３級；擦り傷ややあり、または白紛発生ややあり ４級；擦り傷ほとんどなし、または白紛発生ほとんどな
し ５級；擦り傷発生なし、または白紛発生なし ここで、擦り傷と白紛発生量の得られた結果のランクが
異なる場合、悪いほうのランクを採用する。(7) Abrasion resistance of film When running while rubbing the tape roll on which the film is slit into a narrow width on a metal guide roll, the tape tension after the guide roll is rubbed with a constant supply tension. The magnitude of the amount of white powder generated on the surface of the guide roll is evaluated on a scale of 1 to 5, and is expressed by the following ranking. Grade 1; Scratches or white dust are very common Class 2; Scratches are fairly or white powder are often generated Tier 3; Scratches are slightly or white dust are slightly generated Class 4; Scratches are almost nonexistent or white powder is almost generated None 5th grade: No scratches or no white dust generated Here, if the ranks of the obtained results of the amount of scratches and white powder generated are different, the worse rank is adopted.
【００１８】（８）平均粒子径 滑剤粒子を（株）日立製作所製S-５１０型走査型電子顕
微鏡で観察し、写真撮影したものを拡大して複写し、滑
剤の外形をトレースし任意に200 個の粒子を黒く塗りつ
ぶした。この像をニコレ（株）製ルーゼックス500 型画
像解析装置を用いて、それぞれの粒子の水平方向のフェ
レ径を測定し、その平均値を平均粒子径とした。また、
粒子径のばらつき度は下記の式により算出した。 ばらつき度＝（粒子径の標準偏差／平均粒子径）×100
（％）(8) Average particle size The lubricant particles were observed with a scanning electron microscope (S-510, manufactured by Hitachi, Ltd.), and the photograph was enlarged and copied, and the outer shape of the lubricant was traced and arbitrarily measured. Individual particles were painted black. This image was measured for the horizontal Feret diameter of each particle using a Luzex 500 image analyzer manufactured by Nicole Co., Ltd., and the average value was defined as the average particle diameter. Also,
The degree of dispersion of the particle diameter was calculated by the following equation. Variation = (standard deviation of particle diameter / average particle diameter) x 100
(%)
【００１９】（９）面積形状係数 平均粒子径の測定に用いたトレース像から任意に２０個
の粒子を選び（８）で用いた画像解析装置を用いて、そ
れぞれの粒子の投影断面積を測定した。また、それらの
粒子に外接する円の面積を算出し、下記の式により算出
した。 面積形状係数＝（粒子の投影断面積／粒子に外接する円
の面積）× 100（％）(9) Area shape factor 20 particles are arbitrarily selected from the trace image used for measuring the average particle diameter, and the projected cross-sectional area of each particle is measured using the image analyzer used in (8). did. Further, the area of a circle circumscribing the particles was calculated, and calculated by the following equation. Area shape factor = (projected cross-sectional area of particle / area of circle circumscribing the particle) x 100 (%)
【００２０】実施例 滑剤として、平均粒子径0.4 μｍ、ばらつき度23% 、面
積形状係数80％のシリカをシンジオタクチックポリスチ
レン（重量平均分子量300000）100 重量％に対して3.0
重量％添加したポリマーチップと、滑剤の添加されてい
ないポリマーチップを重量比で１対９の割合で混合した
後、乾燥し、295 ℃で溶融し、200 μｍのリップギャッ
プのT ダイから押し出し、40℃の冷却ロールに静電印荷
法により密着・ 冷却固化し、77μｍの無定形シートを得
た。該無定形シートをまずロールにより95℃に予熱し、
表面温度750 ℃の赤外線加熱ヒーターを４本使用更に加
熱し、フィルム温度137 ℃で縦方向に3.9 倍延伸し、つ
いで150 ℃のセラミックロールと40℃の金属ロールの間
で15％縦弛緩処理を行ない、テンターで、フィルムを12
0 ℃に予熱し、横方向に延伸温度120 ℃で3.3 倍延伸
し、260 ℃で10秒熱固定した。その後、230 ℃で５％横
弛緩処理し、更に220 ℃のセラミックロールと40℃の金
属ロールの間で３％縦弛緩処理した。得られたフィルム
の厚みは6 μｍであった。EXAMPLE As a lubricant, silica having an average particle diameter of 0.4 μm, a degree of dispersion of 23%, and an area shape factor of 80% was added to 100% by weight of syndiotactic polystyrene (weight average molecular weight: 300,000) by 3.0%.
The polymer chip added with weight% and the polymer chip without added lubricant were mixed at a weight ratio of 1: 9, dried, melted at 295 ° C., and extruded from a T-die having a lip gap of 200 μm. It was adhered to a cooling roll at 40 ° C by an electrostatic imprinting method, cooled and solidified to obtain a 77 µm amorphous sheet. The amorphous sheet is first preheated to 95 ° C by a roll,
Four infrared heaters with a surface temperature of 750 ° C were used. Further heating, stretching 3.9 times in the machine direction at a film temperature of 137 ° C, followed by a 15% longitudinal relaxation treatment between a ceramic roll at 150 ° C and a metal roll at 40 ° C. Perform and use a tenter to remove 12 films.
The film was preheated to 0 ° C, stretched 3.3 times in the transverse direction at a stretching temperature of 120 ° C, and heat-set at 260 ° C for 10 seconds. Thereafter, it was subjected to a 5% transverse relaxation treatment at 230 ° C., and further a 3% longitudinal relaxation treatment between a 220 ° C. ceramic roll and a 40 ° C. metal roll. The thickness of the obtained film was 6 μm.
【００２１】比較例 押し出し量を変え、無定形シートの厚みを60μｍとし、
縦方向の延伸において、ロールによりフィルム温度を10
5℃に加熱し、3.0倍延伸し、熱固定処理を270℃で30秒
行い、熱固定処理後の弛緩処理を行わなかった以外は実
施例と同様の操作を行なった。Comparative Example The thickness of the amorphous sheet was changed to 60 μm by changing the extrusion amount.
In the longitudinal stretching, the film temperature was set to 10
Heating to 5 ° C, stretching 3.0 times, heat-setting at 270 ° C for 30 seconds, and performing the same operation as in the example except that the relaxation after the heat-setting was not performed.
【００２２】[0022]
【表１】 [Table 1]
【００２３】[0023]
【発明の効果】以上、記載のとおり、本発明は前記特許
請求の範囲に記載のとおりの構成を採用することによ
り、透明性及び耐熱性に優れ、且つフィルム表面の平滑
性に優れ、フィルムの厚みに関係なくハンドリング特性
に優れ、更にフィルム表面の耐摩耗性に優れたシンジオ
タクチックポリスチレン系二軸延伸フィルムが提供さ
れ、従って、本発明の工業的価値は大である。As described above, according to the present invention, by adopting the constitution described in the claims, the film has excellent transparency and heat resistance, and excellent film surface smoothness. The present invention provides a syndiotactic polystyrene-based biaxially stretched film having excellent handling characteristics irrespective of thickness and further having excellent abrasion resistance on the film surface. Therefore, the industrial value of the present invention is great.
【図面の簡単な説明】[Brief description of the drawings]
【図１】この発明の空気抜け速さを測定するための装置
の断面図である。FIG. 1 is a sectional view of an apparatus for measuring an air bleed speed according to the present invention.
１：台盤 ２：ガラス平板 ３：吸引パイプ ４：真空ポンプ ５：フィルム試料 ６：粘着テープ 1: Base plate 2: Glass plate 3: Suction pipe 4: Vacuum pump 5: Film sample 6: Adhesive tape
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平３−74437（ＪＰ，Ａ) 特開 平６−57015（ＪＰ，Ａ) 特開 平６−57016（ＪＰ，Ａ) 特開 平６−57017（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C08J 5/18 B29C 55/12 - 55/16 ────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-3-74437 (JP, A) JP-A-6-57015 (JP, A) JP-A-6-57016 (JP, A) JP-A-6-57016 57017 (JP, A) (58) Field surveyed (Int. Cl. 7 , DB name) C08J 5/18 B29C 55/12-55/16
Claims (1)
るスチレン系重合体から成り、表面ヘーズと内部ヘーズ
（１０μｍ当り）の和が１０％以下で、２００℃３０分
後の熱収縮率が２％以下、少なくとも片面の三次元表面
粗さＳＲａが０．０１７μｍ以上０．０５μｍ以下であ
り、更に粗さの中心面における単位面積当たりの突起数
ＰＣＣ値が１２００個／ｍｍ2以上であり、且つ空気抜
け速さが５００秒以下であることを特徴とするシンジオ
タクチックポリスチレン系二軸延伸フィルム。1. A styrenic polymer substantially having a syndiotactic structure, wherein the sum of surface haze and internal haze (per 10 μm) is 10% or less, and 200 ° C. for 30 minutes
The heat shrinkage rate after that is 2% or less , the three-dimensional surface roughness SRa of at least one surface is 0.017 μm or more and 0.05 μm or less, and the number of protrusions PCC value per unit area on the central surface of the roughness is 1200 / mm 2 or more, and the air bleeding speed is 500 seconds or less, a syndiotactic polystyrene-based biaxially stretched film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21269992A JP3287417B2 (en) | 1992-08-10 | 1992-08-10 | Syndiotactic polystyrene biaxially stretched film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21269992A JP3287417B2 (en) | 1992-08-10 | 1992-08-10 | Syndiotactic polystyrene biaxially stretched film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0657013A JPH0657013A (en) | 1994-03-01 |
| JP3287417B2 true JP3287417B2 (en) | 2002-06-04 |
Family
ID=16626967
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21269992A Expired - Fee Related JP3287417B2 (en) | 1992-08-10 | 1992-08-10 | Syndiotactic polystyrene biaxially stretched film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3287417B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| JPH06107812A (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 |
| JPH06107813A (en) * | 1992-09-28 | 1994-04-19 | Toyobo Co Ltd | Biaxially oriented syndiotactic polystyrene film |
| JPH0724911A (en) * | 1993-07-08 | 1995-01-27 | Toyobo Co Ltd | Syndyotactic polystyrene film |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1785449A3 (en) | 1998-07-22 | 2007-08-29 | Toyo Boseki Kabushiki Kasisha | Aliphatic polyester film and gas barrier film |
| WO2008156210A1 (en) | 2007-06-21 | 2008-12-24 | Teijin Limited | Insulating film |
-
1992
- 1992-08-10 JP JP21269992A patent/JP3287417B2/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| JPH06107812A (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 |
| JPH06107813A (en) * | 1992-09-28 | 1994-04-19 | Toyobo Co Ltd | Biaxially oriented syndiotactic polystyrene film |
| JPH0724911A (en) * | 1993-07-08 | 1995-01-27 | Toyobo Co Ltd | Syndyotactic polystyrene film |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0657013A (en) | 1994-03-01 |
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