JPH0796626B2 - Biaxially oriented polyester film - Google Patents
Biaxially oriented polyester filmInfo
- Publication number
- JPH0796626B2 JPH0796626B2 JP62065455A JP6545587A JPH0796626B2 JP H0796626 B2 JPH0796626 B2 JP H0796626B2 JP 62065455 A JP62065455 A JP 62065455A JP 6545587 A JP6545587 A JP 6545587A JP H0796626 B2 JPH0796626 B2 JP H0796626B2
- Authority
- JP
- Japan
- Prior art keywords
- film
- particles
- sharpness
- present
- 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
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- 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)
- Polyesters Or Polycarbonates (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、更に詳しく
は、耐摩耗性に優れた包装用、コンデンサ用、および磁
気テープ用ベースフィルムとして好適な二軸配向ポリエ
ステルフィルムに関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial application] The present invention relates to a biaxially oriented polyester film, and more particularly, to a biaxially oriented polyester film suitable for use as a base film for packaging, capacitors, and magnetic tape, which has excellent abrasion resistance. It relates to an axially oriented polyester film.
［従来の技術］ 従来、二軸配向ポリエステルフィルムとしては、加工時
や、製品としてときに滑り性、走行性を持たせるために
炭酸カルシウム粒子やカオリン粒子などを含有したポリ
エステルフィルム（例えば、特公昭59-29610号公報や、
特公昭58-19934号公報など）が知られている。[Prior Art] Conventionally, as a biaxially oriented polyester film, a polyester film containing calcium carbonate particles, kaolin particles or the like in order to have slipperiness and running property when processed or as a product (for example, Japanese Patent Publication No. 59-29610 bulletin,
Japanese Patent Publication No. 58-19934, etc.) is known.
［発明が解決しようとする問題点］ しかしながら、ポリエステルフィルムに要求される耐摩
耗性は益々厳しくなっているため、上述の如きポリエス
テルフィルムでは品質的に十分とは言えなかった。[Problems to be Solved by the Invention] However, since the abrasion resistance required for polyester films is becoming more and more severe, the polyester films as described above cannot be said to have sufficient quality.
本発明の目的は、かかる問題点を解消せしめ、耐摩耗性
に優れた二軸配向ポリエステルフィルムを提供せんとす
るものである。An object of the present invention is to solve the above problems and provide a biaxially oriented polyester film having excellent abrasion resistance.
［問題点を解決するための手段］ 本発明は、平均粒径0.05〜2.0μｍ、モース硬度７以上
の粒子を含有した二軸配向ポリエステルフィルムであ
り、２次イオン質量分析装置で測定した該フィルムの表
皮厚さが100〜300Å、表面突起尖頭度が0.02〜0.50であ
ることを特徴とする二軸配向ポリエステルフィルムに関
するものである。[Means for Solving Problems] The present invention is a biaxially oriented polyester film containing particles having an average particle diameter of 0.05 to 2.0 μm and a Mohs hardness of 7 or more, and the film is measured by a secondary ion mass spectrometer. Of the biaxially oriented polyester film having a surface skin thickness of 100 to 300Å and a surface protrusion sharpness of 0.02 to 0.50.
本発明のポリエステルは、特に限定されないが、通常ポ
リエチレンテレフタレート、ポリエチレン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、ポリエチレン2,6ナフタレート、ポリブチレ
ンテレフタレート等が用いられる。中でもポリエチレン
テレフタレートが好ましい。The polyester of the present invention is not particularly limited, but usually polyethylene terephthalate, polyethylene α, β-bis (2-chlorophenoxy) ethane-4,4′-dicarboxylate, polyethylene 2,6 naphthalate, polybutylene terephthalate, etc. are used. To be Among them, polyethylene terephthalate is preferable.
本発明フィルムに含有される粒子は平均粒径が0.05〜2.
0μｍ、好ましくは0.10〜1.2μｍである必要がある。粒
子の平均粒径が上記範囲より小さいと走行性が悪く、ま
た上記範囲より大きいと耐摩耗性が悪くなるので好まし
くない。The particles contained in the film of the present invention have an average particle diameter of 0.05 to 2.
It should be 0 μm, preferably 0.10 to 1.2 μm. If the average particle size of the particles is smaller than the above range, the running property is poor, and if it is larger than the above range, the wear resistance is deteriorated, which is not preferable.
本発明フィルムに含有される粒子は、モース硬度が７以
上、好ましくは８以上である。モース硬度が上記範囲よ
り小さいとフィルムの耐摩耗性が悪くなるので好ましく
ない。またモース硬度の上限は製造上の制約から10程度
が限界である。The particles contained in the film of the present invention have a Mohs hardness of 7 or more, preferably 8 or more. When the Mohs hardness is less than the above range, the abrasion resistance of the film is deteriorated, which is not preferable. The upper limit of Mohs hardness is about 10 due to manufacturing restrictions.
尚、本発明フィルムは、本発明の目的を阻害しない範囲
であれば他の粒子が含有されていても良いし、内部析出
粒子と併用してもよい。The film of the present invention may contain other particles as long as the object of the present invention is not impaired, or may be used in combination with the internally precipitated particles.
本発明フィルムの２次イオン質量分析装置で測定した表
皮厚さは100〜3000Å、好ましくは200〜2500Åである。
表皮厚さが上記範囲より小さいと、耐摩耗性が悪いばか
りではなく、フィルム加工時や製品としたときのフィル
ム走行時に、金属ロールやプラスチックロールに傷が付
き、ロールが摩耗してしまうので好ましくない。また表
皮厚さが上記範囲より大きいと走行性が悪く好ましくな
い。The skin thickness of the film of the present invention measured by a secondary ion mass spectrometer is 100 to 3000Å, preferably 200 to 2500Å.
If the skin thickness is smaller than the above range, not only the wear resistance is poor, but also during film running during film processing or as a product, the metal roll or the plastic roll is scratched, and the roll is worn, which is preferable. Absent. On the other hand, when the skin thickness is larger than the above range, the running property is deteriorated, which is not preferable.
本発明フィルムの表面突起尖頭度は0.02〜0.50、好まし
くは0.03〜0.25の範囲である。表面突起尖頭度が上記範
囲より小さいと走行性が不良となるので好ましくない。
また表面突起尖頭度が上記範囲より大きいと耐摩耗性が
不良となるので好ましくない。The sharpness of the surface projections of the film of the present invention is in the range of 0.02 to 0.50, preferably 0.03 to 0.25. If the sharpness of the surface protrusions is smaller than the above range, the running property becomes poor, which is not preferable.
If the sharpness of the surface projections is larger than the above range, the abrasion resistance will be poor, which is not preferable.
更に、本発明フィルムの平均表面粗さは特に限定されな
いが、少なくとも片面の平均表面粗さが0.0030〜0.060
μｍの範囲にある場合が走行性及び耐摩耗性を共により
一層良好となるので望ましい。Furthermore, the average surface roughness of the film of the present invention is not particularly limited, but the average surface roughness of at least one surface is 0.0030 to 0.060.
When it is in the range of μm, the running property and the wear resistance are further improved, which is desirable.
また本発明フィルムの静摩擦係数は、特に限定されない
が、少なくとも片面の静摩擦係数が0.2〜3.0の範囲にあ
る場合が走行性、耐摩耗性ともにより一層良好となるの
で望ましい。The coefficient of static friction of the film of the present invention is not particularly limited, but it is desirable that the coefficient of static friction of at least one surface is in the range of 0.2 to 3.0 because the running property and abrasion resistance are further improved.
次に本発明フィルムの製造方法をポリエチレンテレフタ
レートを例にとって説明する。Next, the method for producing the film of the present invention will be described by taking polyethylene terephthalate as an example.
まず所定の粒子は前処理を行なうことが好ましい。モー
ス硬度の高い粒子は凝集しやすい性質があるので、大量
のエチレングリコール中に分散させ、沸騰加熱処理を行
なうことが特に好ましい。処理時間が12〜48時間の範囲
である場合が、表皮厚さ及び表面突起尖頭度を本発明の
範囲内とするのに非常に有効である。First, it is preferable that the predetermined particles are pretreated. Since particles having a high Mohs hardness tend to agglomerate, it is particularly preferable to disperse the particles in a large amount of ethylene glycol and to perform boiling heat treatment. When the treatment time is in the range of 12 to 48 hours, it is very effective in keeping the epidermal thickness and the surface projection sharpness within the range of the present invention.
次にこのスラリーを微細なガラスビーズのメディアを用
いて、十分に分散、過処理を行なう。このとき、トリ
エチルアンモニウムリン酸塩などの分散剤を粒子に対し
て１〜15重量％添加することが、表皮厚さ及び表面突起
尖頭度を本発明の範囲内とするのに有効である。Next, this slurry is sufficiently dispersed and overtreated using a medium of fine glass beads. At this time, it is effective to add a dispersant such as triethylammonium phosphate in an amount of 1 to 15% by weight with respect to the particles so that the skin depth and the sharpness of the surface protrusions fall within the scope of the present invention.
次にポリエステルの重合を行なう。Next, the polyester is polymerized.
ジメチルテレフタレートとエチレングリコールに触媒と
して酢酸マンガン等を加え、常法によりメタノールを留
去させつつ、エステル交換反応を行なう。Manganese acetate or the like is added as a catalyst to dimethyl terephthalate and ethylene glycol, and an ester exchange reaction is carried out while distilling off methanol by a conventional method.
その後、粒子を含有したエチレングリコールスラリー及
び重合触媒等を加え、真空下で加熱しつつ重縮合を行な
い、ペレット状ポリマを得る。Then, ethylene glycol slurry containing particles, a polymerization catalyst, and the like are added, and polycondensation is performed while heating under vacuum to obtain a pelletized polymer.
ポリマーの固有粘度は特に限定されないが、0.60〜0.93
の範囲にあるときが表皮厚さを本発明の範囲とするのに
特に好ましい。The intrinsic viscosity of the polymer is not particularly limited, but 0.60 to 0.93
It is particularly preferred that the skin depth is within the range of the present invention.
また、粒子の含有量を調節する方法としては、高濃度の
粒子含有ペレットを製膜時に希釈する方法が好ましく、
希釈するポリマーより粒子含有ポリマーの固有粘度を高
くしておくことは、表皮厚さと表面突起尖頭度を本発明
の範囲内とするのに有効である。Further, as a method for adjusting the content of particles, a method of diluting a high-concentration particle-containing pellet during film formation is preferable,
Keeping the intrinsic viscosity of the particle-containing polymer higher than that of the polymer to be diluted is effective in keeping the skin depth and the sharpness of the surface protrusion within the range of the present invention.
また結晶化促進度を０〜10の範囲とすることは、表皮厚
さと表面突起尖頭度を本発明の範囲内とするのに特に有
効である。結晶化促進度は添加する粒子の表面処理や分
散剤の種類、添加量などによって変えることができる。Further, setting the degree of crystallization acceleration in the range of 0 to 10 is particularly effective for keeping the skin thickness and the sharpness of the surface projections within the range of the present invention. The degree of crystallization acceleration can be changed by the surface treatment of particles to be added, the type of dispersant, the amount added, and the like.
次にこのペレット状ポリマを十分乾燥したのち、これを
押出機に供給して口金から溶融押出し、冷却ドラムに巻
きつけ冷却固化させ未延伸フィルムを作る。Next, the pelletized polymer is sufficiently dried, and then it is supplied to an extruder, melt-extruded from a die, wound around a cooling drum, and cooled and solidified to form an unstretched film.
このとき、押出機のスクリューやシリンダーは粒子によ
り摩耗しないよう、表面を硬度化処理したものを使用す
るのが望ましい。At this time, it is desirable to use a screw or cylinder of the extruder whose surface is hardened so as not to be worn by particles.
次にこの未延伸フィルムを二軸延伸し配向せしめる。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が、特に好ましいのは逐次二軸延
伸法である。この場合の延伸条件としては、長手方向に
3.0〜4.0倍、好ましくは3.0〜3.6倍延伸したのち、幅方
向に3.2〜4.5倍、好ましくは3.3〜4.0倍延伸する方法が
好適である。延伸速度は103〜107％／分の範囲が好適で
ある。延伸温度は長手方向がポリマのガラス転移温度以
上冷結晶化温度未満、好ましくは（ガラス転移温度＋５
℃）以上、（冷結晶化温度−10℃）未満、また幅方向
は、（ガラス転移点＋10℃）以上、（冷結晶化温度＋10
℃）未満で延伸することが、表皮厚さ及び表面突起尖頭
度を本発明の範囲内とするのに有効である。Next, this unstretched film is biaxially stretched and oriented. As the stretching method, a sequential biaxial stretching method or a simultaneous biaxial stretching method can be used, but the sequential biaxial stretching method is particularly preferable. In this case, the stretching conditions are as follows:
A method is suitable in which after stretching 3.0 to 4.0 times, preferably 3.0 to 3.6 times, stretching in the width direction is 3.2 to 4.5 times, preferably 3.3 to 4.0 times. The stretching speed is preferably in the range of 10 3 to 10 7 % / min. The stretching temperature is not less than the glass transition temperature of the polymer in the longitudinal direction and less than the cold crystallization temperature, preferably (glass transition temperature + 5
℃) and less than (cold crystallization temperature -10 ℃), and the width direction is (glass transition point +10 ℃) or more, (cold crystallization temperature +10
Stretching at a temperature of less than 0 ° C.) is effective for keeping the skin thickness and the sharpness of the surface protrusion within the range of the present invention.
また、この延伸フィルムを少なくとも一方向にさらに延
伸しても良い。Further, this stretched film may be further stretched in at least one direction.
次にこの延伸フィルムは熱処理する。この場合の熱処理
条件としては、定長下で180〜250℃、好ましくは190〜2
30℃の範囲で0.5〜60秒熱処理するのが好ましい。The stretched film is then heat treated. The heat treatment conditions in this case are 180 to 250 ° C. under constant length, preferably 190 to 2
It is preferable to perform heat treatment for 0.5 to 60 seconds in the range of 30 ° C.
［作用］ 本発明は、ポリエステルと無機粒子とからなる二軸延伸
フィルムにおいて、無機粒子の平均粒径とモース硬度を
特定の範囲とし、かつ、表皮厚さと表面突起尖頭度を特
定の範囲としたので、フィルム表面突起の粘弾性挙動を
コントロールでき、突起の衝撃吸収力が飛躍的に向上し
たため、本発明の効果が得られたものと推定される。[Operation] In the biaxially stretched film composed of polyester and inorganic particles, the present invention sets the average particle diameter and Mohs hardness of the inorganic particles to a specific range, and the skin thickness and the surface protrusion sharpness to a specific range. Therefore, the viscoelastic behavior of the film surface protrusions can be controlled, and the impact absorbing power of the protrusions is dramatically improved. Therefore, it is presumed that the effect of the present invention was obtained.
［特性の測定法］ 本発明の特性値は次の測定法、評価基準によるものであ
る。[Measurement Method of Characteristic] The characteristic value of the present invention is based on the following measuring method and evaluation criteria.
（１） 表皮厚さ ２次イオン質量分析装置（ATOMIKA社製Ａ−DIDA3000）
を用いてフィルムの深さ方向の元素分析を行ない、粒子
に含有される金属元素の強度とポリエステルの炭素の強
度比を測定する。その結果を横軸に表面からの深さを、
縦軸に上記強度比を対数でプロットしたときに、表面付
近で上記強度比が急激に減少し始める深さを表皮厚さと
した。測定条件は次の通りである。(1) Skin thickness secondary ion mass spectrometer (A-DIDA3000 manufactured by ATOMIKA)
Is used to perform elemental analysis in the depth direction of the film, and the strength ratio of the metal element contained in the particles and the carbon strength ratio of the polyester are measured. The horizontal axis is the result and the depth from the surface is
When the intensity ratio is plotted logarithmically on the vertical axis, the depth at which the intensity ratio begins to decrease rapidly near the surface is defined as the skin depth. The measurement conditions are as follows.
１次イオン種：O2 + １次イオン加速電圧:12KV ラスター領域:400μｍ口 （２） モース硬度 フィルムに添加する粒子と同じ組成、構造をもった試験
片を製造し、または粒子に粉砕する前の鉱物を試験片と
し、モース硬度測定用の標準鉱物と互いに引っかいて、
引っかきが行なわれるかどうかで硬さ数を0.1の単位ま
で測定する。Primary ion species: O 2 + Primary ion Accelerating voltage: 12KV Raster area: 400μm mouth (2) Mohs hardness Before producing a test piece having the same composition and structure as the particles added to the film, or crushing into particles As a test piece, use the above minerals to scratch the standard minerals for Mohs hardness measurement,
The hardness number is measured to a unit of 0.1 depending on whether scratching is performed.
（３） 表面突起尖頭度 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
として走査した時の突起の高さ測定値を256階調のグレ
ー値として画像処理装置［IBAS2000、カールツァイス
（株）製］に送り、このグレー値を元にIBAS2000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10階調以上のものを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、突起の平均径に対する
高さの比を表面突起尖頭度として、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
れた全ての突起についての平均値を表面突起尖頭度とし
て用いた。また１階調の高さは、任意設定値Ｈを256で
割った値であり、任意設定値Ｈは、通常測定するフィル
ム表面のRa（単位：μｍ）に30を乗じた値を用いる。ま
た走査型電子顕微鏡の倍率は、2000〜8000倍の間の値を
選択し、フィルム表面のRaに応じて変更する。(3) Scanning electron microscope [ESM-3200, manufactured by Elionix Co., Ltd.] with a surface projection sharpness 2 detector system and cross-section measurement device [PMS-1, manufactured by Elionix Co., Ltd.] Height 0
As a gray value of 256 gradations, the height measurement value of the projection when scanned as is sent to the image processing device [IBAS2000, Carl Zeiss Co., Ltd.], and based on this gray value, the projection image on the film surface is re-created on the IBAS2000. To construct. Next, the equivalent circle diameter is calculated from the area of each protrusion obtained by binarizing 10 or more gradations in this surface protrusion image, and this is taken as the average diameter of the protrusion. Further, the highest value among the binarized individual projection portions is taken as the height of the projection, and the ratio of the height to the average diameter of the projection is taken as the surface projection sharpness to obtain for each projection. This measurement was repeated 500 times at different places, and the average value of all the measured protrusions was used as the surface protrusion sharpness. The height of one gradation is a value obtained by dividing the arbitrary set value H by 256. As the arbitrary set value H, a value obtained by multiplying Ra (unit: μm) of the film surface to be normally measured by 30 is used. The magnification of the scanning electron microscope is selected to be a value between 2000 and 8000 times and changed according to Ra on the film surface.
（４） 走行性 フィルムを1/2インチにスリットし、テープ走行性試験
機TBT-300型（（株）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を下記
の式より求めた。(4) Runnability The film was slit into 1/2 inch, and tape runnability tester TBT-300 type (manufactured by Yokohama System Laboratory Co., Ltd.) was used to run at 20 ° C, 60% RH atmosphere. ΜK was calculated from the following formula.
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0.2S）、巻
き付け角は180°、走行速度は3.3cm/秒である。μK = 0.733log (T 1 / T 0 ) where T 0 is the inlet tension and T 1 is the outlet tension. Guide diameter is
The guide material is SUS27 (surface roughness 0.2S), the winding angle is 180 °, and the running speed is 3.3 cm / sec.
上記μＫが0.35以下であるものを走行性良好とした。μ
Ｋが0.35という値はフィルム加工時または、製品とした
ときの走行性が極端に悪くなるかどうかの臨界の値であ
る。When the above μK was 0.35 or less, the running property was good. μ
A value of K of 0.35 is a critical value of whether or not the running property during film processing or as a product is extremely deteriorated.
（５） ロール摩耗値 フィルムを1/2インチにスリットし、前記テープ走行性
試験を使用し、ガイドピンにプラスチックガイド（ポリ
アセタール製）を用いて繰返し走行を行なう。走行速度
3.3cm/秒で60分間走行させた後、プラスチックガイド表
面を光学顕微鏡で観察し、表面にできるスリキズを見
る。スリキズがない場合はロール摩耗度：良好、スリキ
ズが多数発生した場合はロール摩耗度：不良とした。(5) Roll wear value The film is slit into 1/2 inch, the tape running test is used, and the running is repeated using a plastic guide (made of polyacetal) for the guide pin. Traveling speed
After running for 60 minutes at 3.3 cm / sec, the surface of the plastic guide is observed with an optical microscope to see any scratches on the surface. When there were no scratches, the roll wear degree was good, and when many scratches were generated, the roll wear degree was bad.
（６） 耐摩耗性 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
に片刃を垂直に押しあて、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）。この削れ量が８μｍ以下の場合は耐摩耗性：良
好、８μｍを越える場合は耐摩耗性：不良と判定した。
この８μｍという値は、フィルム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発生する摩耗粉が
製品の品質に影響を及ぼすか否かの臨界値である。(6) Abrasion resistance A film is slit into a tape width of 1/2 inch, a single blade is pressed vertically, and the product is run for 20 cm while being pushed 0.5 mm (running tension: 500 g, running speed: 6.7 cm /
Seconds). At this time, the height of the shavings on the surface of the film attached to the tip of the single-edged blade was read with a microscope and used as the shaving amount (unit: μ
m). When the abrasion amount was 8 μm or less, abrasion resistance was good, and when it was more than 8 μm, abrasion resistance was poor.
The value of 8 μm is a critical value as to whether or not abrasion powder generated due to abrasion of the film surface during film processing or running as a product affects the quality of the product.
（７） 結晶化促進度 パーキンエルマー社製のDSC（示差走査熱量計）II型を
用いて測定したポリマの冷結晶化温度Tccとガラス転移
点Tgの差（Tcc-Tg）をΔTcgと定義し、１重量％の無機
粒子を含有するポリエステルのΔTcg（Ｉ）、およびこ
れと同粘度の不活性無機粒子を含有しないポリエステル
のΔTcg（II）を測定し、ΔTcg（II）とΔTcg（Ｉ）の
差［ΔTcg（II）‐ΔTcg（Ｉ）］をもって、結晶化促進
度とした。なお、DSCの測定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、液体窒素中に急冷する。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。(7) Degree of crystallization acceleration The difference (Tcc-Tg) between the cold crystallization temperature Tcc of the polymer and the glass transition point Tg (Tcc-Tg) measured using DSC (Differential Scanning Calorimeter) II type manufactured by Perkin Elmer Co., Ltd. is defined as ΔTcg. The ΔTcg (I) of the polyester containing 1% by weight of the inorganic particles and the ΔTcg (II) of the polyester containing no inert inorganic particles of the same viscosity were measured, and the ΔTcg (II) and ΔTcg (I) of The difference [ΔTcg (II) -ΔTcg (I)] was defined as the degree of crystallization acceleration. The measurement conditions of DSC are as follows. That is, 10 mg of a sample is set in a DSC apparatus, melted at a temperature of 300 ° C. for 5 minutes, and then rapidly cooled in liquid nitrogen. The temperature of this quenched sample is raised at 10 ° C./min, and the glass transition point Tg is detected. The temperature was further raised, and the crystallization exothermic peak temperature from the glass state was set as the cold crystallization temperature Tcc.
（８） 平均粒径 粒子をエチレングリコール中に均一に分散してスラリー
とし、これを測定に便利な濃度に希釈し、遠心沈降式粒
子径測定装置（島津製作所製SA-CP2型）で測定する。得
られた粒子径分布を対数確率紙にプロットし、積算通過
百分率が50％となった点のメジアン径を、その粒子の平
均粒径とした。(8) Average particle size Particles are evenly dispersed in ethylene glycol to form a slurry, which is diluted to a convenient concentration for measurement and measured with a centrifugal sedimentation particle size analyzer (SA-CP2 type manufactured by Shimadzu Corporation). . The obtained particle size distribution was plotted on a logarithmic probability paper, and the median diameter at the point where the cumulative passage percentage became 50% was taken as the average particle size of the particles.
（９） 平均表面粗さ JIS-B-0601に準じて、触針式表面粗さ計を用いて測定し
た。なお、カットオフは0.08mm、測定長は4mmとした。(9) Average surface roughness Measured using a stylus type surface roughness meter according to JIS-B-0601. The cutoff was 0.08 mm and the measurement length was 4 mm.
（10） 静摩擦係数 ASTM-D-1894-63に準じ、スリップテスターを用いて、静
摩擦係数を測定した。荷重は200グラムとした。(10) Static friction coefficient According to ASTM-D-1894-63, the static friction coefficient was measured using a slip tester. The load was 200 grams.
（11） 固有粘度 ｏ−クロロフェノルを用い、25℃にて測定した。(11) Intrinsic viscosity Using o-chlorophenol, it was measured at 25 ° C.
［実施例］ 次に実施例に基づき、本発明の実施態様を説明する。[Example] Next, an embodiment of the present invention will be described based on an example.
実施例１ 平均粒径0.3μｍモース硬度10.0の窒化チタン粒子をエ
チレングリコール中に分散し、24時間沸騰加熱処理をし
た。このスラリーにトリメチルアンモニウムリン酸塩を
粒子重量の10重量％加え、さらにメディア分散法で均一
に分散させ、ジメチルテレフタレートと重合した。固有
粘度は0.85であった。また、ポリマに対する粒子の含有
量は１重量％であった。Example 1 Titanium nitride particles having an average particle size of 0.3 μm and a Mohs hardness of 10.0 were dispersed in ethylene glycol and subjected to a boiling heat treatment for 24 hours. Trimethylammonium phosphate was added to this slurry in an amount of 10% by weight based on the weight of the particles, and the mixture was further uniformly dispersed by a media dispersion method and polymerized with dimethyl terephthalate. The intrinsic viscosity was 0.85. Further, the content of particles with respect to the polymer was 1% by weight.
次に粒子をまったく含有しないポリエチレンテレフタレ
ートを重合し（固有粘度0.62）、上記粒子含有ポリエチ
レンテレフタレートと同重量で混ぜ合せ十分に乾燥させ
た後、押出機に供給し300℃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
に巻きつけて冷却固化し、厚さ約150μｍの未延伸フィ
ルムを作った。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。Next, polyethylene terephthalate containing no particles was polymerized (intrinsic viscosity 0.62), mixed with the same weight of polyethylene terephthalate containing the particles described above and thoroughly dried, and then supplied to an extruder and melt-extruded at 300 ° C., electrostatic application. The film was wound around a casting drum having a surface temperature of 30 ° C. by a casting method and cooled and solidified to prepare an unstretched film having a thickness of about 150 μm. This unstretched film was stretched 3.4 times in the longitudinal direction at 90 ° C.
この延伸は２組のロールの周速差で行なわれ、延伸速度
10000％／分であった。この一軸フィルムをステンタを
用いて延伸速度2000％／分で100℃で幅方向に3.6倍延伸
し、定長下で210℃にて５秒間熱処理し、厚さ12μｍの
フィルムを得た。This stretching is performed by the difference in peripheral speed between the two rolls,
It was 10000% / min. The uniaxial film was stretched 3.6 times in the width direction at 100 ° C. at a stretching rate of 2000% / min using a stenter and heat-treated at 210 ° C. for 5 seconds under a constant length to obtain a film having a thickness of 12 μm.
このフィルムの平均表面粗さは0.0065μｍ、静摩擦係数
は1.4であった。This film had an average surface roughness of 0.0065 μm and a static friction coefficient of 1.4.
また２次イオン質量分析装置で測定した表皮厚さは820
Åであり、表面突起尖頭度は0.09であった。The skin depth measured by the secondary ion mass spectrometer is 820.
It was Å, and the surface prominence was 0.09.
このフィルムの耐摩耗性は2.3と良好であり、走行性も
0.29と良好であった。またロールの摩耗も全く見られな
かった（第１表）。The abrasion resistance of this film is as good as 2.3, and the running property is also
It was as good as 0.29. No roll wear was observed (Table 1).
実施例２、比較例１〜５ 実施例１と同様にして第１表に示す平均粒径とモース硬
度を持った粒子を含有する二軸延伸ポリエステルフィル
ムを製造した。表皮厚さ及び表面突起尖頭度は第１表に
示した。また、耐摩耗性、走行性及びロールの摩耗度も
第１表に示した。Example 2, Comparative Examples 1 to 5 In the same manner as in Example 1, a biaxially stretched polyester film containing particles having the average particle size and the Mohs hardness shown in Table 1 was produced. The skin depth and the degree of sharpness of the surface projections are shown in Table 1. Further, Table 1 also shows the wear resistance, the running property and the degree of roll wear.
第１表からわかるように含有する粒子の平均粒径とモー
ス硬度が本発明の範囲内にあり、かつフィルムの表皮厚
さと表面突起尖頭度が本発明の範囲内にある場合には、
耐摩耗性と走行性が両立でき、かつロールの摩耗もない
フィルムとなった。しかし、粒子の平均粒径、モース硬
度及びフィルムの表皮厚さ、表面突起尖頭度のいずれか
が本発明の範囲外である場合には、耐摩耗性と走行性及
びロール摩耗度の全てを良好にするフィルムは得られな
かった。As can be seen from Table 1, when the average particle size and Mohs hardness of the contained particles are within the scope of the present invention, and the skin depth and the surface projection sharpness of the film are within the scope of the present invention,
The film has both abrasion resistance and running properties, and has no roll wear. However, if any of the average particle size of the particles, Mohs hardness and the skin depth of the film, and the sharpness of the surface protrusion is outside the scope of the present invention, all of the wear resistance and the running property and the roll wear degree are determined. No film was found to be good.
実施例３〜４、比較例６〜８ 平均粒径0.5μｍ、モース硬度9.0のα−アルミナ粒子を
用いて、分散条件、重合条件、製膜条件を種々変更し、
表皮厚さ及び表面突起尖頭度の異なるフィルムを製造し
た（第２表）。Examples 3 to 4, Comparative Examples 6 to 8 Using α-alumina particles having an average particle size of 0.5 μm and a Mohs hardness of 9.0, the dispersion conditions, polymerization conditions, and film forming conditions were variously changed,
Films with different skin thickness and surface prominence were produced (Table 2).
第２表からわかるように、フィルムの表皮厚さと表面突
起尖頭度が本発明の範囲内にある場合には、耐摩耗性と
走行性が両立でき、かつロールの摩耗もないフィルムと
なった。しかし、フィルムの表皮厚さ、表面突起尖頭度
のいずれかが本発明の範囲外である場合には、耐摩耗性
と走行性およびロール摩耗度の全てを良好にするフィル
ムは得られなかった。As can be seen from Table 2, when the skin depth of the film and the sharpness of the surface projections are within the range of the present invention, both the abrasion resistance and the running property are compatible with each other, and the film has no abrasion of the roll. . However, when either the skin depth of the film or the sharpness of the surface protrusions is outside the scope of the present invention, a film that improves all of the wear resistance and the running property and the roll wear degree could not be obtained. .
［発明の効果］ 本発明は、ポリエステルと無機粒子とからなるフィルム
において、粒子の平均粒径とモース硬度を特定の値と
し、かつフィルムの表皮厚さと表面突起尖頭度を特定の
値としたので、耐摩耗性に優れ、かつ走行性も良好であ
り、しかもロールの摩耗もないフィルムとなった。 [Advantages of the Invention] In the present invention, in a film composed of polyester and inorganic particles, the average particle size of particles and Mohs hardness are set to specific values, and the skin thickness of the film and the sharpness of surface protrusion are set to specific values. Therefore, the film was excellent in abrasion resistance, had good running properties, and had no roll abrasion.
───────────────────────────────────────────────────── 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 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI technical display location B29L 7:00
Claims (1)
上の粒子を含有した二軸配向ポリエステルフィルムであ
り、２次イオン質量分析装置で測定した該フィルムの表
皮厚さが100〜3000Å、表面突起尖頭度が0.02〜0.50で
あることを特徴とする二軸配向ポリエステルフィルム。1. A biaxially oriented polyester film containing particles having an average particle size of 0.05 to 2.0 μm and a Mohs hardness of 7 or more, and having a skin thickness of 100 to 3000Å measured by a secondary ion mass spectrometer. A biaxially oriented polyester film having a surface protrusion sharpness of 0.02 to 0.50.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62065455A JPH0796626B2 (en) | 1987-03-19 | 1987-03-19 | Biaxially oriented polyester film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62065455A JPH0796626B2 (en) | 1987-03-19 | 1987-03-19 | Biaxially oriented polyester film |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29871592A Division JPH05222217A (en) | 1992-11-09 | 1992-11-09 | Biaxially oriented polyester film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63230741A JPS63230741A (en) | 1988-09-27 |
| JPH0796626B2 true JPH0796626B2 (en) | 1995-10-18 |
Family
ID=13287628
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62065455A Expired - Lifetime JPH0796626B2 (en) | 1987-03-19 | 1987-03-19 | Biaxially oriented polyester film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0796626B2 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02129230A (en) * | 1988-11-08 | 1990-05-17 | Diafoil Co Ltd | Oriented polyester film |
| JPH0755534B2 (en) * | 1988-07-21 | 1995-06-14 | ダイアホイルヘキスト株式会社 | Polyester film |
| JPH0625268B2 (en) * | 1988-10-28 | 1994-04-06 | ダイアホイルヘキスト株式会社 | Polyethylene-2,6-naphthalate film |
| JPH07100742B2 (en) * | 1988-12-07 | 1995-11-01 | ダイアホイルヘキスト株式会社 | Biaxially stretched polyester film |
| US5284699A (en) * | 1989-01-11 | 1994-02-08 | Toray Industries, Inc. | Biaxially oriented polyester film |
| EP0378154B1 (en) * | 1989-01-11 | 1995-11-08 | Toray Industries, Inc. | Biaxially oriented polyester film |
| JPH0661918B2 (en) * | 1989-05-30 | 1994-08-17 | ダイアホイルヘキスト株式会社 | Laminated polyester film |
| JP2507606B2 (en) * | 1989-06-22 | 1996-06-12 | ダイアホイルヘキスト株式会社 | Polyester film for magnetic recording media |
| JPH0639535B2 (en) * | 1989-06-23 | 1994-05-25 | ダイアホイルヘキスト株式会社 | Oriented polyester film for magnetic disks |
| JP3017230B2 (en) * | 1989-12-29 | 2000-03-06 | 東レ株式会社 | Polyester composition and method for producing the same |
| US7368523B2 (en) * | 2004-11-12 | 2008-05-06 | Eastman Chemical Company | Polyester polymer and copolymer compositions containing titanium nitride particles |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61239930A (en) * | 1985-04-17 | 1986-10-25 | Teijin Ltd | Polyester film for magnetic recording |
-
1987
- 1987-03-19 JP JP62065455A patent/JPH0796626B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61239930A (en) * | 1985-04-17 | 1986-10-25 | Teijin Ltd | Polyester film for magnetic recording |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63230741A (en) | 1988-09-27 |
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Legal Events
| Date | Code | Title | Description |
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| EXPY | Cancellation because of completion of term |