JP2576321B2 - Biaxially oriented laminated film - Google Patents
Biaxially oriented laminated filmInfo
- Publication number
- JP2576321B2 JP2576321B2 JP3271807A JP27180791A JP2576321B2 JP 2576321 B2 JP2576321 B2 JP 2576321B2 JP 3271807 A JP3271807 A JP 3271807A JP 27180791 A JP27180791 A JP 27180791A JP 2576321 B2 JP2576321 B2 JP 2576321B2
- Authority
- JP
- Japan
- Prior art keywords
- particles
- particle size
- film
- biaxially oriented
- laminated film
- 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
- Laminated Bodies (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Magnetic Record Carriers (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、二軸配向積層フイルム
に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a biaxially oriented laminated film.
【０００２】[0002]
【従来の技術】二軸配向積層フイルム、例えば二軸配向
ポリエステルフイルムとしては、ポリエステルにコロイ
ド状シリカに起因する実質的に球形のシリカ粒子を含有
せしめたフイルムが知られている（たとえば特開昭５９
−１７１６２３号公報）。2. Description of the Related Art As a biaxially oriented laminated film, for example, a biaxially oriented polyester film, a film in which a polyester contains substantially spherical silica particles originating from colloidal silica is known (for example, see Japanese Patent Application Laid-Open No. H10-163,873). 59
171623).
【０００３】[0003]
【発明が解決しようとする課題】しかし、フイルムの加
工工程、特に磁気媒体用途における磁性層塗布・カレン
ダー及び巻取、カセット組み込み工程などの工程速度の
増大に伴い、接触するロールやガイドでフイルム表面、
とくに微小凹凸を有するフイルム表面が削り取られやす
いという欠点があった。また、従来のものでは、高速磁
界転写などによるダビングの増速化にともない、ダビン
グ時の画質低下のために、画質すなわちＳ／Ｎ（シグナ
ル／ノイズ比）も不十分という欠点があった。However, as the processing speed of the film processing step, especially the application of a magnetic layer for magnetic media, such as the coating and calendering of a magnetic medium, the winding step, and the cassette assembling step, increases, the film surface is contacted by rolls and guides that come into contact. ,
In particular, there is a disadvantage that the film surface having minute irregularities is easily scraped off. Further, the conventional one has a disadvantage that the image quality, that is, the S / N (signal / noise ratio) is insufficient because the image quality at the time of dubbing decreases due to the increase in dubbing due to high-speed magnetic field transfer or the like.
【０００４】本発明は、かかる問題点を解決し、特に高
速工程でフイルム表面が削り取られにくく（以下高速削
れ性に優れるという）、しかも磁気媒体用途とした時に
ダビング時等の画質低下の少ない、つまり電磁変換特性
のよい（以下電磁変換特性に優れるという）二軸配向積
層フイルムを提供することを目的とする。The present invention solves such a problem, and in particular, the film surface is hardly scraped off in a high-speed process (hereinafter referred to as excellent in high-speed shaving property). That is, an object of the present invention is to provide a biaxially oriented laminated film having good electromagnetic conversion characteristics (hereinafter referred to as excellent in electromagnetic conversion characteristics).
【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
二軸配向積層フイルムは、少なくとも３層の積層構造を
有し、その少なくとも片面の最表層部に、少なくとも３
種類の粒子Ａ、Ｂ、Ｃを含有してなる二軸配向積層フイ
ルムであって、粒子Ａはジルコニア、鎖状シリカまたは
アルミナから選ばれた一次粒径が１〜１００ｎｍの粒子
であり、粒子Ｂは一次粒径が０．１〜２μｍ、含有量が
０．００５〜２重量％のカルサイト型炭酸カルシウムで
あり、粒子Ｃはコロイダルシリカ、架橋型有機粒子また
はバテライト型炭酸カルシウムから選ばれた一次粒径が
０．１〜２μｍ、含有量が０．００５〜２重量％の粒子
であり、前記粒子Ｂの粒径ｄと粒子Ｂが含有される該層
部の厚さｔとの関係が ０．５ｄ≦ｔ≦５ｄ であるものから成る。A biaxially oriented laminated film according to the present invention for this purpose has a laminated structure of at least three layers, and has at least three layers on at least one surface thereof.
A biaxially oriented laminated film containing particles A, B, and C, wherein the particles A are particles having a primary particle diameter of 1 to 100 nm selected from zirconia, chain silica or alumina, and particles B Is calcite-type calcium carbonate having a primary particle size of 0.1 to 2 μm and a content of 0.005 to 2% by weight, and the particle C is a primary particle selected from colloidal silica, crosslinked organic particles, and vaterite-type calcium carbonate. Particles having a particle size of 0.1 to 2 μm and a content of 0.005 to 2% by weight, wherein the relationship between the particle size d of the particles B and the thickness t of the layer containing the particles B is 0. .5d ≦ t ≦ 5d.
【０００６】まず、本発明のフイルムは少なくとも３層
以上の積層構造である必要がある。３層以上であれば、
４層でも５層でもかまわないが３層構造の場合に本発明
の効果がより一層良好となり好ましい。しかし、単層や
２層構造のフイルムでは高速削れ性や電磁変換特性を満
足させることはできない。First, the film of the present invention needs to have a laminated structure of at least three layers. If there are three or more layers,
Four or five layers may be used, but a three-layer structure is preferable because the effects of the present invention are further improved. However, a film having a single-layer or two-layer structure cannot satisfy high-speed shaving properties and electromagnetic conversion characteristics.
【０００７】次に、本発明のフイルムは、これを構成す
る上記各層の少なくとも一層が二軸に配向している必要
がある。３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。Next, in the film of the present invention, it is necessary that at least one of the layers constituting the film is biaxially oriented. It is particularly preferable that all the layers of the three or more layered structure are biaxially oriented. If all the layers are non-oriented or uniaxially oriented, the properties of the present invention cannot be satisfied.
【０００８】本発明の二軸配向積層フイルムを構成する
ポリマーは特に限定されないが、磁気媒体用途としては
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。[0008] The polymer constituting the biaxially oriented laminated film of the present invention is not particularly limited, but polyester is preferred for use in magnetic media. The polyester is not particularly limited, but ethylene terephthalate, ethylene α,
β-bis (2-chlorophenoxy) ethane-4,4′-
It is particularly preferred when at least one structural unit selected from dicarboxylate and ethylene 2,6-naphthalate units is the main constituent. Among them, a polyester containing ethylene terephthalate as a main component is particularly preferable. In addition, two or more types of polyesters may be mixed or a copolymer may be used within a range not to impair the present invention.
【０００９】本発明の二軸配向積層フイルムの少なくと
も片面の最表層部には、少なくとも３種類の粒子Ａ、
Ｂ、Ｃが含有される。粒子Ａは比較的粒径の小さな粒子
からなり、主として最表層部の地肌を補強する役目を担
う。粒子Ｂは、粒子Ａよりも粒径の大きな粒子からな
り、最表層部の表面に突起を形成して、耐削れ性を向上
させつつ、高速走行性を向上する役目を担う。粒子Ｃ
は、粒子Ｂによるよりは低い表面突起を形成し、表面粗
面化の効果をさらに向上して一層低摩擦係数とし、フイ
ルムの高速走行性をより改良する役目を担う。In the biaxially oriented laminated film of the present invention, at least one type of particles A,
B and C are contained. The particles A are composed of particles having a relatively small particle diameter, and mainly serve to reinforce the surface of the outermost layer. The particles B are composed of particles having a larger particle size than the particles A, and form projections on the surface of the outermost layer portion, and play a role of improving high-speed running while improving abrasion resistance. Particle C
Has a role of forming lower surface projections than the particles B, further improving the effect of surface roughening, further reducing the friction coefficient, and further improving the high-speed running property of the film.
【００１０】粒子Ａは、ジルコニア、鎖状シリカ、また
はアルミナ粒子から選ばれる。この材質により、最表層
部の地肌が効果的に補強される。粒子Ａの平均一次粒径
は１〜１００ｎｍであり、より好ましくは１０〜４０ｎ
ｍである。一次粒径が１ｎｍよりも小さいと、地肌補強
効果が薄れ、１００ｎｍよりも大きいと、表面突起形成
作用が現われ、高速削れ性が悪化するおそれがある。The particles A are selected from zirconia, chain silica, or alumina particles. With this material, the ground of the outermost layer is effectively reinforced. The average primary particle size of the particles A is 1 to 100 nm, more preferably 10 to 40 n.
m. When the primary particle size is smaller than 1 nm, the background reinforcing effect is weakened, and when the primary particle size is larger than 100 nm, a surface projection forming effect appears, and high-speed shaving property may be deteriorated.
【００１１】この粒子Ａは、地肌補強効果の面からは、
ある程度凝集している方が望ましい。凝集状態での粒
径、すなわち二次粒径が、二次粒径／一次粒径の比で３
〜６０の範囲であると、最表層部の地肌が効果的に補強
される。単分散又はそれに近い状態、つまり二次粒径／
一次粒径の比が３未満であると、粒子凝集による地肌補
強向上効果が殆どなくなる。該比が６０を越えると、凝
集粒子が大きくなりすぎ、それがもろい突起を形成し
て、高速削れ性が悪化する。From the viewpoint of the background reinforcing effect, the particles A
It is desirable that the particles are aggregated to some extent. The particle size in the agglomerated state, that is, the secondary particle size is 3 in the ratio of secondary particle size / primary particle size.
When it is in the range of ~ 60, the ground of the outermost layer is effectively reinforced. Monodisperse or close to it, ie secondary particle size /
When the ratio of the primary particle diameters is less than 3, the effect of improving the ground reinforcement by the aggregation of the particles is almost eliminated. If the ratio exceeds 60, the aggregated particles become too large, and they form fragile projections, deteriorating high-speed scraping.
【００１２】粒子Ａの含有量は、好ましくは０．０５〜
２重量％、より好ましくは０．１〜１重量％である。含
有量が０．０５重量％未満であると、層内粒子密度が低
くなりすぎるため、期待した地肌補強効果が得られない
おそれがある。含有量が２重量％を越えると、粒子量が
多くなりすぎ、層が逆に脆くなるおそれがある。The content of the particles A is preferably from 0.05 to
It is 2% by weight, more preferably 0.1 to 1% by weight. If the content is less than 0.05% by weight, the density of the particles in the layer becomes too low, so that the expected background reinforcing effect may not be obtained. If the content exceeds 2% by weight, the amount of particles becomes too large, and the layer may be brittle.
【００１３】この粒子Ａは、上述の如く地肌補強効果を
担うものであるから、最表層部の中でも、とくに表面近
傍に集まっていることが望ましい。このようにすること
により、最表層部表面の地肌が効果的に補強され、粒子
Ａを含有させた効果が顕著に現われる。粒子Ａがどの程
度表面近傍に集まっているかを定量的に表わすため、本
発明では表層粒子濃度をその指標としている。粒子Ａの
表層粒子濃度が０．１以上のとき、上記地肌補強効果が
顕著になる。Since the particles A are responsible for the background reinforcing effect as described above, it is desirable that the particles A are gathered particularly near the surface in the outermost layer. By doing so, the background on the surface of the outermost layer is effectively reinforced, and the effect of including the particles A is remarkably exhibited. In the present invention, the surface layer particle concentration is used as an index in order to quantitatively express how much particles A are gathered near the surface. When the surface particle concentration of the particles A is 0.1 or more, the above-described background reinforcing effect becomes remarkable.
【００１４】粒子Ｂは、カルサイト型炭酸カルシシウム
の粒子とされる。この粒子材質の特定により、削れにく
い表面突起が効率よく形成される。カルサイト型炭酸カ
ルシウムは、六法晶系の結晶形態を有する、方解石等天
然の材料として存在するもので、安定した天然晶形態を
有する。変質等が生じないので、フイルムの延伸等機械
的、熱的負荷を受けても、安定して表面突起形成に寄与
できる。したがって、削れにくい、安定した表面突起が
形成される。なお、カルサイト型炭酸カルシウムの密度
は２．７１ｇ／ｃｍ3 程度で、複屈折率は１．６５８と
比較的大きい。The particles B are calcite-type calcium carbonate particles. By specifying the particle material, surface projections that are difficult to cut are efficiently formed. Calcite-type calcium carbonate exists as a natural material such as calcite having a hexagonal crystal form, and has a stable natural crystal form. Since there is no deterioration or the like, even if a mechanical or thermal load such as stretching of the film is applied, it can contribute to the formation of surface projections stably. Therefore, stable surface projections that are hard to be removed are formed. The calcite calcium carbonate has a density of about 2.71 g / cm 3 and a relatively large birefringence of 1.658.
【００１５】粒子Ｂの平均一次粒径は、０．１〜２μｍ
であり、より好ましくは０．６〜１μｍである。０．１
μｍよりも小さいと、形成される突起の高さが低くなり
すぎ、摩擦係数低減効果が小さくなって良好な走行性が
得られない。２μｍを越えると、突起高さが高くなりす
ぎるため、高速削れ性に劣る。The average primary particle size of the particles B is 0.1 to 2 μm.
And more preferably 0.6 to 1 μm. 0.1
If it is smaller than μm, the height of the formed projections becomes too low, and the effect of reducing the friction coefficient becomes small, so that good running properties cannot be obtained. If it exceeds 2 μm, the height of the projections becomes too high, so that high-speed shaving is inferior.
【００１６】粒子Ｂの含有量は、０．００５〜２重量
％、より好ましくは０．２〜０．５重量％である。含有
量が０．００５重量％未満であると、表面突起個数が少
なくなりすぎるので、突起以外の地肌の接触面積が大き
くなりすぎ、摩擦係数が高くなって走行性が悪くなる。
逆に２重量％を越えると、粒子数が多くなりすぎ、層自
身が脆くなるとともに、粒子が脱落しやすくなるおそれ
がある。The content of the particles B is 0.005 to 2% by weight, more preferably 0.2 to 0.5% by weight. If the content is less than 0.005% by weight, the number of surface projections becomes too small, so that the contact area of the background other than the projections becomes too large, the friction coefficient becomes high, and the running property deteriorates.
Conversely, if it exceeds 2% by weight, the number of particles becomes too large, the layer itself becomes brittle, and the particles may easily fall off.
【００１７】この粒子Ｂが、少なくとも一方の最表層部
に含有されて、該層表面に突起を形成する。全粒子Ｂ
が、完全に該層中に埋没しているような状態では、表面
突起は形成されにくいので、粒子Ｂ含有により所望の表
面突起を形成するためには、粒子Ｂの粒径と粒子Ｂを含
有する層の厚さとの間に相対的な関係を特定する必要が
ある。本発明では、粒子Ｂの一次粒径ｄと粒子Ｂが含有
される層部の厚さｔとの関係が、０．５ｄ≦ｔ≦５ｄに
設定される。相対関係をこの範囲とすることにより、粒
子Ｂにより高さの揃った、しかも所望高さの表面突起が
形成される。この均一な所望の表面突起形成によって、
高速削れ性とともに電磁変換特性が向上される。The particles B are contained in at least one of the outermost layers to form projections on the surface of the layer. All particles B
However, in a state where the particles are completely buried in the layer, surface projections are hardly formed. Therefore, in order to form desired surface projections by containing particles B, the particle diameter of particles B and the particle It is necessary to specify a relative relationship between the thickness of the layer to be formed. In the present invention, the relationship between the primary particle size d of the particles B and the thickness t of the layer containing the particles B is set to 0.5d ≦ t ≦ 5d. By setting the relative relationship within this range, the surface protrusions having a uniform height and a desired height are formed by the particles B. By this uniform desired surface projection formation,
Electromagnetic conversion characteristics are improved together with high-speed shaving.
【００１８】粒子Ｃは、コロイダルシリカ、架橋型有機
粒子またはバテライト型炭酸カルシウム粒子から選ばれ
る。このような材質の粒子は、比較的粒径をそろえやす
いので、均一粒径の粒子により形成される突起が、粒子
Ｂにより形成される突起を補うように、表面突起形成が
行われる。すなわち、粒子Ｂにより比較的高い突起を形
成し、それを補うように（その突起間に又はその突起に
上のせされるように）粒子による突起が形成されるの
で、表面が一層均一にしかも粗大突起を形成することな
く粗面化され、摩擦係数が大幅に低減されて優れた走行
性が得られる。また、このような材質の粒子Ｃは、ポリ
エステル等フイルム母材との親和性も高いので、粒子Ｂ
による突起を補強することもできる。上記材質のうち、
バテライト型炭酸カルシウムは、六方晶系の結晶形態を
有し、自然界では巻貝の一種に見られるのみであるの
で、通常、合成品として製造されている。加熱下あるい
は水の存在下でカルサイト型になるので、合成は通常ア
ルコール中で行われる。合成品で品質上均一化されてい
るが、不安定な（活性が高い）ため、ポリエステル等と
の親和性が高い。密度は２．５４ｇ／ｃｍ3 程度で、複
屈折率は１．５５０と小さい。特に本発明では、均一品
質、均一粒径、およびポリエステル等と親和性が高い点
が有効に利用され、該粒子Ｃにより、粒子Ｂによる突起
よりは小さく均一な高さで削られにくい突起が形成され
る。架橋型有機粒子も、均一粒径に形成しやすく、ポリ
エステル等フイルム母材との親和性も極めて高い。架橋
型有機粒子の材質としては、例えば架橋ポリスチレンや
架橋ジビニルベンゼン等が挙げられる。The particles C are selected from colloidal silica, crosslinked organic particles and vaterite-type calcium carbonate particles. Since particles of such a material are relatively easy to have a uniform particle size, surface protrusions are formed such that protrusions formed by particles having a uniform particle size compensate for protrusions formed by particles B. That is, relatively high projections are formed by the particles B, and the projections of the particles are formed so as to supplement (be placed between or on the projections), so that the surface is more uniform and coarse. The surface is roughened without forming projections, the friction coefficient is significantly reduced, and excellent running properties are obtained. Further, since the particles C of such a material have a high affinity with a film base material such as polyester, the particles B
Can be reinforced. Of the above materials,
Vaterite-type calcium carbonate has a hexagonal crystal form and is found only in a kind of snail in the natural world, and is usually manufactured as a synthetic product. The synthesis is usually carried out in alcohol since it becomes calcite-type under heating or in the presence of water. Synthetic products are uniform in quality, but are unstable (high in activity) and have high affinity with polyester and the like. The density is about 2.54 g / cm 3 and the birefringence is as small as 1.550. In particular, in the present invention, the uniform quality, uniform particle size, and high affinity with polyester and the like are effectively used, and the particles C form projections smaller than the projections by the particles B and hard to be cut at a uniform height. Is done. The crosslinked organic particles are also easily formed into a uniform particle size, and have an extremely high affinity for a film base material such as polyester. Examples of the material of the crosslinked organic particles include crosslinked polystyrene and crosslinked divinylbenzene.
【００１９】粒子Ｃの平均一次粒径も、０．１〜２μｍ
であり、より好ましくは０．６〜１μｍである。０．１
μｍよりも小さいと、形成される突起の高さが低くなり
すぎ、走行性改良効果が小さくなる。２μｍを越える
と、粒子Ｂによる突起よりも突出する部分が生じ、高速
削れ性が悪くなるおそれがある。The average primary particle size of the particles C is also 0.1 to 2 μm.
And more preferably 0.6 to 1 μm. 0.1
If it is smaller than μm, the height of the projections formed is too low, and the effect of improving running properties is reduced. If it exceeds 2 μm, a portion protruding from the projections due to the particles B is formed, and the high-speed scraping property may be deteriorated.
【００２０】粒子Ｃの含有量は、０．００５〜２重量
％、より好ましくは０．２〜０．５重量％である。含有
量が０．００５重量％未満であると、粒子Ｃによる突起
個数が少なくなりすぎるので、走行性改良効果が期待で
きない。逆に２重量％を越えると、粒子数が多くなりす
ぎ、層自身が脆くなるとともに、粒子が脱落しやすくな
るおそれがある。The content of the particles C is 0.005 to 2% by weight, more preferably 0.2 to 0.5% by weight. If the content is less than 0.005% by weight, the number of projections due to the particles C becomes too small, so that a running property improving effect cannot be expected. Conversely, if it exceeds 2% by weight, the number of particles becomes too large, the layer itself becomes brittle, and the particles may easily fall off.
【００２１】この粒子Ｃは、粒子Ｂによる突起形成を阻
害しないように比較的小さな突起を形成して表面をより
粗面化するものであるから、極力均一な粒径、つまり粗
大粒子のない方が好ましい。そのためには、粒子Ｃの粒
径分布による規制を設けることが望ましい。粒子Ｃの粒
径分布をシャープな分布とするため、粒径分布を相対標
準偏差で０．６以下にすることが好ましい。Since the surface of the particle C is formed by forming relatively small protrusions so as not to hinder the formation of protrusions by the particles B, the surface of the particle C is made as uniform as possible. Is preferred. For that purpose, it is desirable to provide a regulation based on the particle size distribution of the particles C. In order to make the particle size distribution of the particles C sharp, it is preferable that the particle size distribution be 0.6 or less in relative standard deviation.
【００２２】さらに本発明フイルムにおいては、中間層
は特に限定されないが、最表層部において、上述の如く
高速削れ性に優れ、均一な所望突起高さの突起が形成さ
れ電磁変換特性に優れた表面を形成できるので、中間層
にいわゆるリサイクルポリマを含有させることが好まし
い。なおここでリサイクルポリマとは、たとえばポリエ
ステルの場合、ポリエステルの末端カルボン酸が５５当
量／１０6 ｇ以上でポリマの溶液ヘイズが１８％以下の
ものをいう。Further, in the film of the present invention, the intermediate layer is not particularly limited, but the surface layer is excellent in high-speed scraping properties as described above, and has a uniform projection height at the outermost layer, and has excellent electromagnetic conversion characteristics. Therefore, it is preferable to include a so-called recycled polymer in the intermediate layer. Here, in the case of polyester, for example, in the case of polyester, the terminal carboxylic acid of the polyester is 55 equivalents / 10 6 g or more and the solution haze of the polymer is 18% or less.
【００２３】また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、異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, different polymers may be blended as long as the object of the present invention is not impaired, and organic films such as antioxidants, heat stabilizers, lubricants and ultraviolet absorbers may be used. It may be added to the extent that additives are usually added.
【００２４】次に本発明フイルムの製造方法を、ポリエ
ステルフイルムの場合について説明する。まず、ポリエ
ステルに粒子Ａ、Ｂ、Ｃ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粒子
Ａ、Ｂ、Ｃを別々に所定割合にて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、高速削れ性、電磁変換特性を共に良好
とすることができる。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, the method for producing the film of the present invention will be described for the case of a polyester film. First, as a method for incorporating particles A, B, and C into polyester,
For example, a method is preferred in which particles A, B, and C are separately dispersed in a predetermined ratio in the form of a slurry in ethylene glycol, which is a diol component, and the ethylene glycol is polymerized with a predetermined dicarboxylic acid component. When adding the particles, for example, if the water sol or alcohol sol obtained during the synthesis of the particles is added without drying once, the dispersibility of the particles is very good, and the high-speed scraping property and the electromagnetic conversion characteristics are both good. be able to. A method of directly mixing a water slurry of particles with predetermined polyester pellets, supplying the mixture to a vent-type twin-screw kneading extruder, and kneading the resulting mixture with polyester is also very effective for further improving the effects of the present invention. As a method of adjusting the content of particles, a method of preparing a high-concentration particle master by the above method and diluting it with a polyester substantially containing no particles during film formation to adjust the content of particles is known. It is valid.
【００２５】次にこのポリエステルのペレットを用いて
３層以上の積層構造をもったポリエステルフイルムとす
る。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、公知の溶融積層用
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。すなわち、２または３台以上の押出
機、３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３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。Next, a polyester film having a laminated structure of three or more layers is formed using the polyester pellets. The polyester pellets obtained by the above method are mixed at a predetermined ratio, dried, fed to a known extruder for melt lamination, extruded from a slit die into a sheet, and cooled and solidified on a casting roll. At least make an unstretched film. That is, two or three or more extruders, three or more layers are stacked using a manifold or a merging block (for example, a merging block having a square merging portion),
Three or more layers of the sheet are extruded from a die and cooled by a casting roll to produce an unstretched film. In this case, a method of installing a static mixer and a gear pump in the polymer flow path 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. than that on the base layer side.
【００２６】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
〜５．０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 and biaxially oriented. As the stretching method, a sequential biaxial stretching method or a simultaneous biaxial stretching method can be used. However, using a sequential biaxial stretching method in which stretching in the longitudinal direction and then in the width direction is performed first, the stretching in the longitudinal direction is divided into 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 unconditionally determined.
It is effective to set the temperature to 30 ° C. and to increase the temperature after the second stage. The longitudinal stretching speed is 5,000 to 50,000% /
A range of minutes is preferred. As a stretching method in the width direction, a method using a stenter is generally used. Stretch ratio is 3.0
A range of up to 5.0 times is appropriate. The stretching speed in the width direction is
The temperature is preferably in the range of 1000 to 20000% / min and the temperature is in the range of 80 to 160 ° C. Next, this stretched film is heat-treated. The heat treatment temperature in this case is 170 to 220 ° C., particularly 1
The temperature is preferably from 80 to 200 ° C. and the time is preferably from 0.2 to 20 seconds.
【００２７】［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Ａ、Ｂ、Ｃの平均一次粒径 Ｂ．Ｅ．Ｔ法により粒子の比表面積を求め、この比表面
積から粒子を球としたときの粒径を下式により求め、こ
れを平均一次粒径とした。 粒径＝６／（粒子密度×比表面積） この方法で測定することが困難な場合、電子顕微鏡など
による粒子の観察から一次粒径を求めることもできる。[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) Average primary particle size of particles A, B and C E. FIG. The specific surface area of the particles was determined by the T method, and the particle diameter when the particles were made into spheres was determined from the specific surface area by the following equation, and this was defined as the average primary particle diameter. Particle size = 6 / (particle density × specific surface area) When it is difficult to measure by this method, the primary particle size can also be obtained by observing the particles with an electron microscope or the like.
【００２８】（２）粒子Ａの二次粒径 粒子を含有したフイルムを、フイ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、１０
万倍程度で粒子を観察し、粒子の円相当径を求め、５０
視野について平均した値を粒子の二次粒径とした。(2) Secondary Particle Size of Particle A The film containing the particles is formed into an ultra-thin section perpendicular to the plane of the film and having a thickness of 1000 °, and is measured using a transmission electron microscope (for example, JEM-1200EX manufactured by JEOL Ltd.). Ten
Observe the particles at about 10,000 times, find the equivalent circle diameter of the particles,
The value averaged over the visual field was taken as the secondary particle size of the particles.
【００２９】（３）粒子の含有量 フイルム母材を溶解し粒子は溶解させない溶媒を選択
し、粒子をフイルム母材から遠心分離し、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。
また、必要に応じて熱分解ガスクロマトグラフィーや赤
外分光法や、蛍光Ｘ線分析法、ラマン散乱、ＳＥＭ−Ｘ
ＭＡなどを利用して定量することもできる。積層部およ
び基層部の粒子の含有は、各積層部を削りとることによ
り区別できる。また、必要に応じてＴＥＭを用いて各断
面に観察される粒子の個数から計算することもできる。(3) Content of Particles A solvent in which the film base material is dissolved but the particles are not dissolved is selected, the particles are centrifuged from the film base material, and the particle content is defined as a ratio (% by weight) to the total weight of the particles. I do.
If necessary, pyrolysis gas chromatography, infrared spectroscopy, fluorescent X-ray analysis, Raman scattering, SEM-X
It can also be determined using MA or the like. The content of the particles in the laminated portion and the base layer portion can be distinguished by shaving each laminated portion. Further, if necessary, it can be calculated from the number of particles observed in each cross section using a TEM.
【００３０】（４）表層粒子濃度 ２次イオンマススペクトル（ＳＩＭＳ）を用いて、フイ
ルム中の粒子に起因する元素のうち最も高濃度の元素
と、熱可塑性樹脂の炭素元素の濃度比を、深さ方向表層
から３ｎｍにおいて求め、粒子濃度とした。測定装置、
条件は下記のとおりである。 １次イオン種 ：１２ＫＶ １次イオン加速電圧：１２ＫＶ １次イオン電流 ：２００ｎＡ ラスター領域 ：４００μｍ□ 分析領域 ：ゲート３０％ 測定真空度 ：６．０×１０-9Ｔｏｒｒ Ｅ−ＧＵＮ ：０．５ＫＶ−３．０Ａ(4) Surface Particle Concentration Using a secondary ion mass spectrum (SIMS), the concentration ratio of the highest concentration element among the elements originating from the particles in the film to the carbon element of the thermoplastic resin is determined by the following method. The particle concentration was determined at 3 nm from the surface layer in the direction of the direction, and was defined as the particle concentration. measuring device,
The conditions are as follows. Primary ion species: 12 KV Primary ion acceleration voltage: 12 KV Primary ion current: 200 nA Raster area: 400 μm □ Analysis area: Gate 30% Measurement vacuum degree: 6.0 × 10 −9 Torr E-GUN: 0.5 KV− 3.0A
【００３１】（５）最表層部の厚さ ２次イオン質量分析装置（ＳＩＭＳ）を用いて、フイル
ム中の粒子の内最も高濃度の粒子に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層の表面から深さ（厚さ）方向の
分析を行なう。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。なお、フイルム中
にもっとも多く含有する粒子が有機高分子粒子の場合は
ＳＩＭＳでは測定が難しいので、表面からエッチングし
ながらＸＰＳ（Ｘ線光電子分光法）、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し、上記同様の手法から
積層厚さを求めても良い。さらに上述のデプスプロファ
イルからではなく、フイルムの断面観察あるいは薄膜段
差測定機等によって求めることができる。(5) Thickness of Outermost Layer Using a secondary ion mass spectrometer (SIMS), the concentration ratio (M) of the element resulting from the highest concentration of the particles in the film and the carbon element of the polyester is determined. + / C + ) is defined as the particle concentration, and the analysis is performed in the depth (thickness) direction from the surface of the polyester A layer. In the surface layer, the particle concentration is low due to the interface of the surface, and the particle concentration increases as the distance from the surface increases. In the case of the film of the present invention, the particle concentration that has once reached the maximum value at the depth [I] starts to decrease again. Based on this concentration distribution curve, the depth at which the particle concentration of the maximum value becomes 1/2 [II]
(Where II> I) was taken as the lamination thickness. In addition, when the particles most contained in the film are organic polymer particles, it is difficult to measure by SIMS. Therefore, while etching from the surface, XPS (X-ray photoelectron spectroscopy), IR (infrared spectroscopy) or a confocal microscope is used. For example, the depth profile of the particle concentration may be measured, and the layer thickness may be obtained by the same method as described above. Furthermore, it can be obtained not from the above-mentioned depth profile but by observation of a cross section of a film or a thin film step measuring device.
【００３２】（６）粒子Ｃの粒径分布 上記（１）の方法で一次粒径を、粒子１０００個につい
て求め、その相対標準偏差で粒径分布を表わした。(6) Particle Size Distribution of Particle C The primary particle size was determined for the 1000 particles by the method described in (1) above, and the particle size distribution was represented by the relative standard deviation.
【００３３】（７）高速削れ性 フイルムを１／２インチ幅のテープ状にスリットしたも
のに角度９０°で片刃を押しあて、０．５mm押し込んで
２００ｍ走行させる（速度：２００m/min 、張力：１０
０ｇ）。片刃に削りとられた粉の付着高さを顕微鏡で読
み取り、削れ量（μｍ）とした。この削れ量が１８０μ
ｍ以下の場合耐削れ性が良好、それを越える場合耐削れ
性が不良である。(7) High-speed scalability One edge of the film is slit into a tape having a width of 1/2 inch and pressed at an angle of 90 °, and the film is pushed in by 0.5 mm and run for 200 m (speed: 200 m / min, tension: 10
0 g). The adhering height of the powder shaved on one blade was read with a microscope, and the shaved amount (μm) was determined. This shaving amount is 180μ
When it is less than m, the abrasion resistance is good, and when it exceeds it, the abrasion resistance is poor.
【００３４】（８）電磁変換特性 フイルムに下記組成の磁性塗料をグラビヤロールにより
塗布し、磁気配向させ、乾燥させる。さらに、小型テス
トカレンダー装置（スチールロール／ナイロンロール、
５段）で、温度：７０℃、線圧：２００kg/cm でカレン
ダー処理した後、７０℃、４８時間キュアリングする。
上記テープ原反を１／２インチにスリットし、パンケー
キを作成した。このパンケーキから長さ２５０ｍの長さ
をＶＴＲカセットに組み込みＶＴＲカセットテープとし
た。 （磁性塗料の組成） ・Ｃｏ含有酸化鉄 ：１００重量部 ・塩化ビニル／酢酸ビニル共重合体： １０重量部 ・ポリウレタンエラストマ ： １０重量部 ・ポリイソシアネート ： ５重量部 ・レシチン ： １重量部 ・メチルエチルケトン ： ７５重量部 ・メチルイソプチルケトン ： ７５重量部 ・トルエン ： ７５重量部 ・カーボンブラック ： ２重量部 ・ラウリン酸 ：１．５重量部 このテープに家庭用ＶＴＲを用いてテレビ試験波形発生
器により１００％クロマ信号を記録し、その再生信号か
らカラービデオノイズ測定器でクロマＳ／Ｎを測定し
た。このＳ／Ｎを市販のＶＨＳテープと比較して、下記
の基準で判定した。 ＋１．５（ｄＢ）以上 ：優 ０（ｄＢ）以上、＋１．５（ｄＢ）未満 ：良 ０（ｄＢ）未満 ：不良 (8) Electromagnetic conversion characteristics A magnetic paint having the following composition is applied to a film by a gravure roll, magnetically oriented, and dried. In addition, a small test calendar device (steel roll / nylon roll,
5), a calendar treatment is performed at a temperature of 70 ° C. and a linear pressure of 200 kg / cm 2, and then curing is performed at 70 ° C. for 48 hours.
The raw tape was slit into 1/2 inch to prepare a pancake. A length of 250 m from this pancake was incorporated into a VTR cassette to form a VTR cassette tape. (Composition of magnetic paint) Co-containing iron oxide: 100 parts by weight Vinyl chloride / vinyl acetate copolymer: 10 parts by weight Polyurethane elastomer: 10 parts by weight Polyisocyanate: 5 parts by weight Lecithin: 1 part by weight Methyl ethyl ketone : 75 parts by weight-Methylisobutyl ketone: 75 parts by weight-Toluene: 75 parts by weight-Carbon black: 2 parts by weight-Lauric acid: 1.5 parts by weight Using a home VTR on this tape, using a TV test waveform generator A 100% chroma signal was recorded, and the chroma S / N was measured from the reproduced signal using a color video noise measuring instrument. Compare this S / N with a commercially available VHS tape,
It was determined based on the following criteria. +1.5 (dB) or more: excellent 0 (dB) or more, less than +1.5 (dB) : good less than 0 (dB): bad
【００３５】[0035]
【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） 粒子Ａとして一次粒径２０ｎｍのジルコニア粒子をエチ
レングリコール中にて、５０μｍ径のガラスビーズをメ
ディアとして分散させ、ガラスビーズを除去したのちテ
レフタル酸と重合し、ポリエチレンテレフタレートのマ
スターペレットとした。Next, embodiments of the present invention will be described based on examples. Example 1 (Table 1) Zirconia particles having a primary particle diameter of 20 nm as particles A were dispersed in ethylene glycol using glass beads having a diameter of 50 µm as a medium. After removing the glass beads, the resulting mixture was polymerized with terephthalic acid to obtain polyethylene terephthalate. A master pellet was used.
【００３６】次に、粒子Ｂとして一次粒径０．８μｍの
カルサイト型炭酸カルシウム粒子を上記メディア分散法
を用いてエチレングリコール中に均一に分散させ、上記
と同様にして粒子Ｂのマスターペレットを得た。Next, calcite-type calcium carbonate particles having a primary particle size of 0.8 μm as particles B are uniformly dispersed in ethylene glycol using the above-mentioned media dispersion method, and a master pellet of particles B is prepared in the same manner as described above. Obtained.
【００３７】粒子Ｃとして一次粒径０．４μｍのコロイ
ダルシリカ粒子を同様の方法でエチレングリコール中に
均一分散させ、上記と同様にして粒子Ｃのマスターペレ
ットを得た。Colloidal silica particles having a primary particle size of 0.4 μm as particles C were uniformly dispersed in ethylene glycol by the same method, and a master pellet of particles C was obtained in the same manner as described above.
【００３８】上記粒子Ａのマスターペレット、粒子Ｂの
マスターペレット、粒子Ｃのマスターペレット、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、とくに粒子Ｂ、粒子Ｃの含有量がそれぞれ０．４
重量％、０．１重量％になるように混ぜ合わせ、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、リサイ
クルポリマ３０重量部と粒子を含有しないペレット７０
重量部を混ぜ合わせた後、１８０℃で３時間減圧乾燥
（３Ｔｏｒｒ）し、押出機に供給して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３層合流ブロックに
て、基層部にポリマIIを、両面表層積層部にポリマ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。The master pellet of the particle A, the master pellet of the particle B, the master pellet of the particle C, and the pellet of polyethylene terephthalate containing no particles are used.
% By weight and 0.1% by weight, and supplied to the vented twin-screw kneading extruder 1 to dissolve at 280 ° C. (Polymer I). Further, another extruder 2 was prepared, and 30 parts by weight of the recycled polymer and pellets 70 containing no particles were used.
After mixing the parts by weight, the mixture was dried under reduced pressure (3 Torr) at 180 ° C. for 3 hours, supplied to an extruder and dissolved at 290 ° C. (Polymer II). These two polymers are each subjected to high-precision filtration, and then, in a three-layer merging block having a rectangular laminated portion, polymer II is laminated on the base layer so that polymer I comes on the double-sided surface laminated portion. And extruded it into a sheet from a die, wound around a casting drum having a surface temperature of 30 ° C. using an electrostatic application casting method, and cooled and solidified to produce an unstretched film having a thickness of about 160 μm. The draft ratio at this time was 6.5.
【００３９】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秒間熱処理し、厚さ１３μｍのフイルムを得
た。得られたフイルムの最表層部積層厚さｔは、１．０
μｍで、粒子Ｂの粒径ｄとの関係はｔ＝２．５ｄであっ
た。また粒子Ａの平均一次粒径は２０nm、二次粒径／一
次粒径の比は７であった。また粒子Ｃの粒径分布は０．
５であった。This unstretched film is divided into three stages in the longitudinal direction, 1.2 times at 123 ° C., 1.45 times at 126 ° C.,
Each was stretched 2.3 times at 14 ° C. This uniaxial film is divided into two stages in the width direction using a stenter, stretched 3.7 times at 111 ° C. and 1.2 times at 113 ° C., and stretched 200 times at a constant length.
C. for 5 seconds to obtain a film having a thickness of 13 .mu.m. The outermost layer portion laminated thickness t of the obtained film is 1.0
In μm, the relation with the particle diameter d of the particles B was t = 2.5d. The average primary particle size of the particles A was 20 nm, and the ratio of secondary particle size / primary particle size was 7. The particle size distribution of the particles C is 0.
It was 5.
【００４０】このフイルムの電磁変換特性を測定する
と、クロマＳ／Ｎで＋２．３ｄＢであった。また、高速
削れ性も３５μｍと良好であった。このように、最表層
積層部に含有される粒子の種類、粒子径、含有量、及び
積層厚さとの関係等が本発明の範囲内である場合には、
電磁変換特性、高速削れ性ともに良好なフイルムとする
ことができる。When the electromagnetic conversion characteristics of this film were measured, the chroma S / N was +2.3 dB. In addition, the high-speed scraping property was as good as 35 μm. In this manner, when the type of the particles contained in the outermost layer laminated portion, the particle size, the content, and the relationship with the laminated thickness are within the scope of the present invention,
A film having both good electromagnetic conversion characteristics and high-speed scraping properties can be obtained.
【００４１】実施例２〜４、比較例１〜４（表１） 実施例１と同様にして、最表層部に含有される粒子の種
類、粒子径、含有量、粒径分布及び積層厚さ等を種々変
えて二軸配向積層ポリエステルフイルムとした。最表層
積層部に含有される粒子の種類、粒子径、含有量、粒径
分布及び積層厚さの関係等が本発明の範囲内でない場合
には、電磁変換特性、高速削れ性ともに良好なフイルム
とすることができなかった。Examples 2 to 4, Comparative Examples 1 to 4 (Table 1) In the same manner as in Example 1, the type, particle size, content, particle size distribution and lamination thickness of the particles contained in the outermost layer portion Various changes were made to obtain a biaxially oriented laminated polyester film. If the type of the particles contained in the outermost layer laminated portion, the particle size, the content, the relationship between the particle size distribution and the layer thickness are not within the scope of the present invention, both the electromagnetic conversion characteristics and the high-speed shaving properties are good. And could not.
【００４２】[0042]
【表１】 [Table 1]
【００４３】[0043]
【発明の効果】本発明の二軸配向積層フイルムによれ
ば、少なくとも片面の薄層最表層部表面に所定含有量、
所定粒径の粒子Ａと、所定含有量、所定粒径、最表層部
厚さと所定の大小関係を有する粒子Ｂと、所定含有量、
所定粒径の粒子Ｃの、少なくとも特定の３粒子成分を含
有させ、粒子Ａに主として地肌補強、粒子Ｂに所望高さ
の表面突起形成、粒子Ｃに一層の表面粗面化の役割を担
わせるようにしたので、地肌が強く、しかも均一かつ削
れにくい突起が形成された、摩擦係数の極めて低い望ま
しい表面形態とすることができ、高速での優れた耐削れ
性を発揮させつつ、磁気媒体用としての優れた電磁変換
特性を発揮することができる。According to the biaxially oriented laminated film of the present invention, at least one surface of the thin layer outermost surface has a predetermined content,
Particles A having a predetermined particle size, a predetermined content, a predetermined particle size, particles B having a predetermined magnitude relationship with the outermost layer thickness, and a predetermined content,
At least three specific particle components of the particles C having a predetermined particle diameter are contained, and the particles A mainly play the role of reinforcing the background, the particles B form the surface projections of a desired height, and the particles C play the role of further roughening the surface. As a result, it is possible to obtain a desirable surface morphology with a strong background, uniform and hard-to-cut projections, and a very low coefficient of friction. As a result, excellent electromagnetic conversion characteristics can be exhibited.
【００４４】また、最表層部に上記のような優れた特性
をもたせることができるので、中間層に、問題を生じる
ことなくリサイクルポリマを含有させることができ、生
産性の向上を図ることもできる。Further, since the outermost layer can have the above-mentioned excellent characteristics, the intermediate layer can contain the recycled polymer without causing any problem, and the productivity can be improved. .
───────────────────────────────────────────────────── 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 (56)参考文献 特開 昭62−264947（ＪＰ，Ａ) 特開 平４−278349（ＪＰ，Ａ) 特開 平４−62151（ＪＰ，Ａ)──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification number Office reference number FI Technical display location B29L 9:00 (56) References JP-A-62-264947 (JP, A) JP-A-4- 278349 (JP, A) JP-A-4-62151 (JP, A)
Claims (5)
少なくとも片面の最表層部に、少なくとも３種類の粒子
Ａ、Ｂ、Ｃを含有してなる二軸配向積層フイルムであっ
て、粒子Ａはジルコニア、鎖状シリカまたはアルミナか
ら選ばれた一次粒径が１〜１００ｎｍの粒子であり、粒
子Ｂは一次粒径が０．１〜２μｍ、含有量が０．００５
〜２重量％のカルサイト型炭酸カルシウムであり、粒子
Ｃはコロイダルシリカ、架橋型有機粒子またはバテライ
ト型炭酸カルシウムから選ばれた一次粒径が０．１〜２
μｍ、含有量が０．００５〜２重量％の粒子であり、前
記粒子Ｂの粒径ｄと粒子Ｂが含有される該層部の厚さｔ
との関係が ０．５ｄ≦ｔ≦５ｄ であることを特徴とする二軸配向積層フイルム。1. A biaxially oriented laminated film having a laminated structure of at least three layers and including at least three types of particles A, B, and C in an outermost layer portion of at least one surface thereof. Are particles having a primary particle size of 1 to 100 nm selected from zirconia, chain silica or alumina, and particles B have a primary particle size of 0.1 to 2 μm and a content of 0.005.
２2% by weight of calcite-type calcium carbonate, and particles C have a primary particle size of 0.1 to 2 selected from colloidal silica, cross-linked organic particles or vaterite-type calcium carbonate.
μm, the content of the particles is 0.005 to 2% by weight, the particle diameter d of the particles B and the thickness t of the layer containing the particles B
Wherein 0.5d ≦ t ≦ 5d.
る請求項１の二軸配向積層フイルム。2. The biaxially oriented laminated film according to claim 1, wherein the intermediate layer contains a recycled polymer.
３〜６０である請求項１又は２の二軸配向積層フイル
ム。3. The biaxially oriented laminated film according to claim 1, wherein the ratio of secondary particle size / primary particle size of the particles A is 3 to 60.
０．６以下である請求項１ないし３のいずれかに記載の
二軸配向積層フイルム。4. The biaxially oriented laminated film according to claim 1, wherein the relative standard deviation of the particle size distribution of the particles C is 0.6 or less.
である請求項１ないし４のいずれかに記載の二軸配向積
層フイルム。5. The biaxially oriented laminated film according to claim 1, wherein the surface particle concentration of the particles A is 0.1 or more.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3271807A JP2576321B2 (en) | 1991-09-25 | 1991-09-25 | Biaxially oriented laminated film |
| US07/847,586 US5336079A (en) | 1991-03-06 | 1992-03-04 | Biaxially oriented laminated film comprising particles in a specific ratio of particle density |
| CA002062480A CA2062480A1 (en) | 1991-03-06 | 1992-03-05 | Biaxially oriented laminated film |
| EP92301933A EP0502745B9 (en) | 1991-03-06 | 1992-03-06 | Biaxially oriented laminated film |
| DE69213052T DE69213052T2 (en) | 1991-03-06 | 1992-03-06 | Biaxially oriented composite film |
| KR1019920003753A KR100194060B1 (en) | 1991-03-06 | 1992-03-06 | Biaxially oriented laminated film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3271807A JP2576321B2 (en) | 1991-09-25 | 1991-09-25 | Biaxially oriented laminated film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0584820A JPH0584820A (en) | 1993-04-06 |
| JP2576321B2 true JP2576321B2 (en) | 1997-01-29 |
Family
ID=17505126
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3271807A Expired - Lifetime JP2576321B2 (en) | 1991-03-06 | 1991-09-25 | Biaxially oriented laminated film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2576321B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3355284B2 (en) * | 1996-12-09 | 2002-12-09 | 帝人株式会社 | Biaxially oriented laminated polyester film for magnetic recording media |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5153585A (en) * | 1974-11-06 | 1976-05-12 | Teijin Ltd | HORIESUTERUFUIRUMUNO SEIZOHO |
| EP0347646B2 (en) * | 1988-06-08 | 2004-05-19 | Toray Industries, Inc. | Biaxially oriented laminated film |
| JPH0684445B2 (en) * | 1988-08-29 | 1994-10-26 | ダイアホイルヘキスト株式会社 | Biaxially oriented polyester film for magnetic recording media |
| EP0378154B1 (en) * | 1989-01-11 | 1995-11-08 | Toray Industries, Inc. | Biaxially oriented polyester film |
| JP3088426B2 (en) * | 1989-02-16 | 2000-09-18 | 帝人株式会社 | Laminated biaxially oriented 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 |
| JP2856283B2 (en) * | 1989-06-02 | 1999-02-10 | 三菱化学ポリエステルフィルム株式会社 | Biaxially oriented polyester film |
-
1991
- 1991-09-25 JP JP3271807A patent/JP2576321B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0584820A (en) | 1993-04-06 |
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