JPS59152952A - Oriented polyester film - Google Patents

Abstract

PURPOSE:The titled film that is obtained by adding kaolin particles of apecific particle sizes and barium sulfate particles of larger average particle sizes than the former, thus showing improved slip properties and non-abrasive qualities without formation of scuff marks and white powder. CONSTITUTION:A polyester mainly composed of recurring units of ethylene terephthalate is combined with 0.01-1.0wt%, preferably 0.1-0.5wt%, of kaolin particles of 0.01-1.5mum, preferably 0.1-0.5mum particle sizes and 0.11-1.0wt%, preferably 0.15-0.5wt%, of barium sulfate particles of 0.5-5.0mum, preferably 0.5- 2.0mum average particle sizes, which is larger than the former particles. These particles are spherical or cubic and less anisotropic. The addition is effected preferably in the form of a slurry.

Description

【発明の詳細な説明】 本発明は滑り性および耐摩耗性に優れた配向ポリエステ
ルフィルムに関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an oriented polyester film having excellent slip properties and abrasion resistance.

−ｆｆにポリエチレンテレフタレートに代表されるごと
きポリエステルは、その優れた物理的および化学的諸特
性の故に１繊維用１成型品用の他、磁気テープ用、写真
用、コンデンサー用１包装用などのフィルム用としても
多種の用途で広く用いられている。Due to its excellent physical and chemical properties, polyesters such as polyethylene terephthalate are used not only for fibers and molded products, but also for films such as magnetic tapes, photographs, and capacitor packaging. It is also widely used for a variety of purposes.

これらのフィルム用として用いられる場合１その滑り性
および耐摩耗特性はフィルムの製造工程および各用途に
おける加工工程の作業性の良否、さらにはその製品品質
の良否を左右する大きな要因となっている。When used for these films, the slipperiness and abrasion resistance properties are major factors that determine the workability of the film manufacturing process and processing process in each application, as well as the quality of the product.

特にポリエステルフィルム表面に磁性層を塗布し磁気テ
ープとして用いる場合には１磁性層塗布時におけるコー
ティングロールとフィルム表面色の摩擦および摩耗が極
めて激しく１フィルム表面へのしわおよび擦り傷が発生
しやすい。In particular, when a magnetic layer is applied to the surface of a polyester film and used as a magnetic tape, the friction and abrasion between the coating roll and the surface color of the film during application of one magnetic layer is extremely severe, and wrinkles and scratches on the surface of the film are likely to occur.

また磁性層塗布後のフィルムをスリットしてオーディ第
１ビデオまたはコンピューター用テープ等に加工した後
でも一リールやカセット等からの引き出し１巻き上げそ
の他の操作の際に、多くのガイド部、再生ヘッド等との
間に摩擦および摩耗が著しく生じ１擦り傷１歪の発生ざ
らにはポリエステルフィルム表面の削れ等による白粉状
物質をイ 析出さｉる結果、磁気記録信号の欠落、即ちドロップア
ウトの大きな要因となる事が多い。Furthermore, even after slitting the film coated with the magnetic layer and processing it into audio, video, computer tape, etc., many guide parts, playback heads, etc. must be removed when pulling out a reel or cassette, winding it up, or other operations. Significant friction and wear occur between the polyester film and the surface of the polyester film, resulting in scratches, scratches, and distortion.As a result, a white powdery substance is deposited due to scratches on the surface of the polyester film, which is a major cause of missing magnetic recording signals, that is, dropouts. It often happens.

一般にフィルム表面の滑り性および耐摩耗性の改良には
１フイルム表面に凹凸を付与する事によりガイドロール
等との間の接触面積を減少せしめる方法が採用されてお
り＼フィルム原料に用いる高分子の触媒残渣から不溶性
の粒子を析出せしめる方法や１不活性の無機粒子を添加
せしめる方法等が用いられている。これら原料高分子中
の粒子はその大きさが大きい程１滑り性の改良効果が大
であるのが一般的であるがへ磁気テープ１特にビデオ用
のごとき精密用途にはその粒子が大きいこと自体がドロ
ップアウト等の欠点発生の原因ともなりつるため１フイ
ルム表面の凹凸は出来るだけ微細である必要があり＼相
反する物性を同時に満足すべき要求がなされているのが
現状である。Generally, to improve the slipperiness and abrasion resistance of a film surface, a method is adopted in which the contact area between guide rolls and the like is reduced by adding irregularities to the film surface. A method in which insoluble particles are precipitated from the catalyst residue, a method in which inert inorganic particles are added, etc. are used. Generally speaking, the larger the size of the particles in these raw polymers, the greater the effect of improving slipperiness. Since this can cause defects such as dropouts, the unevenness on the surface of a film must be as fine as possible, and there are currently demands to satisfy contradictory physical properties at the same time.

性および耐摩耗性の改良が要求されつつある状況下に鑑
み蔦鋭意検討の結果本発明に到達したものである。即ち
本発明は１主たる繰り返し単位がエチレンテレフタレー
トからなるポリエステル中に、平均粒径が０００１−Ｌ
、’５μｍのカオリン粒子を０．０１〜１．０重量％１
および平均粒径が０．５〜５．０μｍでかつ前記カオリ
ン粒子より大である硫酸バリウム粒子を０．１１〜１．
０重量％を含有してなる配向ポリエステルフィルムであ
る。In view of the growing demand for improvements in properties and abrasion resistance, the present invention was arrived at as a result of extensive research. That is, in the present invention, in a polyester in which one main repeating unit is ethylene terephthalate, the average particle size is 0001-L.
, 0.01 to 1.0% by weight of 5 μm kaolin particles1
and barium sulfate particles having an average particle size of 0.5 to 5.0 μm and larger than the above-mentioned kaolin particles.
This is an oriented polyester film containing 0% by weight.

本発明の配向ポリエステルフィルムは、良好す滑り性お
よび耐摩耗性を有しへ擦り傷および白粉発生量が著しく
少ない。The oriented polyester film of the present invention has good sliding properties and abrasion resistance, and produces significantly less scratches and white powder.

本発明における配向ポリエステルフィルムの特徴は１２
梗類の特定成分粒子の特定粒径を有する粒子を特定量ず
つ併用する点にある。即ち特定粒径のカオリン粒子の特
定量と１特定粒径の硫酸バリウム粒子の特定量がフィル
ム中に共存する場合においてのみ１それぞれの粒子の単
独使用や他の粒子類の添加によっては到底達し得ない優
れた効果を発揮し得る事実を見出したものである。The characteristics of the oriented polyester film in the present invention are 12
The point is to use a specific amount of particles having a specific particle size of specific component particles of arborvitae. That is, only when a specific amount of kaolin particles with a specific particle size and a specific amount of barium sulfate particles with a specific particle size coexist in the film, it is possible to achieve this by using each particle alone or by adding other particles. We have discovered the fact that it can exhibit excellent effects.

本発明において）配向ポリエステルフィルムを構成する
ポリエステルは主たる繰り返し単位の８０モル％以上が
エチレンテレフタレートからなるポリエステルであり１
他の構成成分としてはこれと共重合し得るジカルボン酸
類、グリコール類、オキシカルボン酸類等の成分を２０
モル％未満共重合させたものでもよい。なお１配向フイ
ルムとしては二軸配向フィルムが特に好適である。In the present invention), the polyester constituting the oriented polyester film is a polyester in which 80 mol% or more of the main repeating units are ethylene terephthalate;
Other components include dicarboxylic acids, glycols, oxycarboxylic acids, etc. that can be copolymerized with this product.
It may be copolymerized in less than mol%. Note that a biaxially oriented film is particularly suitable as the unidirectionally oriented film.

本発明において、添加すべき不活性無機粒子の第一成分
であるカオリン粒子の平均粒径は０．０１〜１．５μ濯
である必要があり１ ■→ｈ声１ケ平０゜０５〜０．８μ軍がより好ましく、
０．１〜０．５μ翼が特に好ましい。また添加量は該ぎ
りエステルに対し０．０１〜１．０重蓋％とする必要が
あり１０．１〜０．５重量％がより好ましい。In the present invention, the average particle diameter of the kaolin particles, which is the first component of the inert inorganic particles to be added, must be 0.01 to 1.5μ. .8μ force is more preferable,
Particularly preferred are 0.1-0.5μ blades. The amount added needs to be 0.01 to 1.0% by weight, more preferably 10.1 to 0.5% by weight, based on the ester.

また第２成分である硫酸バリウム粒子の平均粒径はＯ９
５〜５゜０μ禦の範囲が必要であり）０・５〜２．０μ
冒がより好ましく１かつ第１成分であるカオリン粒子の
平均粒径より大である事が必要である。添加量は、該ポ
リエステルに対し０．１１〜１．０重量％となる必要が
あり、０゜１５〜０．５重量％がより好ましい。第１成
分であるカオリン粒子および第２成分である硫酸バリウ
ム粒子のそれぞれがこれらの適正範囲を逸脱する場合に
は、本発明の目的とする良好な滑り性および１１１１耗
性付与による擦り傷発生防止効果を発揮し得ないか為ま
たは粒子自体によるドロップアウト発生の原因となる粗
大粒子混入を防ぎ得ない結果となる。In addition, the average particle size of barium sulfate particles, which is the second component, is O9
A range of 5~5゜0μ is required) 0.5~2.0μ
It is more preferable that the average particle size of the kaolin particles is larger than the average particle size of the kaolin particles, which is the first component. The amount added must be 0.11 to 1.0% by weight, more preferably 0.15 to 0.5% by weight, based on the polyester. If the kaolin particles, which are the first component, and the barium sulfate particles, which are the second component, each deviate from these appropriate ranges, the effect of preventing scratches by imparting good slipperiness and 1111 abrasion resistance, which is the objective of the present invention, may not be achieved. As a result, it is not possible to prevent coarse particles from being mixed in, which causes dropout due to the particles themselves.

５０％点における径をさす。Refers to the diameter at the 50% point.

次に１本発明の粒子組成が好ましい理由について述へる
。磁気テープ用ポリエステルフィルムの滑り性および耐
摩耗性を改良する目的でＡポリエステル中に不活性粒子
を添加する方法については従来より多くの提案がなされ
て来ているが１近年の高度化された要求即ち電磁変換特
性として必要な微細で高密度な表面凹凸１フイルムの製
造工程１磁気テープ製造工程および磁気テープ使用時の
滑り性）耐摩耗性を充分に満足し得るには至っていない
。Next, the reason why the particle composition of the present invention is preferable will be described. Many proposals have been made in the past regarding methods of adding inert particles to polyester A for the purpose of improving the slipperiness and abrasion resistance of polyester films for magnetic tapes. That is, it has not yet been possible to fully satisfy the fine and high-density surface irregularities necessary for electromagnetic conversion properties (1) Film manufacturing process (1) Magnetic tape manufacturing process (1) Slipperiness during use of magnetic tape (1) Abrasion resistance.

そこで本発明者らは微細で高密度な表面凹凸１滑り性お
よび耐摩耗性の改良について多種にわたる粒子類の粒径
と添加量およびフィルム特性値との関係を詳細に検討し
た結果、微細で高密度な表　６− 面凹凸形成粒子としてはカオリン粒子が１また滑り性改
良には硫酸バリウム粒子がそれぞれ好ましい串を見出し
た。しかし両粒子単独添加では耐摩耗性は改良されず１
両粒子の共存する状態が最も好ましい事が判明した。Therefore, the present inventors conducted a detailed study on the relationship between the particle size of various types of particles, the amount added, and the film characteristic values in order to improve slipperiness and wear resistance. Table 6 - It has been found that kaolin particles are preferable as surface unevenness forming particles, and barium sulfate particles are preferable for improving slipperiness. However, when both particles were added alone, the wear resistance was not improved.
It has been found that the state where both particles coexist is the most preferable.

なお硫酸バリウム粒子の粒子形状としては一球状または
立方体状に近く異方性の少ない粒子が好ましい。The shape of the barium sulfate particles is preferably unispherical or cubic, and particles with little anisotropy.

以上の様な理由から滑り性および耐摩耗性が良好なポリ
エステルフィルム用不活性粒子としてけ１小粒径成分と
してカオリン１大粒径成分として球も好ましい。For the above reasons, spheres are also preferable as inert particles for polyester films having good slip properties and abrasion resistance, 1 small particle size component and kaolin 1 large particle size component.

本発明における不活性粒子のポリエステル中への添加方
法は、該ポリエステル製造過程における任意の段階でス
ラリー状および粉末状いずれの状態で添加しても良いが
１粒子の飛散防止１均一性向上の点からポリエステル構
成成分の一種であるエチレングリコール中にスラリー状
として分散させて所定量添加する方法が望ましい。また
スラリー状に分散させる場合には）不活性粒子本来の一
次粒径を出来得る限り再現し、粗大凝集粒子の存在を避
けるように留意することが重要である。特に１０μｍ以
上の粗大粒子の存在は磁気テープとした場合のドロップ
アウトの原因となるためＸ分級島分離等適当な手段をこ
うじて除去する必要がある。In the present invention, the inert particles may be added to the polyester at any stage in the polyester manufacturing process in either slurry or powder form, but the following points are important: prevention of scattering of particles, improvement of uniformity, etc. It is preferable to disperse it in the form of a slurry in ethylene glycol, which is a type of polyester component, and add it in a predetermined amount. Furthermore, when dispersing in a slurry form, it is important to reproduce the original primary particle size of the inert particles as much as possible and to avoid the presence of coarse agglomerated particles. In particular, the presence of coarse particles of 10 μm or more causes dropouts when used as a magnetic tape, so it is necessary to remove them by appropriate means such as X-class island separation.

以下実施例によって本発明を説明する。The present invention will be explained below with reference to Examples.

なおＡ平均粒径測定は島津製作所製遠心沈降式粒度分布
測定器によって得た等制球径分布における積算５０％点
の値を採用した。またフィルムの滑り性および耐摩耗性
の評価Ｆｉ、フィルムを細幅にスリットしたテープ状ロ
ールを金属製ガイドロールにこすりつけて高速１長時間
走行させるとき１一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
ンク付けで表わした。Note that for the A average particle size measurement, the value at the cumulative 50% point in the uniform sphere diameter distribution obtained by a centrifugal sedimentation type particle size distribution analyzer manufactured by Shimadzu Corporation was adopted. In addition, the evaluation Fi of the slipperiness and abrasion resistance of the film is when a tape-like roll in which the film is slit into narrow widths is rubbed against a metal guide roll and run at high speed for a long time.1 After the guide roll is rubbed against a constant supply tension. The magnitude of the tape tension and the amount of white powder generated on the surface of the guide roll were each evaluated on a five-point scale) and expressed in the following rankings.

　　− 萎　ｔ　萎　萎　嘔 ｊ１ 喪　　亭−ＩＪｙ エベ　　−ノ　　ぶへ　　−ノ　　ぶへ萎　萎　謁　箋
　萎 Ｈ〜　　　の　　　リ　　　の フィルム中の粗大粒子発生量は得られたフィルムの少量
を２枚のカバーグラス間にはさみ１溶融した後急冷蔦プ
レスし、得られたサンプルの位相差顕微鏡を画像解析処
理装置ルーゼツクス５００（日本レギュレーター製）を
用いて処理し１粒子像内の最大長が１０μｍ以上の二次
凝集粒子の多少によって次の様にランク付けした。- The amount of coarse particles generated in the film is determined by dividing a small amount of the obtained film between two cover glasses. After the scissors 1 are melted, they are rapidly cooled and pressed, and the obtained sample is processed using a phase contrast microscope using an image analysis processing device Luzetx 500 (manufactured by Nippon Regulator) to obtain secondary particles with a maximum length of 10 μm or more in a single particle image. The samples were ranked according to the amount of agglomerated particles as follows.

１級・・・粗大粒子多い ２級・・・粗大粒子やや多い ３級・・・粗大粒子普通 ４級・・・粗大粒子少ない ５級・・・粗大粒子なし 実施例１〜５および比較例１〜４ 平均粒径０゜３μｍのカオリン粒子および平均粒径Ｏ０
８μｍの硫巖バリウム粒子をそれぞれエチレンクリコー
ル中に均一に分散させ１該スラリーをた後反応を完結し
、カオリン粒子および硫酸バリウム粒子を含有したポリ
エチレンテレフタレート−１〇− を得た。次いで得られたポリエチレンテレフタレートを
２８５℃で押出成形し、　９０　’ｃで延伸倍率３．５
倍の縦延伸Ｘ９５“Ｃで延伸倍率３．６倍の横延伸およ
び２２０“Ｃの熱処理を行なって厚さ１５μｍの二軸延
伸ざリエステルフイルムを得た。1st grade...more coarse particles 2nd grade...slightly more coarse particles 3rd grade...coarse particles normal 4th grade...less coarse particles 5th grade...no coarse particles Examples 1 to 5 and Comparative Example 1 ~4 Kaolin particles with an average particle size of 0°3 μm and an average particle size of O0
Barium sulfate particles of 8 μm each were uniformly dispersed in ethylene glycol to form a slurry, and the reaction was completed to obtain polyethylene terephthalate-1 containing kaolin particles and barium sulfate particles. The obtained polyethylene terephthalate was then extruded at 285°C and stretched at a stretching ratio of 3.5 at 90'c.
A biaxially stretched polyester film having a thickness of 15 μm was obtained by performing transverse stretching at a draw ratio of 3.6 times and heat treatment at 220 inches C.

る条件下で得られたフィルムは、いずれも磁気テープ用
として非常に好ましい品質を有していた。All of the films obtained under these conditions had very desirable qualities for use in magnetic tapes.

実施例６〜８および比較例５〜７ カオリン粒子および硫酸バリウム粒子の平均粒径および
所要量をそれぞれ表２に記載したものを採用する以外は
、実施例１〜５と同様の方法で二軸延伸ポリエステルフ
ィルムを得た。得られた各種のフィルムの滑り性、耐摩
耗性および粗大粒子量を評価したところ１本発明を満足
する条件下で得られたフィルムはいずれも磁気テープ用
として非常に好ましい品質を有していた。Examples 6 to 8 and Comparative Examples 5 to 7 Biaxial production was carried out in the same manner as in Examples 1 to 5, except that the average particle diameter and required amount of kaolin particles and barium sulfate particles were those listed in Table 2. A stretched polyester film was obtained. When the slipperiness, abrasion resistance, and amount of coarse particles of the various films obtained were evaluated, it was found that all the films obtained under the conditions satisfying the present invention had very desirable qualities for use in magnetic tapes. .

比較例　８〜１２ 添加すべき不活性無機粒子として〜平均粒径０．３μ講
のカオリン粒子を０．２５重８％１平均粒径０゜８μ篇
の硫酸バリウム粒子を００２０重量％１平均粒径０．６
μ朔の硫酸バリウム粒子を０゜３０重量％、平均粒径１
．５μ雷のシリカ粒子を０００５重童％８よび平均粒径
０゜０４μｍのシリカ粒子を００５０＊量％をそれぞれ
単独で添加した以外は１実施例１　、５と同様の方法で
二軸延伸ポリエステルフィルムを得り。Comparative Examples 8 to 12 As inert inorganic particles to be added, 0.25% by weight of kaolin particles with an average particle size of 0.3μ, 1% by weight of barium sulfate particles with an average particle size of 0°8μ, 1 average particle. Diameter 0.6
0゜30% by weight of barium sulfate particles from μShou, average particle size 1
．． A biaxially stretched polyester film was prepared in the same manner as in Example 1 and 5, except that silica particles with a diameter of 5 μm and silica particles with an average particle size of 0°04 μm were added individually in an amount of 0050*% by weight. I got it.

得られた各種フィルムの滑り性１耐摩耗性および粗大粒
子量を評価したところ表３に示すごとき結果となり１い
ずれも磁気テープ用としては充分とはいえない品質であ
り九本発明を満足する条件以外では磁気テープ用として
好ましい品質が得られないことがわかる。When the slip properties, abrasion resistance, and amount of coarse particles of the obtained various films were evaluated, the results were as shown in Table 3.1 All of these were of a quality that could not be said to be sufficient for use in magnetic tapes.9 Conditions that satisfied the present invention. It can be seen that the preferred quality for magnetic tapes cannot be obtained in other cases.

以下余白 表　　　　１ 表　　　　２ １３− 表　　　　３ 特許出願人　　　東洋紡績株式会社Margin below Table 1 Table 2 13- Table 3 Patent applicant: Toyobo Co., Ltd.

Claims (1)

【特許請求の範囲】[Claims] 主たる繰り返し単位がエチレンテレフタレート粒子より
大である硫酸バリツム粒子を０．１１〜１．０重量％を
含有してなる配向ポリエステルフィルム。An oriented polyester film containing 0.11 to 1.0% by weight of barium sulfate particles whose main repeating unit is larger than ethylene terephthalate particles.