JP2621461B2 - Biaxially oriented polyester film - Google Patents
Biaxially oriented polyester filmInfo
- Publication number
- JP2621461B2 JP2621461B2 JP1035120A JP3512089A JP2621461B2 JP 2621461 B2 JP2621461 B2 JP 2621461B2 JP 1035120 A JP1035120 A JP 1035120A JP 3512089 A JP3512089 A JP 3512089A JP 2621461 B2 JP2621461 B2 JP 2621461B2
- Authority
- JP
- Japan
- Prior art keywords
- particles
- film
- average particle
- alumina
- biaxially oriented
- 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 - Lifetime
Links
Landscapes
- Polyesters Or Polycarbonates (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
【発明の詳細な説明】 [産業上の利用分野] 本発明は、二軸配向ポリエステルフィルムに関し、と
くに磁気テープ用ベースフィルム、包装用、各種産業資
材用フィルムとして好適な、耐スクラッチ性や耐摩耗性
に優れた二軸配向ポリエステルフィルムに関する。Description: FIELD OF THE INVENTION The present invention relates to a biaxially oriented polyester film, which is particularly suitable as a base film for magnetic tape, a film for packaging and a film for various industrial materials, and has scratch resistance and abrasion resistance. The present invention relates to a biaxially oriented polyester film having excellent properties.
[従来の技術] 先に本出願人により、包装用、コンデンサ用あるいは
磁気テープ用ベースフィルムとして、平均粒径0.05〜2.
0μm、モース硬度7以上の粒子を含有させた二軸配向
ポリエステルフィルムが提案されている(特開昭63−23
0741号公報)。このフィルムにおいては、硬い粒子を含
有させることにより、フィルム表面の耐摩耗性を向上し
つつ、該粒子の粒径を比較的大きなものとすることによ
り、フィルム加工時や製品としたときの良好な滑り性、
走行性を確保するようにしている。[Prior art] The applicant has previously reported an average particle size of 0.05 to 2. as a base film for packaging, for a capacitor, or for a magnetic tape.
A biaxially oriented polyester film containing particles of 0 μm and Mohs hardness of 7 or more has been proposed (JP-A-63-23).
No. 0741). In this film, by containing hard particles, while improving the abrasion resistance of the film surface, by making the particle diameter of the particles relatively large, good film processing and when the product Slipperiness,
The runnability is ensured.
[発明が解決しようとする課題] ところが、ポリエステルフィルム、とくに磁気テープ
用ベースフィルムや高い機械的特性が要求される包装用
フィルムとして使用される二軸配向ポリエステルフィル
ムは、さらに高い耐摩耗性、さらに優れた耐スクラッチ
性が要求されてきており、上記特開昭63−230741号公報
提案のフィルムでは、未だ十分とはいえなくなってき
た。[Problems to be Solved by the Invention] However, a polyester film, particularly a biaxially oriented polyester film used as a base film for a magnetic tape or a packaging film requiring high mechanical properties, has higher abrasion resistance, Excellent scratch resistance has been demanded, and the film proposed in Japanese Patent Application Laid-Open No. 63-230741 is no longer sufficient.
たとえば、各種工程等の速度増大に伴い、工程中にあ
る各種高速ロールと接触してもフィルム表面に傷が付か
ないだけの高い耐スクラッチ性が要求されつつあるが、
上記提案フィルムの如く単に比較的粒径の大きな一種類
の硬い粒子を含有させるだけでは、該粒子によりフィル
ム表面上に突起状に突出する部分については硬度が高め
られ耐摩耗性は向上されるものの、フィルムの地肌(上
記突出部以外の表面部)自身については補強されないた
め、この地肌部分にかき傷が入るおそれがある。For example, with the increase in the speed of various processes, a high scratch resistance that does not damage the film surface even when it comes into contact with various high-speed rolls in the process is being demanded,
By simply including one kind of hard particles having a relatively large particle size as in the above proposed film, the hardness of the portion protruding in a projecting manner on the film surface is increased by the particles, but the wear resistance is improved. Since the background of the film (the surface portion other than the protruding portion) itself is not reinforced, there is a possibility that the background portion may be scratched.
また、地肌部分が補強されない結果、フィルム表面部
にある、耐摩耗性向上のための粒子の保持力が十分とは
いえず、接触するロール等から受ける外力によって粒子
部がフィルム粉として削られるおそれがあり、該削れが
生じると、それがロール表面等に付着し該付着物によっ
てさらにフィルム表面が傷付けられるとともに、脱落フ
ィルム粉が異物となって、各種加工工程の外乱となった
り、製品自身の性能を低下させたりするおそれがある。In addition, as a result of the fact that the ground portion is not reinforced, the particle holding force on the film surface portion for improving abrasion resistance cannot be said to be sufficient, and the particle portion may be shaved as film powder by an external force received from a contacting roll or the like. When the scraping occurs, the scraping adheres to the roll surface and the like, and furthermore, the film surface is further damaged by the deposit, and the falling film powder becomes a foreign substance, which may be a disturbance in various processing steps, or the product itself may be damaged. Performance may be reduced.
本発明は、上記のような問題点に着目し、二軸配向ポ
リエステルフィルムの表面の耐スクラッチ性および削れ
等に対する耐摩耗性をさらに向上することを目的とす
る。The present invention pays attention to the above-mentioned problems, and aims to further improve the scratch resistance and the wear resistance against abrasion and the like of the surface of the biaxially oriented polyester film.
[課題を解決するための手段] この目的に沿う本発明の二軸配向ポリエステルフィル
ムは、2種の粒子A、Bを含有し、粒子Aは、α−アル
ミナ、γ−アルミナ、δ−アルミナ、ジルコニア、窒化
チタンおよび有機高分子の中から選ばれた一種の粒子か
らなり、平均粒径が5〜400nm、含有量が0.1〜2重量%
であり、粒子Bは、シリカ、炭酸カルシウム、アルミ
ナ、ルチル型酸化チタンおよび有機高分子の中から選ば
れた一種の粒子からなり、平均粒径が400〜1500nm、含
有量が0.01〜0.4重量%であり、かつ、フィルム表面に
形成される突起の高さ分布の標準偏差が250nmよりも小
さいことを特徴とするものから成る。[Means for Solving the Problems] The biaxially oriented polyester film of the present invention for this purpose contains two kinds of particles A and B, and the particles A are composed of α-alumina, γ-alumina, δ-alumina, Consisting of one kind of particles selected from zirconia, titanium nitride and organic polymer, the average particle size is 5 to 400 nm, and the content is 0.1 to 2% by weight.
The particles B are composed of one kind of particles selected from silica, calcium carbonate, alumina, rutile-type titanium oxide and an organic polymer, and have an average particle diameter of 400 to 1500 nm and a content of 0.01 to 0.4% by weight. And the standard deviation of the height distribution of the projections formed on the film surface is smaller than 250 nm.
本発明におけるポリエステルは、エチレンテレフタレ
ート、エチレンα・β−ビス(2−クロルフェノキシ)
エタン−4、4′−ジカルボキシレート、エチレン2,6
−ナフタレート単位から選ばれた少なくとも一種の構造
単位を主要構成成分とする。ただし、本発明を阻害しな
い範囲内、好ましくは15モル%以内であれば他成分が共
重合されていてもよい。The polyester in the present invention is ethylene terephthalate, ethylene α · β-bis (2-chlorophenoxy)
Ethane-4,4'-dicarboxylate, ethylene 2,6
-At least one structural unit selected from naphthalate units is used as a main component. However, other components may be copolymerized within a range that does not impair the present invention, preferably within 15 mol%.
また、エチレンテレフタレートを主要構成成分とする
ポリエステルの場合に耐スクラッチ性がより良好となる
ので特に望ましい。Further, in the case of a polyester containing ethylene terephthalate as a main component, scratch resistance is further improved, which is particularly desirable.
本発明のフィルムには、二種の粒子A、Bが含有され
る。The film of the present invention contains two types of particles A and B.
粒子Aは、比較的平均粒径の小さな粒子であり、主と
してフィルムの地肌部分を補強するが、この地肌補強効
果を高めるために、硬度の高い粒子あるいはフィルムと
親和性が良好な粒子が選択される。硬度の高い粒子とし
ては、α−アルミナ、γ−アルミナ、δ−アルミナ、ジ
ルコニア、窒化チタンからなる粒子が好ましく、親和性
の良好な粒子としては、有機高分子粒子、たとえば架橋
ポリスチレン粒子、シリコン粒子、4フッ化エチレン粒
子等が挙げられる。Particle A is a particle having a relatively small average particle size and mainly reinforces the background portion of the film. In order to enhance the background reinforcing effect, particles having high hardness or particles having good affinity with the film are selected. You. As particles having high hardness, particles composed of α-alumina, γ-alumina, δ-alumina, zirconia, and titanium nitride are preferable, and as particles having good affinity, organic polymer particles, for example, crosslinked polystyrene particles, silicon particles And tetrafluoroethylene particles.
本発明における有機高分子粒子は、加熱減量曲線にお
ける10%重量減量時温度が360℃、好ましくは380℃、さ
らに好ましくは400℃以上である場合に耐スクラッチ
性、耐ダビング性がより一層良好となるので特に望まし
い。The organic polymer particles in the present invention have a scratch resistance and a dubbing resistance more preferably when the temperature at the time of 10% weight loss in the heating weight loss curve is 360 ° C., preferably 380 ° C., and more preferably 400 ° C. or more. Is particularly desirable.
また、粒子Aは、平均粒径d1が5〜400nmの比較的小
さな粒子である。平均粒径がこの範囲よりも小さいと、
フィルム地肌部の補強効果が薄れ、耐スクラッチ性が不
良となるので好ましくない。また、平均粒径が上記範囲
よりも大きいと、粒子の分布が粗くなりすぎ、フィルム
地肌補強効果が薄れ、粒子Bあるいは粒子Bにより形成
されたフィルム表面突起を保持する強度が低下し、粒子
Bあるいはそれによるフィルム表面突起が削られやすく
なる。また、粒子Aによるフィルム表面突起自身につい
ても削られる機会が増大するので好ましくない。上記平
均粒径d1のより好ましい範囲は、10〜200nmである。The particles A are relatively small particles having an average particle diameter d1 of 5 to 400 nm. If the average particle size is smaller than this range,
This is not preferred because the reinforcing effect of the film background is weakened and the scratch resistance becomes poor. On the other hand, if the average particle size is larger than the above range, the distribution of the particles becomes too coarse, the effect of reinforcing the film background is weakened, the strength of retaining the particle B or the film surface projections formed by the particles B decreases, and the particle B Alternatively, film surface protrusions due to this are likely to be scraped. Further, it is not preferable because the chances of shaving the film surface projections themselves due to the particles A increase. A more preferred range of the average particle diameter d 1 is 10 to 200 nm.
本発明における有機高分子粒子は、加熱減量曲線にお
ける10%重量減量時温度が360℃、好ましくは、380℃、
さらに好ましくは400℃以上である場合に耐スクラッチ
性、耐ダビング性がより一層良好となるので特に望まし
い。Organic polymer particles in the present invention, the temperature at the time of 10% weight loss in the heating weight loss curve is 360 ℃, preferably 380 ℃,
More preferably, the temperature is 400 ° C. or more, since the scratch resistance and the dubbing resistance are further improved.
また粒子Aの含有量は0.1〜2.0重量%の範囲に調製さ
れる。この範囲よりも少ないと、粒子A含有によるフィ
ルム地肌補強効果が薄れ、望ましい耐スクラッチ性が得
られない。この範囲よりも多いと、含有物が多くなりす
ぎるので構造的に脆くなるおそれがあり、フィルム自身
が削り取られやすくなったり、含有粒子が脱落しやすく
なったりするので好ましくない。より好ましい含有量
は、0.3〜1.0重量%である。The content of the particles A is adjusted to a range of 0.1 to 2.0% by weight. If the amount is less than this range, the effect of reinforcing the film background due to the inclusion of the particles A is weakened, and a desirable scratch resistance cannot be obtained. If the content is larger than this range, the content becomes too large, and there is a possibility that the film becomes brittle structurally, and the film itself is easily scraped off or the contained particles are easily dropped off, which is not preferable. A more preferred content is 0.3 to 1.0% by weight.
粒子Bは、粒子Aよりも平均粒径の大きな粒子であ
り、粒子Bによって形成されたフィルム表面突起により
フィルム表面の粗さを増し、表面の摩擦係数を下げるこ
とにより、耐スクラッチ性を向上しつつ、加工時等にロ
ール等の他の面に接触する際の抵抗を減らし、フィルム
表面が削りとられにくいようにすることを狙ったもので
ある。これらを達成可能な粒子Bの材質として、シリ
カ、炭酸カルシウム、アルミナ、ルチル型酸化チタンお
よび有機高分子が挙げられ、有機高分子粒子については
前述の粒子Aと同様の材質を採り得る。Particle B is a particle having a larger average particle diameter than Particle A, and increases the roughness of the film surface due to the film surface protrusions formed by Particle B and reduces the coefficient of friction of the surface, thereby improving the scratch resistance. In addition, it aims at reducing the resistance when the film comes into contact with another surface such as a roll during processing or the like, so that the film surface is hardly scraped off. Examples of the material of the particles B capable of achieving these are silica, calcium carbonate, alumina, rutile-type titanium oxide, and an organic polymer. As the organic polymer particles, the same material as the particles A described above can be used.
また、粒子Bは、平均粒径d2が400〜1500nmの比較的
大きな粒子であり、粒子Aの平均粒径d1よりも大きく設
定される。この粒子Bは、比較的大きな粒子であるた
め、該粒子によって形成されるフィルム表面突起の高さ
を、粒子Aによるものよりは高くでき、その部分の表面
粗さを粗くできる。粗くなると、摩擦係数を低減できる
ので、結果的にフィルム表面の耐スクラッチ性が良くな
るが、平均粒径d2が上記範囲よりも小さいと、フィルム
表面を粗くする効果が小さくなり、その分耐スクラッチ
性が悪くなるので、好ましくない。逆に上記範囲よりも
大きいと、粒子B自身あるいは粒子Bにより形成された
表面突起部分が削りとられやすくなるので、好ましくな
い。Further, the particles B, and the average particle size d 2 are relatively large particles of 400~1500Nm, it is set larger than the average particle size d 1 of particle A. Since the particles B are relatively large particles, the height of the film surface protrusions formed by the particles can be made higher than that of the particles A, and the surface roughness of that portion can be made rough. When the roughness is rough, the coefficient of friction can be reduced, and as a result, the scratch resistance of the film surface is improved.However, when the average particle diameter d 2 is smaller than the above range, the effect of roughening the film surface is reduced, and the resistance to the film is reduced accordingly. It is not preferable because the scratching property is deteriorated. On the other hand, if it is larger than the above range, the particles B themselves or the surface projections formed by the particles B are easily scraped off, which is not preferable.
粒子Bの含有量は0.01〜0.4重量%の範囲に調製され
る。この範囲よりも少ないと、粒子B含有による摩擦係
数低減効果が薄れるので、望ましい耐スクラッチ性が得
られない。逆に上記範囲よりも多いと、粒子Aにより補
強されたフィルム地肌部分の受けもつ、粒子Bあるいは
粒子Bによるフィルム表面突起部分が多くなりすぎ、削
りとられやすくなるので、好ましくない。より好ましい
含有量は、0.01〜0.1重量%である。The content of the particles B is adjusted in the range of 0.01 to 0.4% by weight. If it is less than this range, the effect of reducing the friction coefficient due to the inclusion of the particles B is weakened, so that desirable scratch resistance cannot be obtained. Conversely, if the amount is larger than the above range, the particles B or the film surface projections due to the particles B, which are borne by the film ground portion reinforced by the particles A, become too large, so that it is not easy to scrape off. A more preferred content is 0.01 to 0.1% by weight.
本発明のフィルムにおいては、表面突起の高さ分布の
標準偏差σが250nmより小さいことが必要である。高さ
の高い表面突起は、平均粒径の大きな粒子Bによって形
成されるが、高い突起が多いとそれだけ削りとられやす
くなる。σの測定法については後述するが、現実の測定
においては突起が粒子A、Bのいずれによって形成され
たものかは判定しにくいので、ある表面部分について全
ての突起について測定された分布の標準偏差で規定する
ことが有効であり、σ<250nmとすることによって望ま
しい耐摩耗性が得られる。このような突起の高さ分布の
標準偏差は、たとえば溶融製膜のキャスト工程における
ドラフト比の適正化により達成できる。In the film of the present invention, the standard deviation σ of the height distribution of the surface projections needs to be smaller than 250 nm. The surface protrusions having a high height are formed by particles B having a large average particle diameter. However, if the number of the protrusions is large, the surface protrusions are easily removed. Although the method of measuring σ will be described later, it is difficult to determine whether the projections are formed by particles A or B in the actual measurement, so the standard deviation of the distribution measured for all the projections for a certain surface portion Is effective, and by setting σ <250 nm, desirable wear resistance can be obtained. Such a standard deviation of the height distribution of the protrusions can be achieved, for example, by optimizing the draft ratio in the casting step of the melt film formation.
本発明のフィルムにおいては、粒子Aを含有するポリ
エステルの冷結晶化温度とガラス転移点との差と、粒子
Aを含有しないポリエステルの冷結晶化温度とガラス転
移点との間の差が8℃、好ましくは5℃よりも小さいこ
とが望ましい。この差の測定法については後述するが、
この差が小さいと粒子のフィルムに対する親和性を向上
することが可能である。含有量の多い粒子Aについて親
和性を上げておくことにより、耐削れ性、耐スクラッチ
性ともに一層向上される。In the film of the present invention, the difference between the cold crystallization temperature and the glass transition point of the polyester containing particles A and the difference between the cold crystallization temperature and the glass transition point of the polyester not containing particles A is 8 ° C. , Preferably less than 5 ° C. The method of measuring this difference will be described later,
If this difference is small, the affinity of the particles for the film can be improved. By increasing the affinity of the particles A having a large content, both the abrasion resistance and the scratch resistance are further improved.
本発明は上記組成物を主成分とするが、本発明の目的
を阻害しない範囲内で他種ポリマをブレンドしても良い
し、また酸化防止剤、熱安定剤、滑剤、紫外線吸収剤な
どの無機または有機添加剤が通常添加される程度添加さ
れていてもよい。The present invention is based on the above composition, but may be blended with other polymers within a range that does not impair the object of the present invention, and may also be used as an antioxidant, a heat stabilizer, a lubricant, an ultraviolet absorber, etc. Inorganic or organic additives may be added to the extent that they are usually added.
本発明フィルムは上記組成物を二軸配向せしめたフィ
ルムである。未延伸フィルム、一軸配向フィルムでは、
耐スクラッチ性が不良となり、粒子あるいは粒子により
形成されたフィルム表面突起が脱落しやすくなるので好
ましくない。The film of the present invention is a film in which the above composition is biaxially oriented. For unstretched film and uniaxially oriented film,
It is not preferable because the scratch resistance becomes poor and the particles or the film surface projections formed by the particles easily fall off.
また、その二軸配向の程度を表わす面配向指数は特に
限定されないが、0.935〜0.975、特に0.940〜0.970の範
囲である場合に耐スクラッチ性、耐摩耗性がより一層良
好となるので望ましい。また、本発明フィルムの密度指
数は、0.02〜0.05の範囲である場合に耐スクラッチ性、
耐摩耗性がより一層良好となるので特に望ましい。The plane orientation index indicating the degree of the biaxial orientation is not particularly limited, but is preferably in the range of 0.935 to 0.975, and particularly preferably in the range of 0.940 to 0.970, because the scratch resistance and the wear resistance are further improved. Further, when the density index of the film of the present invention is in the range of 0.02 to 0.05, scratch resistance,
This is particularly desirable because the abrasion resistance is further improved.
また、本発明フィルムは、幅方向の表面平均粗さRaが
0.005〜0.030μm、特に0.007〜0.025μmの範囲にある
場合に耐スクラッチ性がより一層良好となるので特に望
ましい。Further, the film of the present invention has a surface average roughness Ra in the width direction.
It is particularly desirable that the scratch resistance be in the range of 0.005 to 0.030 μm, particularly 0.007 to 0.025 μm, because the scratch resistance will be further improved.
本発明におけるフィルムの摩擦係数μkが0.20〜0.35
の範囲にある場合に、耐スクラッチ性がより一層良好と
なるので特に望ましい。The coefficient of friction μk of the film in the present invention is 0.20 to 0.35
It is particularly preferable that the ratio is within the range, since the scratch resistance is further improved.
また本発明フィルムの表面固有抵抗が1×1015Ω・cm
よりも小さい場合に耐スクラッチ性、耐摩耗性が一層良
好となるので特に望ましい。この値以上になると、仮に
フィルム粉が削りとられた場合、該フィルム粉が静電気
等により塊状になりやすくなり、塊状になったフィルム
粉がフィルム面を傷付けやすくなるので、好ましくな
い。The surface specific resistance of the film of the present invention is 1 × 10 15 Ω · cm
It is particularly desirable that the ratio be smaller than the above, since the scratch resistance and the wear resistance are further improved. Above this value, if the film powder is scraped off, the film powder is likely to be clumped due to static electricity or the like, and the clumped film powder is likely to damage the film surface, which is not preferable.
次に本発明フィルムの製造方法について説明する。 Next, a method for producing the film of the present invention will be described.
まず、所定のポリエステルに粒子A、Bを含有せしめ
る方法としては、重合前、重合中、重合後のいずれに添
加してもよいが、ポリエステルのジオール成分であるエ
チレングリコールに、スラリーの形で混合、分散せしめ
て添加する方法が有効である。また、粒子の含有量を調
節する方法としては、高濃度のマスターペレットを製膜
時に稀釈する方法が有効である。粒子A、Bを用いて、
高濃度、好ましくは1〜5重量%のマスターペレットの
溶融粘度、共重合成分を調整して、ガラス転移点Tgと冷
却晶化温度Tccとの差(Tcc−Tg)を、65〜110℃、とく
に75〜100℃にしておくことが、きわめて有効である。First, as a method for incorporating particles A and B into a predetermined polyester, the particles may be added before, during, or after the polymerization, but they are mixed in a slurry form with ethylene glycol, which is a diol component of the polyester. It is effective to disperse and add. As a method of adjusting the content of particles, a method of diluting a high-concentration master pellet at the time of film formation is effective. Using particles A and B,
The melt viscosity of the master pellet at a high concentration, preferably 1 to 5% by weight, the copolymerization component is adjusted, and the difference between the glass transition point Tg and the cooling crystallization temperature Tcc (Tcc−Tg) is 65 to 110 ° C. It is extremely effective to keep the temperature at 75 to 100 ° C.
また、粒子A、Bは、エチレングリコールに分散させ
たスラリーを重合反応前、または重合反応中に添加する
のが本発明範囲の平均粒径を得るのに有効である。The addition of the particles A and B to the slurry dispersed in ethylene glycol before or during the polymerization reaction is effective for obtaining the average particle size within the range of the present invention.
なお、本発明においては、粒子A、Bをそれぞれ別に
含有する高濃度マスターのポリエステルを製造してもよ
いが、重合時あるいはマスターペレット製造時に予め所
定の混合比で粒子A、Bを高濃度で入れておき、作成さ
れたマスターペレットをフィルム製造段階で他のチッ
プ、ペレットにより稀釈して所定の濃度にする方法が最
も好ましい。In the present invention, a high-concentration master polyester containing the particles A and B separately may be produced. However, the particles A and B may be produced at a high mixing concentration in advance at the time of polymerization or production of a master pellet. The most preferred method is to put the prepared master pellet into a predetermined concentration by diluting the prepared master pellet with other chips and pellets in the film production stage.
かくして、所定量の粒子A、Bを含有するポリエステ
ルペレットを十分乾燥させた後、公知の溶融押出機に供
給し、270℃〜330℃でスリット状のダイからシート状に
押出し、キャスティングロール上で冷却固化せしめて未
延伸フィルムを作る。この未延伸フィルムを作る場合、
キャスト時のドラフト比(口金のスリット幅/未延伸フ
ィルムの厚み)は、16倍以上の高い値であることが好ま
しい。高ドラフトキャストを行なうと粒子が表層部へ集
中するという特異な現象が起こり、粒子A、Bにそれぞ
れねらった機能を発揮させやすくなる。さらに、粒子の
表層部への集中によりフィルム表面の突起高さの標準偏
差が小さくなるため、このような高ドラフトキャストを
行なうことが本発明において特に有効である。Thus, after sufficiently drying the polyester pellets containing a predetermined amount of particles A and B, it is supplied to a known melt extruder, extruded at 270 ° C. to 330 ° C. from a slit die into a sheet, and is cast on a casting roll. Cool and solidify to make an unstretched film. When making this unstretched film,
The draft ratio at the time of casting (slit width of die / thickness of unstretched film) is preferably a high value of 16 times or more. When high draft casting is performed, a peculiar phenomenon occurs in which particles concentrate on the surface layer portion, and it becomes easy for particles A and B to exert their intended functions. Further, since the standard deviation of the projection height on the film surface becomes smaller due to the concentration of the particles on the surface layer, such a high draft casting is particularly effective in the present invention.
次にこの未延伸フィルムを二軸延伸し二軸配向せしめ
る。延伸方法としては、逐次二軸延伸法、または同時二
軸延伸法を用いることができる。逐次二軸延伸法の場合
は長手方向、幅方向の順に延伸するのが一般的である
が、この順を逆にして延伸してもよい。二軸延伸の条件
は延伸方法、ポリマの種類などによって必ずしも一定で
はないが、通常長手方向、幅方向ともに80〜160℃、好
ましくは90〜150℃の範囲で、延伸倍率はそれぞれ3.0〜
5.0倍、好ましくは3.2〜4.5倍の範囲が、また延伸速度
は1000〜70,000%/分の範囲が好適である。Next, the unstretched film is biaxially stretched and biaxially oriented. As the stretching method, a sequential biaxial stretching method or a simultaneous biaxial stretching method can be used. In the case of the sequential biaxial stretching method, the stretching is generally performed in the order of the longitudinal direction and the width direction, but the stretching may be performed in the reverse order. The biaxial stretching conditions are not necessarily constant depending on the stretching method, the type of polymer, etc., but are usually in the longitudinal direction and the width direction at 80 to 160 ° C., preferably in the range of 90 to 150 ° C., and the stretching ratio is 3.0 to
The range is 5.0 times, preferably 3.2 to 4.5 times, and the stretching speed is suitably in the range of 1000 to 70,000% / min.
次にこの延伸フィルムを熱処理する。熱処理条件は定
長下、および幅方向に1〜15%、好ましくは2〜10%の
弛緩下で、また、幅方向に1.01〜1.2倍、好ましくは1.0
5〜1.15倍微延伸下で、150〜230℃、好ましくは170〜22
0℃の範囲で0.5〜60秒間が好適である。Next, this stretched film is heat-treated. The heat treatment conditions are under a fixed length and under a relaxation of 1 to 15%, preferably 2 to 10% in the width direction, and 1.01 to 1.2 times, preferably 1.0 to 1.0 times in the width direction.
Under 5 to 1.15 times fine stretching, 150 to 230 ° C, preferably 170 to 22
0.5 to 60 seconds in the range of 0 ° C is preferred.
[物性の測定方法ならびに効果の評価方法] 本発明の特性値の測定方法ならびに効果の評価方法は
次の通りである。[Method for Measuring Physical Properties and Method for Evaluating Effect] The method for measuring characteristic values and the method for evaluating effect according to the present invention are as follows.
(1)粒子の含有量(重量%) ポリエステル1gをプラズマ装置で灰化させ、原子吸光
分析装置(たとえば島津製作所製AA−680型)を用いて
ポリエステル中の各元素の量を定量し、その元素からな
る粒子の量を粒子の分子量から換算して、重量%として
求める。尚、粒子の化学組成はX線回折などの方法で知
ることができる。(1) Particle content (% by weight) 1 g of polyester was incinerated with a plasma device, and the amount of each element in the polyester was quantified using an atomic absorption spectrometer (for example, AA-680 type manufactured by Shimadzu Corporation). The amount of the particles made of the element is converted from the molecular weight of the particles, and is calculated as% by weight. The chemical composition of the particles can be known by a method such as X-ray diffraction.
また、必要に応じて、螢光X線分析法や、熱分解ガス
クロマトグラフィー、赤外線吸収、ラマン散乱などを用
いて定量することもできる。Further, if necessary, the quantification can be performed using X-ray fluorescence analysis, pyrolysis gas chromatography, infrared absorption, Raman scattering, or the like.
(2)粒子の平均粒径(nm) 粒子を含有したフィルムを、フィルム平面に垂直に厚
さ1000Åの超薄切片とし、透過型電子顕微鏡(例えば日
本電子製JEM−1200EXなど)を用いて粒子を観察し、100
視野について平均した値を平均粒径とした。但し、ここ
で、平均粒径とは一次粒子の平均粒径であり、粒子が凝
集状態にある場合でも個々の一次粒子の実効径から求め
たものをいう。(2) Average particle size (nm) The film containing the particles is made into an ultra-thin section perpendicular to the film plane with a thickness of 1000 mm, and the particles are obtained using a transmission electron microscope (for example, JEM-1200EX manufactured by JEOL Ltd.). Observe 100
The value averaged over the visual field was defined as the average particle size. Here, the average particle size is the average particle size of the primary particles, and is determined from the effective diameter of each primary particle even when the particles are in an aggregated state.
(3)表面突起の高さ分布の標準偏差 2検出器方式の走査型電子顕微鏡[ESM−3200、エリ
オニクス(株)製]と断面測定装置[PMS−1、エリオ
ニクス(株)製]においてフィルム表面の平坦面の高さ
を0として走査したときの突起の高さ測定値を画像処理
装置[IBAS2000、カールツァイス(株)製]に送り、画
像処理装置上にフィルム表面突起画像を再構築する。次
に、この表面突起画像で突起部分を2値化して得られた
個々の突起の面積から円相当径を求めこれをその突起の
平均径とする。また、この2値化された個々の突起部分
の中で最も高い値をその突起の高さとし、これを個々の
突起について求める。この測定を場所をかえて500回繰
返し、測定された突起についてその高さ分布を正規分布
(高さ0の点を中心とする正規分布)とみなして最小2
乗法で近似して高さ分布の標準偏差を求めた。また走査
型電子顕微鏡の倍率は、1000〜8000倍の間を選択する。(3) Standard deviation of height distribution of surface protrusions Film surface in a two-detector scanning electron microscope [ESM-3200, manufactured by Elionix Inc.] and a cross-section measuring device [PMS-1, manufactured by Elionix Inc.] The measured value of the height of the projection when scanning is performed with the height of the flat surface set to 0 is sent to an image processing apparatus [IBAS2000, manufactured by Carl Zeiss Co., Ltd.], and the image of the film surface projection is reconstructed on the image processing apparatus. Next, a circle-equivalent diameter is determined from the area of each projection obtained by binarizing the projection portion on the surface projection image, and this is defined as the average diameter of the projection. The highest value among the binarized individual projections is defined as the height of the projection, and this is determined for each individual projection. This measurement is repeated 500 times in different places, and the height distribution of the measured protrusions is regarded as a normal distribution (normal distribution centered on a point having a height of 0), and the minimum is 2
The standard deviation of the height distribution was determined by multiplication. The magnification of the scanning electron microscope is selected between 1000 and 8000 times.
(4)面配向指数 ナトリウムD線(波長589nm)の光源としてアッベ屈
折率計を用いて、二軸配向フィルムの厚さ方向の屈折率
(Aとする)および溶融プレス後10℃の水中へ急冷して
作った無配向(アモルファス)フィルムの厚さ方向の屈
折率(Bとする)を測定し、A/Bをもって面配向指数と
した。マウント液にはヨウ化メチレンを用い、25℃、65
%RHにて測定した。(4) Plane orientation index Using an Abbe refractometer as a light source for sodium D line (wavelength 589 nm), the refractive index (A) in the thickness direction of the biaxially oriented film and quenching into water at 10 ° C after melt pressing. The refractive index (referred to as B) in the thickness direction of the non-oriented (amorphous) film thus produced was measured, and A / B was defined as a plane orientation index. Use methylene iodide as the mounting solution, 25 ° C, 65
It was measured at% RH.
(5)ガラス転移点Tg、冷結晶化温度Tcc パーキンエルマー社製のDSC(示差走査熱量計)II型
を用いて測定した。DSCの条件は次の通りである。すな
わち、試料10mgをDSC装置にセットし、300℃の温度で5
分間溶融した後、液体窒素中で冷却する。この急冷試料
を10℃/分で昇温し、ガラス転移点Tgを検知する。さら
に昇温を続け、ガラス状態からの結晶化発熱ピーク温度
をもって冷結晶化温度Tccとした。ここで、TccとTgの差
(Tcc−Tg)をΔTc gと定義する。(5) Glass transition point Tg, cold crystallization temperature Tcc Measured using a DSC (differential scanning calorimeter) type II manufactured by PerkinElmer. The conditions of DSC are as follows. That is, 10 mg of a sample is set in a DSC device, and 5
After melting for a minute, cool in liquid nitrogen. The quenched sample is heated at a rate of 10 ° C./min, and the glass transition point Tg is detected. The temperature was further increased, and the crystallization exothermic peak temperature from the glassy state was defined as the cold crystallization temperature Tcc. Here, the difference between Tcc and Tg (Tcc−Tg) is defined as ΔTc g.
(6)密度指数 n−ヘプタン/四塩化炭素からなる密度勾配管を用い
て測定したフィルムの密度をρ1(g/cm3)とし、この
フィルムを溶融プレス後、10℃の水中へ急冷して作った
無配向(アモルファス)フィルムの密度ρ2との差(ρ
1−ρ2)をもって密度指数とした。(6) Density Index The density of the film measured using a density gradient tube composed of n-heptane / carbon tetrachloride is defined as ρ 1 (g / cm 3 ). After melt-pressing the film, the film is rapidly cooled into 10 ° C. water. Difference (ρ) from the density ρ 2 of the non-oriented (amorphous) film
1− ρ 2 ) was used as the density index.
(7)摩擦係数μk テープ走行性試験機TBT−300型[株式会社横浜システ
ム研究所製]を使用し、20℃、60%RH雰囲気で走行さ
せ、初期のμk(摩擦係数)を下記の式より求めた。(7) Coefficient of friction μk Using a tape running property tester TBT-300 type [manufactured by Yokohama System Laboratory Co., Ltd.], run at 20 ° C and 60% RH atmosphere, and the initial μk (coefficient of friction) is expressed by the following formula. I asked more.
μk=0.733log(T1/T0) ここで、T0は入側張力、T1は出側張力である。ガイド
径は6mmΦであり、ガイド材質はSUS27(表面粗度0.2
S)、巻き付け角は180゜、走行速度は3.3cm/秒である。μk = 0.733 log (T 1 / T 0 ) where T 0 is the entrance tension and T 1 is the exit tension. The guide diameter is 6mmΦ, and the guide material is SUS27 (surface roughness 0.2
S), the winding angle is 180 °, and the running speed is 3.3cm / sec.
(8)表面固有抵抗 超絶縁計[川口電機製作所株式会社製]VE−40型を使
用して測定した。(8) Surface specific resistance Measured using a super insulation meter [Kawaguchi Electric Mfg. Co., Ltd.] VE-40.
(9)耐スクラッチ性 テープ走行試験機TBT300D/H型[株式会社横浜システ
ム研究所]を使用し、フィルムを幅1/2インチのテープ
状にスリットし、張力30g、走行速度250m/分で、ビデオ
カセットのテープガイドピン(表面粗さがRtで2500nm程
度の表面を持ったステンレス製ガイドピン)上を巻付角
60゜で60m走行させ、その時につく傷の量を次の基準に
したがい目視で判定した。(9) Scratch resistance Using a tape running tester TBT300D / H type [Yokohama System Laboratory Co., Ltd.], slit the film into a 1/2 inch wide tape, tension 30g, running speed 250m / min. Winding angle on tape guide pin of video cassette (stainless steel guide pin with surface roughness of about 2500nm with Rt surface roughness)
The vehicle was run for 60 m at 60 °, and the amount of scratches formed at that time was visually determined according to the following criteria.
まったく傷のないもの……5点 浅い傷のあるもの…………3点 深い傷のあるもの…………1点 また、5点と3点の中間を4点、3点と1点の中間を
2点とした。この時、3点以上を耐スクラッチ性良好、
3点未満を耐スクラッチ性不良とした。No scratches at all ... 5 points Shallow scratches ... 3 points Deep scratches ... 1 point Also, 4 points at the middle of 5 points and 3 points, 3 points and 1 point The middle was given two points. At this time, three or more points have good scratch resistance,
Less than 3 points were regarded as poor scratch resistance.
この時の判定で3点未満のフィルムは、フィルムの加
工時や製品としたときの走行時にフィルム表面が摩耗し
て深い傷が発生するため、製品の品質が著しく悪くな
る。A film having less than 3 points determined at this time has a severely damaged surface due to abrasion of the film surface during processing of the film or running as a product, so that the quality of the product is significantly deteriorated.
(10)耐削れ性 フィルムを幅1/2インチにテープ状にスリットしたも
のに片切を垂直に押しあて、さらに0.5mm押し込んだ状
態で20cm走行させる(走行張力:500g、走行速度:6.7cm/
秒)。この時片刃の先に付着したフィルム表面の削れ物
の高さを顕微鏡で読みとり、削れ量とした(単位はμ
m)この削れ量の両面の平均値が12μm以下の場合は耐
削れ性:良好、12μmを越える場合は耐削れ性:不良と
判定した。上記境界値は、印刷工程やカレンダー工程な
どの加工工程で、フィルム表面が削れることによって、
工程上、製品性能上のトラブルがおこるか否かを判定す
るための臨界点である。(10) Abrasion resistance A piece of film is slit into a tape with a width of 1/2 inch, and one piece is pressed vertically, and the film is further pushed in by 0.5 mm and run for 20 cm (running tension: 500 g, running speed: 6.7 cm) /
Seconds). At this time, the height of the shavings on the film surface attached to the tip of the single blade was read with a microscope and the shaving amount (unit: μ)
m) When the average value of the abrasion amount on both sides was 12 μm or less, the abrasion resistance: good, and when it exceeded 12 μm, the abrasion resistance: poor. The above boundary values are obtained by processing the film surface in processing steps such as printing and calendaring.
This is a critical point for determining whether or not a trouble in product performance occurs in the process.
[実施例] 本発明を実施例に基づいて説明する。[Examples] The present invention will be described based on examples.
実施例1〜8 粒子Aとして、平均粒径d1がそれぞれ異なるが本発明
範囲内である、α−アルミナ、γ−アルミナ、δ−アル
ミナ、ジルコニア、窒化チタン、有機高分子粒子を選
び、粒子Bとして、平均粒径d2がそれぞれ異なるが本発
明範囲内である、シリカ、炭酸カルシウム、アルミナ、
ルチル型酸化チタン、有機高分子粒子を選び、それぞ
れ、エチレングリコール中に均一に分散させ、195℃で
2時間熱処理したのち、テレフタル酸ジメチルとエステ
ル交換反応後重縮合し、各粒子を本発明で規定した範囲
よりは相当高い濃度で含有するポリエステルを作成し、
それをマスターペレットにした。Examples 1 to 8 As particles A, α-alumina, γ-alumina, δ-alumina, zirconia, titanium nitride, and organic polymer particles having different average particle diameters d 1 but within the scope of the present invention were selected. As B, silica, calcium carbonate, alumina, each having a different average particle diameter d 2 but within the scope of the present invention,
Rutile-type titanium oxide and organic polymer particles were selected, uniformly dispersed in ethylene glycol, respectively, and heat-treated at 195 ° C. for 2 hours. After transesterification with dimethyl terephthalate, polycondensation was performed. Create a polyester containing a considerably higher concentration than the specified range,
It was made into a master pellet.
各マスターペレットと、粒子を含有していないポリエ
ステルペレットとを、粒子Aおよび粒子Bが本発明の含
有率の範囲となるように混合し、混合したペレットを18
0℃で3時間減圧乾燥(3Torr)した。このペレットを押
出機に供給し、290℃で溶融押出し、静電印加キャスト
法を用いて表面温度30℃のキャスティング・ドラムに巻
き付けて冷却固化し厚さ約180μmの未延伸フィルムを
作った。このときのドラフト比は22であった。Each master pellet and a polyester pellet containing no particles were mixed so that the particles A and the particles B were within the range of the content of the present invention, and the mixed pellets were mixed.
It was dried under reduced pressure (3 Torr) at 0 ° C. for 3 hours. The pellets were supplied to an extruder, melt-extruded at 290 ° C., wound around a casting drum having a surface temperature of 30 ° C. by using an electrostatic application casting method, cooled and solidified to form an unstretched film having a thickness of about 180 μm. The draft ratio at this time was 22.
この未延伸フィルムを90℃にて長手方向に3.4倍延伸
した。この延伸は2組のロール周速差で行なわれ、延伸
速度は10000%/分であった。この一軸フィルムをステ
ンターを用いて延伸速度3000%/分で100℃で幅方向に
3.6倍延伸し、幅方向に1.05倍微延伸させつつ、210℃に
て5秒間熱処理し、厚さ15μmの二軸配向ポリエステル
フィルムを得た。これらのフィルムの性能は第1表に示
した通り、粒子A、Bの材質が本発明で規定するもので
あり、平均粒径、含有量が本発明範囲であるので、耐ス
クラッチ性、耐削れ性ともに優れたフィルムが得られ
た。This unstretched film was stretched 3.4 times in the longitudinal direction at 90 ° C. This stretching was performed with two sets of roll peripheral speed differences, and the stretching speed was 10,000% / min. This uniaxial film is stretched in the width direction at 100 ° C at a stretching speed of 3000% / min using a stenter.
The film was heat-treated at 210 ° C. for 5 seconds while being stretched 3.6 times and slightly stretched 1.05 times in the width direction to obtain a biaxially oriented polyester film having a thickness of 15 μm. As shown in Table 1, the performance of these films is such that the materials of the particles A and B are specified in the present invention, and the average particle size and the content are within the range of the present invention. A film excellent in both properties was obtained.
比較例1〜10 粒子A、Bの平均粒径が本発明の範囲から外れるも
の、含有量が本発明の範囲から外れるもの、および粒子
の材質に関し本発明で規定したもの以外を組合わせたも
のについて、それぞれ前記実施例と同一の製造方法にて
厚さ15μmの二軸配向ポリエステルフィルムを得た。こ
れらのフィルムの性能は第2表に示した通り、粒子A、
Bの材質、平均粒径、含有量のいずれが本発明の範囲か
ら外れても、耐スクラッチ性、耐削れ性を両立させるこ
とのできるフィルムは得られなかった。なお、実施例、
比較例ともにポリエステルはポリエチレンテレフタレー
トであった。Comparative Examples 1 to 10 Particles A and B having a mean particle size outside the range of the present invention, a content outside the range of the present invention, and a combination of particles other than those specified in the present invention regarding the material of the particles In each case, a biaxially oriented polyester film having a thickness of 15 μm was obtained in the same manner as in the above examples. The performances of these films were as shown in Table 2, as shown in Particle A,
Even if any of the material, average particle size, and content of B deviated from the range of the present invention, a film capable of achieving both scratch resistance and abrasion resistance was not obtained. Note that the embodiment,
In both comparative examples, the polyester was polyethylene terephthalate.
[発明の効果] 以上説明したように、本発明によれば、特定の材質か
ら選ばれ、特定の範囲の平均粒径、含有量および突起の
高さ分布を有する二種の粒子A、Bを含有する二軸配向
ポリエステルフィルムとしたので、最近の苛酷な使用条
件にも耐え得る、優れた耐スクラッチ性、耐削れ性(耐
摩耗性)を備えたフィルムが得られる。[Effects of the Invention] As described above, according to the present invention, two types of particles A and B selected from a specific material and having a specific range of an average particle size, a content, and a projection height distribution are used. Since the biaxially oriented polyester film is contained, a film having excellent scratch resistance and abrasion resistance (abrasion resistance) that can withstand recent severe use conditions can be obtained.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 FI 技術表示箇所 B29L 7:00 (56)参考文献 特開 平1−311131(JP,A) 特開 昭63−278939(JP,A) 特開 平2−129230(JP,A)────────────────────────────────────────────────── (5) Continuation of the front page (51) Int.Cl. 6 Identification code Agency reference number FI Technical display location B29L 7:00 (56) References JP-A 1-311131 (JP, A) JP-A 63- 278939 (JP, A) JP-A-2-129230 (JP, A)
Claims (2)
−アルミナ、γ−アルミナ、δ−アルミナ、ジルコニ
ア、窒化チタンおよび有機高分子の中から選ばれた一種
の粒子からなり、平均粒径が5〜400nm、含有量が0.1〜
2重量%であり、粒子Bは、シリカ、炭酸カルシウム、
アルミナ、ルチル型酸化チタンおよび有機高分子の中か
ら選ばれた一種の粒子からなり、平均粒径が400〜1500n
m、含有量が0.01〜0.4重量%であり、かつ、フィルム表
面に形成される突起の高さ分布の標準偏差が250nmより
も小さいことを特徴とする二軸配向ポリエステルフィル
ム。(1) It contains two kinds of particles A and B, and the particle A has α
-Alumina, γ-alumina, δ-alumina, zirconia, composed of one kind of particles selected from titanium nitride and an organic polymer, the average particle size is 5 to 400 nm, the content is 0.1 to
2% by weight, and particles B are silica, calcium carbonate,
Alumina, composed of a kind of particles selected from rutile type titanium oxide and organic polymer, the average particle size is 400 ~ 1500n
m, a biaxially oriented polyester film having a content of 0.01 to 0.4% by weight and a standard deviation of a height distribution of protrusions formed on the film surface being smaller than 250 nm.
い請求項1記載の二軸配向ポリエステルフィルム。2. The biaxially oriented polyester film according to claim 1, having a surface resistivity of less than 1 × 10 15 Ω · cm.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1035120A JP2621461B2 (en) | 1989-02-16 | 1989-02-16 | Biaxially oriented polyester film |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1035120A JP2621461B2 (en) | 1989-02-16 | 1989-02-16 | Biaxially oriented polyester film |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP27304293A Division JPH06279599A (en) | 1993-10-04 | 1993-10-04 | Biaxially oriented polyester film |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH02214734A JPH02214734A (en) | 1990-08-27 |
JP2621461B2 true JP2621461B2 (en) | 1997-06-18 |
Family
ID=12433071
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP1035120A Expired - Lifetime JP2621461B2 (en) | 1989-02-16 | 1989-02-16 | Biaxially oriented polyester film |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2621461B2 (en) |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2585494B2 (en) * | 1991-11-13 | 1997-02-26 | 帝人株式会社 | Polyethylene-2,6-naphthalate film |
KR100255141B1 (en) * | 1991-12-09 | 2000-05-01 | 히라이 가쯔히꼬 | Polyester composition and biaxially oriented polyester film made therefrom |
DE69324303T2 (en) * | 1992-01-24 | 1999-09-23 | Toray Industries, Inc. | THERMOPLASTIC POLYESTER COMPOSITION AND FILM MADE THEREOF |
JPH05310964A (en) * | 1992-04-30 | 1993-11-22 | Diafoil Co Ltd | Biaxially oriented polyester film |
JPH06279599A (en) * | 1993-10-04 | 1994-10-04 | Toray Ind Inc | Biaxially oriented polyester film |
KR950023662A (en) * | 1994-01-20 | 1995-08-18 | 박홍기 | Manufacturing method of high transparency polyester film excellent in winding property |
KR100290820B1 (en) * | 1994-12-21 | 2001-10-24 | 구광시 | Method for producing polyester film |
DE60034864T2 (en) * | 1999-06-08 | 2008-02-07 | Teijin Ltd. | COMPOSITE FILM FOR CONDENSER, MANUFACTURING METHOD AND SUPPORT FILM THEREFOR |
KR100381261B1 (en) | 1999-12-20 | 2003-04-23 | 주식회사 코오롱 | Polyester resin composition for film |
FR2810987B1 (en) * | 2000-07-03 | 2002-08-16 | Rhodianyl | POLYMERIC COMPOSITIONS WITH IMPROVED MECHANICAL PROPERTIES |
US7368523B2 (en) * | 2004-11-12 | 2008-05-06 | Eastman Chemical Company | Polyester polymer and copolymer compositions containing titanium nitride particles |
US7300967B2 (en) | 2004-11-12 | 2007-11-27 | Eastman Chemical Company | Polyester polymer and copolymer compositions containing metallic titanium particles |
CZ2006666A3 (en) * | 2006-10-20 | 2008-05-14 | Vcelák@Pavel | CORPLASTEN material range - thermoplastic polymers filled with powder corundum and intended for rotary molding |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63278939A (en) * | 1987-05-11 | 1988-11-16 | Teijin Ltd | Biaxially oriented polyester film |
JPH02129230A (en) * | 1988-11-08 | 1990-05-17 | Diafoil Co Ltd | Oriented polyester film |
-
1989
- 1989-02-16 JP JP1035120A patent/JP2621461B2/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
JPH02214734A (en) | 1990-08-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US5998004A (en) | Biaxially oriented polyester film | |
JP2621461B2 (en) | Biaxially oriented polyester film | |
JPH0780282B2 (en) | Biaxially oriented thermoplastic resin film | |
JP2615974B2 (en) | Biaxially oriented polyester film | |
JPS63230741A (en) | Biaxially oriented polyester film | |
US5284699A (en) | Biaxially oriented polyester film | |
JPH06279599A (en) | Biaxially oriented polyester film | |
JP2734601B2 (en) | Biaxially oriented polyester film | |
JP2513826B2 (en) | Biaxially oriented polyester film | |
JPH0768370B2 (en) | Biaxially oriented polyester film | |
JP2525461B2 (en) | Biaxially oriented polyester film | |
JPH0751637B2 (en) | Biaxially oriented polyester film | |
JP3072717B2 (en) | Biaxially oriented polyester film | |
JP2515782B2 (en) | Biaxially oriented polyester film | |
JP2988580B2 (en) | Polyester film and method for producing the same | |
JP2988579B2 (en) | Polyester film and method for producing the same | |
JPH0198634A (en) | Biaxially oriented polyester film | |
JP3353542B2 (en) | Biaxially oriented polyester film | |
JP2519345B2 (en) | Biaxially oriented polyester film for computer memory | |
JP2975881B2 (en) | Biaxially oriented thermoplastic resin film | |
JPH0768369B2 (en) | Biaxially oriented polyester film | |
JPH0577318A (en) | Biaxially oriented polyester film | |
JP2525396B2 (en) | Biaxially oriented thermoplastic resin film | |
JP2616048B2 (en) | Biaxially oriented polyester film | |
JPS63230740A (en) | Biaxially oriented polyester film |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080404 Year of fee payment: 11 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090404 Year of fee payment: 12 |
|
EXPY | Cancellation because of completion of term |