JPH0788952A - Biaxially oriented thermoplastic resin film - Google Patents
Biaxially oriented thermoplastic resin filmInfo
- Publication number
- JPH0788952A JPH0788952A JP26566593A JP26566593A JPH0788952A JP H0788952 A JPH0788952 A JP H0788952A JP 26566593 A JP26566593 A JP 26566593A JP 26566593 A JP26566593 A JP 26566593A JP H0788952 A JPH0788952 A JP H0788952A
- Authority
- JP
- Japan
- Prior art keywords
- film
- thermoplastic resin
- particles
- biaxially oriented
- thickness
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、二軸配向熱可塑性樹脂
フイルムに関し、特に、フイルムをロール状に巻き取る
際、フイルム層間から空気が抜け易く、良好な巻姿の得
られる二軸配向熱可塑性樹脂フイルムに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a biaxially oriented thermoplastic resin film, and in particular, when the film is wound into a roll, air is easily released from between the film layers and a biaxially oriented thermoplastic film having a good winding shape is obtained. It relates to a plastic resin film.
【０００２】[0002]
【従来の技術】二軸配向熱可塑性樹脂フイルムとして
は、少なくとも片面に粒子に起因する突起を形成したフ
イルムが知られている（例えば、特開平２−７７４３１
号公報等）。このような表面突起を有するフイルムは、
特に磁気記録媒体用のベースフイルム等として適してい
る。2. Description of the Related Art As a biaxially oriented thermoplastic resin film, there is known a film in which projections caused by particles are formed on at least one surface (for example, JP-A-2-77431).
No. A film having such surface protrusions is
In particular, it is suitable as a base film for magnetic recording media.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、上記従
来の二軸配向熱可塑性樹脂フイルムにあっては、フイル
ム表面に均一な高さの突起を形成できるものの、粒子含
有量を０．５重量％以上としていたため、突起が密に形
成されすぎ、フイルムをロール状に巻き取る際、フイル
ム層間の空気が抜けにくく、巻きずれやしわが発生する
おそれがあるという問題があった。However, in the above-mentioned conventional biaxially oriented thermoplastic resin film, although the projections of uniform height can be formed on the film surface, the particle content is 0.5% by weight or more. Therefore, there is a problem that the protrusions are formed too densely, and when the film is wound into a roll, the air between the film layers is difficult to escape, and winding misalignment or wrinkles may occur.
【０００４】本発明は、このような問題点に着目し、磁
気記録媒体用のベースフイルム等として好適な表面突起
を形成しつつ、ロール状に巻き取る際の空気抜けを容易
にし、良好な巻姿が得られる二軸配向熱可塑性樹脂フイ
ルムを提供することを目的とする。Focusing on such problems, the present invention forms a surface projection suitable as a base film for a magnetic recording medium, facilitates air release when wound into a roll, and favorably winds. It is an object of the present invention to provide a biaxially oriented thermoplastic resin film capable of obtaining a figure.
【０００５】[0005]
【課題を解決するための手段】この目的に沿う本発明の
二軸配向熱可塑性樹脂フイルムは、不活性粒子を含有す
る熱可塑性樹脂Ａからなるフイルムであって、該粒子の
含有量が０．００１重量％以上０．５重量％未満、該粒
子の平均粒径がフイルム厚さの０．１〜１０倍、フイル
ム厚さが３μｍ以下であることを特徴とするものからな
る。The biaxially oriented thermoplastic resin film of the present invention for this purpose is a film made of a thermoplastic resin A containing inert particles, and the content of the particles is 0. 001 wt% or more and less than 0.5 wt%, the average particle size of the particles is 0.1 to 10 times the film thickness, and the film thickness is 3 μm or less.
【０００６】本発明に係る二軸配向熱可塑性樹脂フイル
ムは、もちろん単層でも構成可能であるが、とくに２層
以上の積層フイルム構成とすることが好ましい。すなわ
ち、熱可塑性樹脂Ｂからなるフイルムの少なくとも片面
に、上記熱可塑性樹脂Ａからなるフイルムが積層された
構成である。このような積層フイルムにおいては、上記
熱可塑性樹脂Ａからなる積層フイルムの厚さは、上記同
様３μｍ以下で、かつ、フイルム全体の厚さの３０％以
下であることが好ましい。このような積層フイルム構成
とすることにより、薄層の表層フイルム層である熱可塑
性樹脂Ａからなるフイルム層に所定の不活性粒子を所定
量含有させ、所望の表面突起を効率よくかつ効果的に形
成することができる。The biaxially oriented thermoplastic resin film according to the present invention can be composed of a single layer, of course, but it is particularly preferable to have a laminated film structure of two or more layers. That is, the film made of the thermoplastic resin A is laminated on at least one surface of the film made of the thermoplastic resin B. In such a laminated film, the thickness of the laminated film made of the thermoplastic resin A is preferably 3 μm or less as described above and 30% or less of the total thickness of the film. By using such a laminated film structure, a film layer made of the thermoplastic resin A, which is a thin surface film layer, contains a predetermined amount of predetermined inert particles to efficiently and effectively produce desired surface protrusions. Can be formed.
【０００７】積層フイルムとする場合には、これを構成
する各層の少なくとも一層、とくに熱可塑性樹脂Ａから
なるフイルム層が二軸に配向している必要がある。２層
以上の積層構造の内、全部の層が二軸に配向していると
特に好ましい。全ての層が無配向や一軸配向では本発明
の特性を満足することはできない。In the case of a laminated film, it is necessary that at least one of the layers constituting the film, especially the film layer made of the thermoplastic resin A, is biaxially oriented. It is particularly preferable that all layers in a laminated structure of two or more layers are biaxially oriented. When all layers are non-oriented or uniaxially oriented, the characteristics of the present invention cannot be satisfied.
【０００８】本発明フイルムを構成する熱可塑性樹脂と
しては、ポリエステル、ポリオレフィン、ポリアミド、
ポリフェニレンスルフィドなど特に限定されるものでは
ないが、磁気記録媒体のベースフイルム用としては、と
くにポリエステルが好ましい。ポリエステルとしては、
特に限定されないが、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
構成成分とする場合に特に好ましい。中でもエチレンテ
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
が特に好ましい。なお、本発明を阻害しない範囲内で、
２種以上のポリエステルを混合しても良いし、共重合ポ
リマを用いても良い。The thermoplastic resin constituting the film of the present invention includes polyester, polyolefin, polyamide,
Polyphenylene sulfide is not particularly limited, but polyester is particularly preferable for the base film of the magnetic recording medium. As for polyester,
Although not particularly limited, ethylene terephthalate, ethylene α, β-bis (2-chlorophenoxy) ethane-4,
It is particularly preferable when at least one structural unit selected from 4'-dicarboxylate and ethylene 2,6-naphthalate units is the main constituent. Of these, polyesters containing ethylene terephthalate as a main constituent are particularly preferable. Incidentally, within the range that does not inhibit the present invention,
Two or more kinds of polyesters may be mixed, or a copolymer polymer may be used.
【０００９】本発明における熱可塑性樹脂Ａからなるフ
イルムには、不活性粒子が含有される。不活性粒子の種
類としては、特に限定されず、炭酸カルシウム、α型、
γ型、δ型、θ型アルミナ、ジルコニア、シリカ、チタ
ン粒子等の無機粒子、あるいは、架橋ポリスチレン、ジ
ビニルベンゼン、シリコーン粒子等の有機粒子から選ぶ
ことができる。The film made of the thermoplastic resin A in the present invention contains inert particles. The type of inert particles is not particularly limited, calcium carbonate, α type,
It can be selected from inorganic particles such as γ type, δ type, θ type alumina, zirconia, silica and titanium particles, or organic particles such as crosslinked polystyrene, divinylbenzene and silicone particles.
【００１０】この不活性粒子の熱可塑性樹脂Ａからなる
フイルム中での含有量は、０．００１重量％以上０．５
重量％未満である必要がある。０．００１重量％未満で
は、粒子含有の効果が小さく、目標とする表面突起が形
成されない。０．５重量％以上になると、形成される表
面突起の数が多くなりすぎ、つまり突起が密に形成され
すぎ、フイルムをロール状に巻き取る際に、フイルム層
間から空気が抜けにくくなって、巻ずれやしわの原因に
なる。含有量を０．５重量％未満とすることによって、
所望の表面突起が形成されつつ、突起間に空気の抜け道
が形成されるので、巻取時に空気が抜け易くなり、良好
な巻姿が得られるようになる。The content of the inert particles in the film made of the thermoplastic resin A is 0.001% by weight or more and 0.5
Must be less than wt%. If it is less than 0.001% by weight, the effect of containing particles is small and the target surface projections are not formed. When it is 0.5% by weight or more, the number of surface protrusions formed is too large, that is, the protrusions are too densely formed, and when the film is wound into a roll, it becomes difficult for air to escape from the film layers, It may cause misalignment or wrinkles. By setting the content to be less than 0.5% by weight,
Since air passages are formed between the projections while the desired surface projections are formed, it is easy for air to escape during winding, and a good winding appearance can be obtained.
【００１１】本発明においては、上記の如く粒子含有量
を所定の範囲にコントロールしつつ、所望の表面突起、
つまり、均一な高さでかつ均一な密度の表面突起を形成
するために、粒子の平均粒径とフイルム厚さを所定の範
囲にコントロールする必要がある。In the present invention, while controlling the particle content within a predetermined range as described above, desired surface protrusions,
That is, it is necessary to control the average particle size of the particles and the film thickness within a predetermined range in order to form the surface protrusions having a uniform height and a uniform density.
【００１２】すなわち、粒子の平均粒径を、フイルム厚
さ（熱可塑性樹脂Ａからなるフイルムの厚さ）の０．１
〜１０倍に、フイルム厚さを３μｍ以下に制御する必要
がある。このように、比較的に薄いフイルム層に、該フ
イルム層の厚さと同等かそれに近い平均粒径の粒子を含
有させることにより、含有粒子を表面突起形成に有効に
作用させることができ、効率よく、しかも極めて効果的
に所望の均一な高さの表面突起が形成される。含有粒子
の全部あるいは大半が表面突起形成に作用するから、突
起分布も極めて均一なものとなる。しかも、前述の如く
粒子含有量が抑えられているから、形成される突起が密
になりすぎることはない。That is, the average particle diameter is 0.1 of the film thickness (the thickness of the film made of the thermoplastic resin A).
It is necessary to control the film thickness to 3 times or less by 10 times. In this way, the relatively thin film layer contains particles having an average particle diameter equal to or close to the thickness of the film layer, whereby the contained particles can effectively act on the formation of surface protrusions, and the particles can be efficiently formed. Moreover, the surface protrusions having a desired uniform height are formed extremely effectively. Since all or most of the contained particles act on the formation of surface protrusions, the distribution of protrusions becomes extremely uniform. Moreover, since the particle content is suppressed as described above, the projections formed will not be too dense.
【００１３】積層フイルム構成とする場合、熱可塑性樹
脂Ｂからなるフイルム層には、とくに粒子が含有されて
いる必要はないが、粒子を含有させる場合には、薄層の
熱可塑性樹脂Ａからなるフイルム層に悪影響を及ぼさな
いよう、その含有量を２重量％以下に抑えることが好ま
しい。In the case of a laminated film structure, the film layer made of the thermoplastic resin B does not need to contain particles in particular, but in the case of containing particles, it is made of a thin layer of the thermoplastic resin A. It is preferable to control the content to 2% by weight or less so as not to adversely affect the film layer.
【００１４】本発明フイルムにおいては、熱可塑性樹脂
Ａからなるフイルムの表面粗さＲａは、５ｎｍ以上であ
ることが好ましい。Ｒａが５ｎｍ未満であると、表面突
起形成による効果が少なく、表面が平坦になりすぎて、
走行性不良等の不都合が生じる。In the film of the present invention, the surface roughness Ra of the film made of the thermoplastic resin A is preferably 5 nm or more. If Ra is less than 5 nm, the effect of forming surface protrusions is small, and the surface becomes too flat,
Inconvenience such as poor running property occurs.
【００１５】また、本発明フイルムにおいては、その面
配向係数ｆn が０．１５０以上であることが好ましい。
熱可塑性樹脂Ａからなるフイルム層に不活性粒子を含有
させても、ある程度以上配向させないと所望の表面突起
が形成されにくいため、これを面配向係数で規定したも
のである。Further, in the film of the present invention, the plane orientation coefficient f n is preferably 0.150 or more.
Even if the film layer made of the thermoplastic resin A contains inert particles, desired surface protrusions are difficult to be formed unless the particles are oriented to a certain extent. Therefore, this is defined by the plane orientation coefficient.
【００１６】さらに、本発明フイルムにおいては、熱収
縮率があるレベル以下に抑えられることが好ましい。と
くに、１００℃、３０分における長手方向熱収縮率が、
５％以下であることが好ましい。熱収縮率がこの値を越
えると、ロール状にきれいに巻きにくくなり、とくに経
時的に巻姿が悪化するおそれが生じる。Further, in the film of the present invention, it is preferable that the heat shrinkage rate be suppressed to a certain level or less. In particular, the heat shrinkage in the longitudinal direction at 100 ° C for 30 minutes is
It is preferably 5% or less. When the heat shrinkage ratio exceeds this value, it becomes difficult to wind the roll neatly, and there is a possibility that the winding shape deteriorates with time.
【００１７】なお、本発明のフイルム中には、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
もよいし、また酸化防止剤、熱安定剤、滑剤、紫外線吸
収剤などの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。In the film of the present invention, other polymers may be blended within the range not impairing the object of the present invention, and antioxidants, heat stabilizers, lubricants, ultraviolet absorbers, etc. The organic additive may be added to the extent that it is usually added.
【００１８】本発明の熱可塑性樹脂Ａからなるフイルム
の層（Ａ）のポリマＩＶは、０．４〜０．９の範囲であ
ると巻姿をより一層良好とするので特に好ましい。さら
に積層フイルムにおける他の層（Ｂ）とのポリマＩＶの
差が０．１以内であるとより一層巻姿が良好となるので
非常に好ましい。The polymer IV of the layer (A) of the film made of the thermoplastic resin A of the present invention is particularly preferably in the range of 0.4 to 0.9 because the winding shape is further improved. Furthermore, when the difference of the polymer IV from the other layer (B) in the laminated film is 0.1 or less, the winding shape is further improved, which is very preferable.
【００１９】次に本発明フイルムの製造方法について説
明するが、これに限定されるものではない。まず、所定
のポリマ、たとえばポリエステルに粒子を含有せしめる
方法としては、例えば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分散せしめ、このエチレングリ
コールを所定のジカルボン酸成分と重合せしめる方法が
好ましい。粒子を添加する際には、例えば、粒子を合成
時に得られる水ゾルやアルコールゾルを一旦乾燥させる
ことなく添加すると粒子の分散性が非常によく、所望の
表面突起を均一に形成することができる。また粒子の水
スラリーを直接所定のポリエステルペレットと混合し、
ベント方式の２軸混練押出機に供給しポリエステルに練
り込む方法も本発明の効果をより一層良好とするのに非
常に有効である。粒子の含有量を調節する方法として
は、上記方法で高濃度の粒子マスターを作っておき、そ
れを製膜時に粒子を実質的に含有しないポリエステルで
希釈して粒子の含有量を調節する方法が有効である。Next, a method for producing the film of the present invention will be described, but the method is not limited to this. First, as a method for incorporating particles into a predetermined polymer such as polyester, it is preferable to disperse ethylene glycol which is a diol component in the form of a slurry and polymerize the ethylene glycol with a predetermined dicarboxylic acid component. When the particles are added, for example, if the water sol or alcohol sol obtained during the synthesis is added without once drying, the dispersibility of the particles is very good and desired surface protrusions can be formed uniformly. . In addition, the water slurry of particles is directly mixed with the predetermined polyester pellets,
A method of supplying the mixture to a vent type twin-screw kneading extruder and kneading it into polyester is also very effective for further improving the effect of the present invention. As a method for adjusting the content of particles, there is a method of preparing a high-concentration particle master by the above method, and diluting it with a polyester that does not substantially contain particles during film formation to adjust the content of particles. It is valid.
【００２０】上記の方法にて得られたポリエステルのペ
レットを所定の割合で混合し、乾燥したのち、公知の溶
融押出機に供給し、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
伸フイルムを作る。積層フイルムとする場合には、２台
以上の押出機、２層以上のマニホールドまたは合流ブロ
ック（例えば角型合流部を有する合流ブロック）を用い
て積層し、口金から２層以上のシートを押し出し、キャ
スティングロールで冷却して積層未延伸フイルムを作
る。この場合、ポリマ流路にスタティックミキサー、ギ
ヤポンプを設置する方法は有効である。また、最表層積
層部側のポリマーを押出す押出機の溶融温度を基層部側
より５〜１０℃低くすることが、有効である。The polyester pellets obtained by the above method are mixed at a predetermined ratio, dried, and then fed to a known melt extruder, extruded into a sheet form from a slit die, and cooled on a casting roll. An unstretched film is made by solidifying. In the case of a laminated film, two or more extruders, two or more layers of manifolds or merging blocks (for example, a merging block having a square merging portion) are used for lamination, and two or more layers of sheets are extruded from a die, Cool on a casting roll to make a laminated unstretched film. In this case, the method of installing a static mixer and a gear pump in the polymer channel is effective. Further, it is effective to lower the melting temperature of the extruder for extruding the polymer on the outermost layer laminated portion side by 5 to 10 ° C. lower than that on the base layer portion side.
【００２１】次にこの未延伸フイルムを二軸延伸し、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。ただし、最
初に長手方向、次に幅方向の延伸を行なう逐次二軸延伸
法を用い、長手方向の延伸を３段階以上に分けて、総縦
延伸倍率を３．５〜６．５倍で行なう方法は特に好まし
い。長手方向延伸温度はポリエステルの種類によって異
なり一概には言えないが、通常、その１段目を５０〜１
３０℃とし、２段目以降はそれより高くすることが有効
である。長手方向延伸速度は５０００〜５００００％／
分の範囲が好適である。幅方向の延伸方法としてはステ
ンタを用いる方法が一般的である。延伸倍率は、３．０
〜６．０倍の範囲が適当である。幅方向の延伸速度は、
１０００〜２００００％／分、温度は８０〜１６０℃の
範囲が好適である。次にこの延伸フイルムを熱処理す
る。この場合の熱処理温度は１７０〜２２０℃、特に１
８０〜２００℃、時間は０．２〜２０秒の範囲が好適で
ある。Next, the unstretched film is biaxially stretched to be biaxially oriented. As a stretching method, a sequential biaxial stretching method or a simultaneous biaxial stretching method can be used. However, a sequential biaxial stretching method of first stretching in the longitudinal direction and then in the width direction is used, and stretching in the longitudinal direction is performed in three or more stages, and the total longitudinal stretching ratio is 3.5 to 6.5 times. The method is particularly preferred. The stretching temperature in the longitudinal direction varies depending on the type of polyester and cannot be generally stated, but the first stage is usually 50 to 1
It is effective to set the temperature to 30 ° C. and raise the temperature from the second stage onward. The longitudinal stretching speed is 5000 to 50000% /
The range of minutes is preferred. As a stretching method in the width direction, a method using a stenter is generally used. The draw ratio is 3.0
The range of up to 6.0 times is appropriate. The stretching speed in the width direction is
The range of 1000 to 20000% / min and the temperature of 80 to 160 ° C are suitable. Next, this stretched film is heat-treated. The heat treatment temperature in this case is 170 to 220 ° C., especially 1
The range of 80 to 200 ° C. and the time of 0.2 to 20 seconds are suitable.
【００２２】［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並びに効果の評価方法は
次の通りである。 （１）粒子の平均粒径 フイルムからポリマをプラズマ低温灰化処理法で除去
し、粒子を露出させる。処理条件はポリマは灰化される
が粒子は極力ダメージを受けない条件を選択する。その
粒子を走査型電子顕微鏡（ＳＥＭ）で観察し、粒子画像
をイメージアナライザで処理する。ＳＥＭの倍率はおよ
そ２０００〜１００００倍、また、１回の測定での視野
は１辺がおよそ１０〜５０μｍから適宜選択する。観察
箇所をかえて粒子数５０００個以上で粒径とその体積分
率から、次式で体積平均径ｄを得る。 ｄ＝Σｄｉ・Ｎｖｉ ここで、ｄｉは粒径、Ｎｖｉはその体積分率である。粒
子がプラズマ低温灰化処理法で大幅にダメージを受ける
場合には、以下の方法を用いても良い。フイルム断面を
透過型電子顕微鏡（ＴＥＭ）を用い、３０００〜１００
０００倍で観察する。ＴＥＭの切片厚さは約１０００オ
ングストロームとし、場所をかえて５００視野以上測定
し、上記式から体積平均径ｄを求める。[Physical property measuring method and effect evaluating method] The characteristic value measuring method and effect evaluating method of the present invention are as follows. (1) Average particle size of particles The polymer is removed from the film by a plasma low temperature ashing method to expose the particles. The processing conditions are such that the polymer is incinerated but the particles are not damaged as much as possible. The particles are observed with a scanning electron microscope (SEM) and the particle image is processed with an image analyzer. The magnification of SEM is approximately 2000 to 10000 times, and the visual field in one measurement is appropriately selected from approximately 10 to 50 μm on each side. The volume average diameter d is obtained from the particle diameter and its volume fraction when the number of particles is 5,000 or more by changing the observation location. d = Σdi · Nvi Here, di is the particle size, and Nvi is the volume fraction thereof. When the particles are significantly damaged by the plasma low temperature ashing method, the following method may be used. The cross section of the film is 3000 to 100 by using a transmission electron microscope (TEM).
Observe at 000 times. The section thickness of the TEM is set to about 1000 Å, the location is changed and 500 or more visual fields are measured, and the volume average diameter d is calculated from the above formula.
【００２３】（２）粒子の含有量 ポリエステルは溶解し粒子は溶解させない溶媒を選択
し、粒子をポリエステルから遠心分離し、粒子の全体重
量に対する比率（重量％）をもって粒子含有量とする。
場合によっては赤外分光法の併用も有効である。(2) Content of Particles A solvent in which the polyester is dissolved but the particles are not dissolved is selected, the particles are centrifuged from the polyester, and the ratio (% by weight) to the total weight of the particles is taken as the particle content.
In some cases, the combined use of infrared spectroscopy is also effective.
【００２４】（３）フイルム積層厚み 表面からエッチングしながらＸＰＳ（Ｘ線光電子光
法）、ＩＲ（赤外分光法）あるいはコンフォーカル顕微
鏡などで、その粒子濃度のデプスプロファイルを測定す
る。片面に積層したフイルムにおける表層では、表面と
いう界面のために粒子濃度は低く、表面から遠ざかるに
つれて粒子濃度は高くなる。本発明の片面に積層したフ
イルムの場合は、深さ［Ｉ］で一旦極大値となった粒子
濃度がまた減少し始める。この濃度分布曲線をもとに極
大値の粒子濃度の１／２になる深さ［ＩＩ］（ここで、
ＩＩ＞Ｉ）を積層厚さとした。さらに、無機粒子などが
含有されている場合には、二次イオン質量分析装置（Ｓ
ＩＭＳ）を用いて、フイルム中の粒子のうち最も高濃度
の粒子の起因する元素とポリエステルの炭素元素の濃度
比（Ｍ+ ／Ｃ+ ）を粒子濃度とし、ポリエステルＡ層の
表面からの深さ（厚さ）方向の分析を行う。そして上記
同様の手法から積層厚さを得る。なお、フイルム断面観
察あるいは薄膜段差測定機などによって求めることもで
きる。(3) Film Laminate Thickness While etching from the surface, the depth profile of the particle concentration is measured by XPS (X-ray photoelectron spectroscopy), IR (infrared spectroscopy) or confocal microscope. In the surface layer of the film laminated on one side, the particle concentration is low due to the interface called the surface, and the particle concentration increases as the distance from the surface increases. In the case of the film laminated on one side of the present invention, the particle concentration once reaching the maximum value at the depth [I] starts to decrease again. Based on this concentration distribution curve, the depth [II] at which the maximum particle concentration is halved (here,
The layer thickness was II> I). Furthermore, when inorganic particles are contained, a secondary ion mass spectrometer (S
Using IMS), the concentration ratio (M + / C + ) of the element causing the highest concentration of particles in the film and the carbon element of polyester is defined as the particle concentration, and the depth from the surface of the polyester A layer is determined. Analyze in the (thickness) direction. Then, the laminated thickness is obtained from the same method as described above. Alternatively, it can be obtained by observing the film cross section or a thin film step measuring machine.
【００２５】（４）中心線平均表面粗さＲａ 小坂研究所製の高精度薄膜段差測定器ＥＴ−１０を用い
て測定した。条件は下記とおりであり、２０回の測定の
平均値をもって値とした。 ・触針先端半径 ： ０．５μｍ ・触針荷重 ： ５ｍｇ ・測定長 ： １ｍｍ ・カットオフ値 ： ０．０８ｍｍ なお、Ｒａの定義は、たとえば、奈良治郎著「表面粗さ
の測定・評価法」（総合技術センター、１９８３）に示
されているものである。(4) Center Line Average Surface Roughness Ra It was measured using a high precision thin film step measuring instrument ET-10 manufactured by Kosaka Laboratory. The conditions are as follows, and the average value of 20 measurements was taken as the value.・ Stylus tip radius: 0.5 μm ・ Stylus load: 5 mg ・ Measuring length: 1 mm ・ Cutoff value: 0.08 mm Ra is defined, for example, by Jiro Nara, "Measurement and Evaluation Method of Surface Roughness". (Comprehensive Technology Center, 1983).
【００２６】（５）ポリマＩＶ ｏ−クロロフェノールを溶媒として２５℃にて測定し
た。(5) Polymer IV O-chlorophenol was measured as a solvent at 25 ° C.
【００２７】（６）面配向係数ｆn フイルムを約５０μｍの厚さに積層してＸ線回折用試料
とし、Ｘ線表面回折装置（理学電気（株）製Ｇｅｉｇｅ
ｒｆｌｅｘ）の試料ホルダーに設置する。フイルムの長
手方向に垂直な面内で、Ｘ線の照射角を変え、反射法で
フイルム表面回折強度を測定する。測定条件は次の通り
である。 ・時定数 ： ２秒 ・走引速度 ： １度／分 ・Divergency Slit ： １．５ｍｍφ ・Scattering Slit ： １度 ・Receiving Slit ： ０．３ｍｍ ・Ｘ線 ： Ｃｕ対電極によるＣｕ−Ｋα
線 （３５ｋＶ、１５ｍＡ、Ｎｉ−フイルター） ＰＥＴ結晶の［１００］、［ＩＴＯ］面の回折角に相当
する２６．０°、２２．５°での回折強度をそれぞれＩ
1 、Ｉ2 とすると、面配向係数はそれらの比（Ｉ2 ／Ｉ
1 ）で与えられる。(6) A plane orientation coefficient f n film is laminated to a thickness of about 50 μm to prepare a sample for X-ray diffraction, which is obtained by an X-ray surface diffractometer (Geige manufactured by Rigaku Denki Co., Ltd.).
rflex) sample holder. The X-ray irradiation angle is changed in a plane perpendicular to the longitudinal direction of the film, and the film surface diffraction intensity is measured by the reflection method. The measurement conditions are as follows.・ Time constant: 2 seconds ・ Travel speed: 1 degree / minute ・ Divergency Slit: 1.5 mmφ ・ Scattering Slit: 1 degree ・ Receiving Slit: 0.3 mm ・ X-ray: Cu-Kα by Cu counter electrode
Line (35 kV, 15 mA, Ni-filter) The diffraction intensity at 26.0 ° and 22.5 ° corresponding to the diffraction angles of the [100] and [ITO] planes of the PET crystal is I, respectively.
1 and I 2 , the plane orientation coefficient is the ratio (I 2 / I
Given in 1 ).
【００２８】（７）熱収縮率（フイルム長手方向） 熱風オーブン中に無緊張状態で１００℃雰囲気下にて３
０分間放置する熱処理を行い、冷却後の長さを測定し
た。そして熱処理前後の長さから熱収縮率を求めた。試
料長さは１０ｃｍとし、カセドメーターを用いて前後の
長さを測定した。(7) Thermal shrinkage (longitudinal direction of film) 3 in a hot air oven without tension at 100 ° C.
A heat treatment of leaving for 0 minutes was performed, and the length after cooling was measured. Then, the heat shrinkage ratio was obtained from the length before and after the heat treatment. The sample length was 10 cm, and the front and back length was measured using a cassette meter.
【００２９】（８）空気抜け時間 図１に示すような、真空計２、時間計３を有する東洋精
機（株）製、ベック平滑度試験器１を用いて測定した。
図２に示すように、減圧室４の穴５を２枚のフイルム
６、７でふさぎ（下の１枚７は減圧室の穴５に合わせて
穴があけてある。）、３８３ｍｍＨｇまで減圧にする。
減圧を止めると、フイルム６とフイルム７の間を空気が
通りぬけて徐々に減圧室４の中に入り、気圧が上昇して
いく。この時３８１ｍｍＨｇになった時点から３７９ｍ
ｍＨｇになるまでの時間を空気抜け時間とした。この時
間が短いほどフイルムは巻き易い。(8) Evacuation time The Beck smoothness tester 1 manufactured by Toyo Seiki Co., Ltd. having a vacuum gauge 2 and an hour meter 3 as shown in FIG. 1 was used for measurement.
As shown in FIG. 2, the hole 5 of the decompression chamber 4 is covered with two films 6 and 7 (the lower one 7 is perforated to match the hole 5 of the decompression chamber), and the pressure is reduced to 383 mmHg. To do.
When the decompression is stopped, air passes between the film 6 and the film 7 and gradually enters the decompression chamber 4, and the atmospheric pressure rises. At this time, 379 m from the time when it reached 381 mmHg
The time until reaching mHg was defined as the air bleeding time. The shorter this time, the easier the film is to wind.
【００３０】（９）巻姿 二軸延伸後のフイルムを５０ｃｍ巾に裁断し、６インチ
径のコアに２０００ｍ巻き取る。この元巻を６０℃、３
０％ＲＨのオーブンに４８時間放置し、２４時間室温に
て放冷後以下の基準で巻姿を判定した。 × ： 表層にたてじわが入っているか、巻心部に横じ
わがある。 △ ： 表層にしわはないが、巻心部に弱い横じわがあ
る。 ○ ： 表層にも巻心部にもしわが見られない。(9) Winding shape The biaxially stretched film is cut into a width of 50 cm and wound around a 6-inch diameter core for 2000 m. This original roll at 60 ℃, 3
After being left in an oven of 0% RH for 48 hours and allowed to cool at room temperature for 24 hours, the winding shape was judged according to the following criteria. ×: There are vertical wrinkles on the surface or horizontal wrinkles at the core. Δ: There are no wrinkles on the surface layer, but there are weak horizontal wrinkles in the core. ○: No wrinkles are observed on the surface or the core.
【００３１】[0031]
【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。 実施例１（表１） 平均粒径０．３μｍの架橋ポリスチレン粒子を含有する
ポリエチレンテレフタレートのペレットを５０重量部、
さらに粒子を含有しないポリエチレンテレフタレートの
ペレットを５０重量部混ぜ合わせて粒子含有量が０．３
重量％になるようにコントロールし、ベント式二軸混練
押出機１に供給し、２８０℃で溶解した（ポリマＩ）。
更に、もう一台の押出機２を用意し、実質的に粒子を含
有しないポリエチレンテレフタレートのペレットを１８
０℃で３時間減圧乾燥（３Ｔｏｒｒ）し、押出機２に供
給して２９０℃で溶解した（ポリマII）。この２つのポ
リマを、それぞれ高精度濾過した後、矩形積層部を備え
た２層合流ブロックにて、（Ｂ）層部にポリマIIを、
（Ａ）層部にポリマＩがくるように積層し、フィッシュ
テール型の口金よりシート状にして押し出した後、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１６０μｍの
未延伸フイルムを作った。この時のドラフト比は６．５
であった。EXAMPLES Next, the embodiments of the present invention will be explained based on examples. Example 1 (Table 1) 50 parts by weight of polyethylene terephthalate pellets containing crosslinked polystyrene particles having an average particle size of 0.3 μm,
Further, 50 parts by weight of polyethylene terephthalate pellets containing no particles were mixed to obtain a particle content of 0.3.
The content was controlled so as to be wt%, supplied to a vent type twin-screw kneading extruder 1 and melted at 280 ° C. (polymer I).
In addition, another extruder 2 was prepared and 18 pellets of polyethylene terephthalate containing substantially no particles were prepared.
It was dried under reduced pressure (3 Torr) at 0 ° C. for 3 hours, supplied to the extruder 2 and melted at 290 ° C. (polymer II). After filtering these two polymers with high precision, polymer (II) was added to the layer (B) in a two-layer merging block equipped with a rectangular laminate.
(A) Polymer I was laminated on the layer portion, extruded in a sheet form from a fish tail type die, and then wound around a casting drum having a surface temperature of 30 ° C. by an electrostatic applied casting method to be cooled and solidified. Then, an unstretched film having a thickness of about 160 μm was prepared. The draft ratio at this time is 6.5.
Met.
【００３２】この未延伸フイルムを長手方向に３段階に
分け、１２３℃で１．２倍、１２６℃で１．４５倍、１
１４℃で２．３倍それぞれ延伸した。この一軸フイルム
をステンタを用いて幅方向に２段階に分け、１１１℃で
３．７倍、１１３℃で１．２倍延伸し、定長下で２００
℃にて５秒間熱処理（熱固定）し、全体の厚さとして１
４μｍのフイルムを得た。二軸延伸フイルムの全厚（μ
ｍ）に対するＡ層厚さの割合は２．１％であった。ま
た、平均粒径／Ａ層厚さは１．０、Ａ層表面の表面粗さ
Ｒａは８ｎｍ、面配向係数ｆn は０．１６７、長手方向
の１００℃、３０分における熱収縮率は０．５であっ
た。The unstretched film is divided into three stages in the longitudinal direction, 1.2 times at 123 ° C. and 1.45 times at 126 ° C.
Each was stretched 2.3 times at 14 ° C. This uniaxial film was divided into two steps in the width direction using a stenter, and stretched 3.7 times at 111 ° C. and 1.2 times at 113 ° C. to 200 at a fixed length.
Heat treatment (heat setting) for 5 seconds at ℃, total thickness of 1
A 4 μm film was obtained. Total thickness of biaxially stretched film (μ
The ratio of the layer A thickness to m) was 2.1%. Further, the average particle diameter / A layer thickness is 1.0, the surface roughness Ra of the A layer surface is 8 nm, the plane orientation coefficient f n is 0.167, and the thermal shrinkage ratio in the longitudinal direction at 100 ° C. for 30 minutes is 0. It was 0.5.
【００３３】このフイルムの空気抜け時間を測定する
と、５０００秒であり、巻姿は良好であった。このよう
に、一方の層（Ａ）に含有される粒子の含有量、粒子の
平均粒径とフイルム厚さとの関係および該フイルム厚さ
が本発明の範囲内である場合には、良好な巻姿が得られ
るフイルムとすることができる。The air vent time of this film was measured and found to be 5000 seconds, and the winding appearance was good. Thus, when the content of the particles contained in one layer (A), the relationship between the average particle size of the particles and the film thickness, and the film thickness within the range of the present invention, good winding is achieved. It can be a film that can be seen.
【００３４】実施例２〜７（表１） 実施例１と同様にして、含有粒子種、平均粒径、全厚に
対する積層部の厚み比等を変更して二軸配向ポリエステ
ルフイルムを作成した。結果、表１に示すような表面粗
さＲａ、面配向係数ｆn 、熱収縮率、空気抜け時間とな
り、ともに良好な巻姿が得られた。Examples 2 to 7 (Table 1) In the same manner as in Example 1, a biaxially oriented polyester film was prepared by changing the contained particle type, the average particle size, the thickness ratio of the laminated portion to the total thickness, and the like. As a result, the surface roughness Ra, the plane orientation coefficient f n , the heat shrinkage ratio, and the air bleeding time shown in Table 1 were all obtained, and a good winding shape was obtained.
【００３５】比較例１〜５（表２） 表２に示すような条件で二軸配向積層ポリエステルフイ
ルムを作製したが、比較例１、２においては、粒子含有
量が本発明の範囲から外れているため、良好な巻姿が得
られなかった。また、比較例３においては、表面粗さＲ
ａが、本発明の好ましい範囲を外れたため、良好な巻姿
が得られなかった。さらに比較例４、５は、粒子および
フイルム積層条件は実施例７と同じであるが、比較例４
においては熱固定温度を２４０℃とし、比較例５におい
ては熱固定なしとした。その結果、比較例４では、面配
向係数ｆn が本発明の好ましい範囲から外れ、比較例５
では、熱収縮率が本発明の好ましい範囲から外れ、とも
に良好な巻姿を得ることができなかった。Comparative Examples 1 to 5 (Table 2) Biaxially oriented laminated polyester films were prepared under the conditions shown in Table 2, but in Comparative Examples 1 and 2, the particle content was out of the range of the present invention. Therefore, a good winding shape could not be obtained. Further, in Comparative Example 3, the surface roughness R
Since a was outside the preferred range of the present invention, a good winding shape could not be obtained. Further, in Comparative Examples 4 and 5, the particle and film laminating conditions are the same as in Example 7, but Comparative Example 4
In Example 5, the heat setting temperature was 240 ° C., and in Comparative Example 5, no heat setting was performed. As a result, in Comparative Example 4, the surface orientation coefficient f n falls outside the preferred range of the present invention, and Comparative Example 5
Then, the heat shrinkage ratio was out of the preferable range of the present invention, and it was not possible to obtain a good winding shape.
【００３６】[0036]
【表１】 [Table 1]
【００３７】[0037]
【表２】 [Table 2]
【００３８】[0038]
【発明の効果】本発明の二軸配向熱可塑性樹脂フイルム
によれば、特定の厚さ以下のフイルム層に、不活性粒子
を０．００１重量％以上０．５重量％未満含有させ、粒
子含有層の厚さ、および粒子の平均粒径と粒子含有層の
厚さとの関係を特定したので、所望の均一な表面突起を
効率よく形成できるとともに、表面突起密度が高くなり
すぎないようにして、フイルム巻取の際フイルム層間か
ら容易に空気が抜けるようにし、良好な巻姿を得ること
ができる。According to the biaxially oriented thermoplastic resin film of the present invention, the film layer having a specific thickness or less contains 0.001% by weight or more and less than 0.5% by weight of inactive particles, and the particles are contained. Since the relationship between the layer thickness, and the average particle size of the particles and the thickness of the particle-containing layer was specified, a desired uniform surface protrusion can be efficiently formed, and the surface protrusion density should not be too high. When the film is wound, air can be easily released from between the film layers to obtain a good winding appearance.
【図１】本発明における空気抜け時間の測定に用いるベ
ック平滑度試験器の正面図である。FIG. 1 is a front view of a Beck's smoothness tester used for measuring an air escape time in the present invention.
【図２】図１の装置にフイルムをセットし、空気抜け時
間の測定の様子を示す、図１の装置のＩＩ部の概略拡大
構成図である。2 is a schematic enlarged configuration diagram of a portion II of the apparatus of FIG. 1, showing a state of setting a film in the apparatus of FIG. 1 and measuring an air bleeding time.
４ 減圧室 ５ 穴 ６、７ 測定対象フイルム 4 decompression chamber 5 holes 6 and 7 film to be measured
───────────────────────────────────────────────────── 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 9:00 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI technical display location B29L 9:00
Claims (7)
らなるフイルムであって、該粒子の含有量が０．００１
重量％以上０．５重量％未満、該粒子の平均粒径がフイ
ルム厚さの０．１〜１０倍、フイルム厚さが３μｍ以下
であることを特徴とする二軸配向熱可塑性樹脂フイル
ム。1. A film comprising a thermoplastic resin A containing inert particles, wherein the content of the particles is 0.001.
A biaxially oriented thermoplastic resin film, characterized in that the weight average particle diameter is 0.1 to 10 times the film thickness, and the film thickness is 3 μm or less.
くとも片面に、請求項１に記載の熱可塑性樹脂Ａからな
るフイルムが積層されてなることを特徴とする二軸配向
熱可塑性樹脂フイルム。2. A biaxially oriented thermoplastic resin film, characterized in that the film made of the thermoplastic resin B according to claim 1 is laminated on at least one side of the film made of the thermoplastic resin B.
ムの厚さが、３μｍ以下でかつフイルム全体の厚さの３
０％以下である請求項２の二軸配向熱可塑性樹脂フイル
ム。3. The laminated film made of the thermoplastic resin A has a thickness of 3 μm or less and 3 times the total thickness of the film.
The biaxially oriented thermoplastic resin film according to claim 2, which is 0% or less.
に、粒子が２重量％以下含有されている請求項２又は３
の二軸配向熱可塑性樹脂フイルム。4. The film layer made of the thermoplastic resin B contains 2% by weight or less of particles.
Biaxially oriented thermoplastic resin film.
表面粗さＲａが５ｎｍ以上である請求項１ないし４のい
ずれかに記載の二軸配向熱可塑性樹脂フイルム。5. The biaxially oriented thermoplastic resin film according to claim 1, wherein the film made of the thermoplastic resin A has a surface roughness Ra of 5 nm or more.
請求項１ないし５のいずれかに記載の二軸配向熱可塑性
樹脂フイルム。6. The biaxially oriented thermoplastic resin film according to claim 1, which has a plane orientation coefficient f n of 0.150 or more.
縮率が５％以下である請求項１ないし６のいずれかに記
載の二軸配向熱可塑性樹脂フイルム。7. The biaxially oriented thermoplastic resin film according to claim 1, which has a heat shrinkage in the longitudinal direction at 100 ° C. for 30 minutes of 5% or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26566593A JPH0788952A (en) | 1993-09-28 | 1993-09-28 | Biaxially oriented thermoplastic resin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26566593A JPH0788952A (en) | 1993-09-28 | 1993-09-28 | Biaxially oriented thermoplastic resin film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0788952A true JPH0788952A (en) | 1995-04-04 |
Family
ID=17420294
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26566593A Pending JPH0788952A (en) | 1993-09-28 | 1993-09-28 | Biaxially oriented thermoplastic resin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0788952A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0952176A1 (en) * | 1998-04-22 | 1999-10-27 | Mitsubishi Polyester Film GmbH | Multilayer, biaxially oriented polyester film, process for its manufacture and its use |
| US6214440B1 (en) | 1998-10-29 | 2001-04-10 | Mitsubishi Polyester Film Gmbh | Coextruded, biaxially oriented polyester film for metallizing, its use and process for its production |
| US6261663B1 (en) | 1998-04-22 | 2001-07-17 | Mitsubishi Polyster Film Gmbh | Single-layer, biaxially oriented polyester film, its use, and process for its production |
| US6358604B1 (en) | 1998-07-31 | 2002-03-19 | Mitsubishi Polyester Film Gmbh | Matte, coextruded polyester film, its use and process for its production |
| US6409862B1 (en) | 1998-08-27 | 2002-06-25 | Mitsubishi Polyester Film Gmbh | Process for producing biaxially oriented PET films and use of the same for SMD-technology film capacitors |
| US6565936B1 (en) | 1998-11-03 | 2003-05-20 | Mitsubishi Polyester Film Gmbh | Film laminate comprising a biaxially oriented polyester film with high oxygen barrier, its use and a process for its production |
-
1993
- 1993-09-28 JP JP26566593A patent/JPH0788952A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0952176A1 (en) * | 1998-04-22 | 1999-10-27 | Mitsubishi Polyester Film GmbH | Multilayer, biaxially oriented polyester film, process for its manufacture and its use |
| US6261663B1 (en) | 1998-04-22 | 2001-07-17 | Mitsubishi Polyster Film Gmbh | Single-layer, biaxially oriented polyester film, its use, and process for its production |
| US6358604B1 (en) | 1998-07-31 | 2002-03-19 | Mitsubishi Polyester Film Gmbh | Matte, coextruded polyester film, its use and process for its production |
| US6409862B1 (en) | 1998-08-27 | 2002-06-25 | Mitsubishi Polyester Film Gmbh | Process for producing biaxially oriented PET films and use of the same for SMD-technology film capacitors |
| US6214440B1 (en) | 1998-10-29 | 2001-04-10 | Mitsubishi Polyester Film Gmbh | Coextruded, biaxially oriented polyester film for metallizing, its use and process for its production |
| US6565936B1 (en) | 1998-11-03 | 2003-05-20 | Mitsubishi Polyester Film Gmbh | Film laminate comprising a biaxially oriented polyester film with high oxygen barrier, its use and a process for its production |
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