JPS6360732A - Polyethylene-2,6-naphthalate film - Google Patents

Polyethylene-2,6-naphthalate film

Info

Publication number
JPS6360732A
JPS6360732A JP20628886A JP20628886A JPS6360732A JP S6360732 A JPS6360732 A JP S6360732A JP 20628886 A JP20628886 A JP 20628886A JP 20628886 A JP20628886 A JP 20628886A JP S6360732 A JPS6360732 A JP S6360732A
Authority
JP
Japan
Prior art keywords
film
naphthalate
polyethylene
less
unevenness
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
Application number
JP20628886A
Other languages
Japanese (ja)
Inventor
Shigeo Uchiumi
滋夫 内海
Yujiro Fukuda
裕二郎 福田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Diafoil Co Ltd
Original Assignee
Diafoil Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Diafoil Co Ltd filed Critical Diafoil Co Ltd
Priority to JP20628886A priority Critical patent/JPS6360732A/en
Publication of JPS6360732A publication Critical patent/JPS6360732A/en
Pending legal-status Critical Current

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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)
  • Magnetic Record Carriers (AREA)

Abstract

PURPOSE:To obtain a polyethlene-2,6-naphthalate film excellent in smoothness, easily-sliding property and thickness evenness, by including inert fine particles in the film and specifying the film properties within a specified range. CONSTITUTION:A polyethylene-2,6-naphthalate film containing 0.01-10wt% inert fine particles whose average particle diameter is 0.1-10mu has characteristics described as follows. The 1/2 crystallization time is 6.0min or less and the degree of plane orientation DELTAP and the average reflective index-n satisfy the equations 1 and 2 respectively. Moreover, the numbers of unevenness units per 1mm<2> of the film surface area A, where the unevenness is constituted of a projection and a cavity having the projection as its nucleus whose longer diameter is at least 0.2mum or more, satisfy the equation 3 and the longitudinal and the transverse thickness unevenness are both 8% or less. Polyethylene-2,6- naphthalate means polymers constituted of an ethylene-2,6-naphthalate unit and it includes ethylene-2,6-naphthalate polymers modified with small amt., preferably 5% or less of a third component. A film excellent in thickness uniformity and easily-sliding property can be thereby obtained.

Description

【発明の詳細な説明】 〔産業上の利用分野〕 本発明は厚さ斑に優れかつ平坦易滑性に優れたポリエチ
レンーコ、6−ナフタレートフィルムに関する。更に詳
しくは、磁気記録媒体用ベースフィルムとして特に優れ
たポリエチレン一一、6−ナフタレートフィルムに関ス
る。
DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a polyethylene-co-6-naphthalate film that has excellent thickness unevenness and flatness and smoothness. More specifically, the present invention relates to a polyethylene 1-1,6-naphthalate film that is particularly excellent as a base film for magnetic recording media.

〔従来の技術と発明が解決しようとする問題点〕周知の
ごと(、工業用フィルム、特に磁気記録媒体のベースフ
ィルムとしては、ポリエチレンテレフタレートフイルム
が現在主流として用いられている。しかしながら、近年
ポリエチレンテレフタレートフィルムでは1強度及び耐
熱性で不充分な用途が出現し、新しい素材が要望されて
いる。このWmに対していくつかの素材が候補としてさ
げられているが、それらの中でモ、コストと品質の両面
よりポリエチレン−コツ6−ナフタレートフィルムが注
目をあびている。ポリエチレンココ、6−ナフタレート
フィルムは、ポリエチレンテレフタレートに比べて耐熱
性に優れること、高強度化の達成が容易なこと、粗大物
が少ないことによりポリエチレンテレフタレートに代る
素材として種々の用途への展開が考えられており、とり
わけ高品質・高密度の磁気記録媒体用途への展開が注目
されている。
[Prior art and problems to be solved by the invention] As is well known, polyethylene terephthalate film is currently mainly used as an industrial film, especially as a base film for magnetic recording media.However, in recent years polyethylene terephthalate film There are applications where film has insufficient strength and heat resistance, and new materials are required.Several materials have been proposed as candidates for Wm, but among them, Polyethylene Coco 6-naphthalate film is attracting attention because of its quality.Polyethylene Coco 6-naphthalate film has superior heat resistance compared to polyethylene terephthalate, is easy to achieve high strength, and is coarse. Due to the limited availability of polyethylene terephthalate, it is being considered for use in a variety of applications as a substitute for polyethylene terephthalate, with particular attention being focused on its use in high-quality, high-density magnetic recording media.

ところで、これらの用途への展開に際しての最X要課題
はフィルムへの平坦易滑性の付与である。周知のごと(
フィルムの平坦易滑化の手法としては、ポリエチレンテ
レフタレートフィルムにおいて種々検討されてきた。そ
のひとつの手法は、フィルム中に含有せしめる不活性粒
子の種類1粒径9粒子量9粒径分布等を変えて最適条件
を見い出すことである。この方法は。
By the way, the most important issue in developing these applications is to impart flatness and slipperiness to the film. As is well known (
Various methods have been studied for making polyethylene terephthalate films flat and smooth. One method is to find the optimum conditions by changing the type, particle size, particle amount, particle size distribution, etc. of the inert particles contained in the film. This method is.

ポリエチレン−コツ6−ナフタレートフィルムにおいて
も、はぼポリエチレンテレフタレートフィルムでの知見
をそのまま転用出来ることが判明している。これに対し
て別の手法は、フィルムの面内の配向を低下させて9粒
子が形成する突起を核とした窪みを有する突起を形成さ
せることにより、平坦易滑化を達成するものである。
It has been found that the knowledge obtained with the polyethylene terephthalate film can be directly applied to the polyethylene-naphthalate film as well. On the other hand, another method is to reduce the in-plane orientation of the film to form protrusions having depressions with the protrusions formed by nine particles as cores, thereby achieving flattening and smoothing.

該手法をポリエチレン−2,6−ナフタレートフィルム
に対しても適用すべく検討したところ。
We investigated the application of this method to polyethylene-2,6-naphthalate film.

単にフィルムの面内の配向度を下げただけでは。Simply lowering the in-plane orientation of the film is not enough.

同一粒径、同一粒子量、同一粒子分布の同一の不活性粒
子を用いた場合にも、平坦易滑化は達成されるものの厚
さ一斑が極端に悪化してしまい。
Even when the same inert particles having the same particle size, the same amount of particles, and the same particle distribution are used, flattening and smoothing can be achieved, but the unevenness of the thickness becomes extremely worse.

高級なフィルム用途特に磁気記録媒体のベースフィルム
用途としては、使用に耐えないものであることが判明し
た。
It has been found that the film cannot withstand use as a high-grade film, particularly as a base film for magnetic recording media.

本発明は、平坦易滑性と共に厚さ斑にも優れたポリエチ
レン−,2,6−ナフタレートフィルムが備えろべき物
性を見い出すことを目的としたものである。
The object of the present invention is to discover the physical properties that a polyethylene, 2,6-naphthalate film should have, which is excellent in flatness and smoothness as well as thickness unevenness.

〔間頂点を解決するための手段〕[Means for solving intervening vertices]

本発明者らは、上記目的を達成すべ(鋭意検討した結果
、不活性微粒子を含有し、かつフィルムの物性をある特
定の範囲に規定したポリエチレンココ、6−ナフタレー
ドフイルムカ、厚さ斑が良好でかつ平坦易滑化を達成し
得ることを見出し本発明に到達したものである。
The present inventors have achieved the above object (as a result of intensive studies, we have developed a polyethylene coco, 6-naphthalade film containing inert fine particles and with the physical properties of the film defined within a certain range), which has a thickness unevenness. The present invention was achieved by discovering that good and flat smoothing can be achieved.

すなわち本発明の要旨は、平均粒径o、i〜10μの不
活性微粒子をo、oi〜10tミル10t量ポリエチレ
ン−コツ6−ナフタレートフィルムであって、そのフィ
ルムの200℃での/7/コ結晶化時間が6.0分以下
でありかつ面配向度ΔPと平均屈折率nが下記式■及び
■を満たすと共に突起と該突起を核とした長径が少くと
も0.−μm以上の窪みとかうなる凹凸単位のフイ7v
ム表面積1〜当りの数A(個1〜)が下記式[3]を清
だしフィルムのタテ、ヨコの厚さ斑が共に3%以下であ
ることを特徴とする平坦易滑性。
That is, the gist of the present invention is to prepare a polyethylene-cot 6-naphthalate film in which inert fine particles with an average particle diameter of o and i to 10μ are o, oi to 10t mill 10t, and the film has a temperature of /7/ at 200°C. The co-crystallization time is 6.0 minutes or less, the degree of plane orientation ΔP and the average refractive index n satisfy the following formulas (1) and (2), and the length of the protrusion and the major axis of the protrusion as a core are at least 0. - Concave or concave/concave units of 7v
A flat and slippery film characterized in that the number A (1 to 1) per film surface area satisfies the following formula [3] and the vertical and horizontal thickness unevenness of the film is 3% or less.

フィルムの厚さ斑にすぐれたポリエチレン一一、6−ナ
フタレートフィルムに存する。
It is a polyethylene 1-1,6-naphthalate film with excellent film thickness unevenness.

JP≦/護3五−u、 / 、? A   曲面・曲・
・■/、&l、!0≦n≦7.6750 曲面・・・曲
■OくA≦/!000     ・曲・曲面・■本発明
でいうポリエチレン−2,6−ナフタレートとは、その
構成単位が実質的にエチレンーー、6−ナフタレート単
位から構成されているポリマーを指すが、少量例えば1
0モル%、以下好ましくは3モルチ以下の第3成分によ
って変性すしたエチレン−2,6−ナフタレートポリマ
ー機能的誘導体1例えばナフタレンーコ、6−ジカルボ
ン酸メチル等とエチレングリコールとを触媒の存在下で
適当な反応条件の下に縮合させることによって改造され
る。この場合ナフタレンーー、6−ジカルボン酸及びエ
チレングリコール以外の第3成分としては例えばアジピ
ン酸、シュウ酸、イノフタル酸、テレフタル酸、ナフタ
レンーコ、7−ジカルポン酸、ジフェニルエーテルジカ
ルボン酸のごときジカルボン酸又はその低級アルキルエ
ステル:p−オキシ安息香酸。
JP≦/Mamoru 35-u, / ,? A Curved surface/curve/
・■/, &l,! 0≦n≦7.6750 Curved surface... Song■OkuA≦/! 000 ・Curves・Curved surfaces・■Polyethylene-2,6-naphthalate as used in the present invention refers to a polymer whose constitutional units are substantially composed of ethylene-6-naphthalate units.
Ethylene-2,6-naphthalate polymer functional derivatives modified with 0 mol %, preferably 3 mol % or less of a third component 1, such as naphthalene, methyl 6-dicarboxylate, etc., and ethylene glycol in the presence of a catalyst. modified by condensation under appropriate reaction conditions. In this case, the third component other than naphthalene, 6-dicarboxylic acid, and ethylene glycol is dicarboxylic acid or lower alkyl ester thereof such as adipic acid, oxalic acid, inophthalic acid, terephthalic acid, naphthalene, 7-dicarboxylic acid, and diphenyl ether dicarboxylic acid. :p-oxybenzoic acid.

p−オキンエトキシ安息香識のごときオキシカルボン酸
又はその低級アルキルエステル;或いはプロピレングリ
コール、トリメチレングリコール、テトラメチレングリ
コール、ペンタメチレングリコール、ヘキサメチレング
リコ−/L/。
Oxycarboxylic acids or lower alkyl esters thereof such as p-oxybenzoate; or propylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol/L/.

ジエチレングリコール、/、lI−シクロヘキサンジメ
タツールのごときポリアルキレングリコール等を挙げる
ことができる。又1重合に際して艶消剤、遮光剤、安定
剤、酸化防止剤1重合調節剤、可塑剤等を添加しても差
しつかえない。
Examples include polyalkylene glycols such as diethylene glycol and lI-cyclohexane dimetatool. Further, during the first polymerization, a matting agent, a light shielding agent, a stabilizer, an antioxidant, a polymerization regulator, a plasticizer, etc. may be added.

又9本発明で用いるポリエチレンココ、6−ナフタレー
トは1重合度が低すぎると機械的性質が低下するので、
その極限粘度は0.110以上好ましくは0.33〜O
,デのものである。
Furthermore, if the degree of monopolymerization of the polyethylene coco, 6-naphthalate used in the present invention is too low, the mechanical properties will deteriorate.
Its intrinsic viscosity is 0.110 or more, preferably 0.33 to O
, De's.

本発明のフィルムは、各種用途とりわけ磁気記録媒体ベ
ースフィルム用途に好適に用いることができるが、いず
れの用途に用いる場合も。
The film of the present invention can be suitably used for various purposes, particularly as a magnetic recording medium base film, but it can be used for any purpose.

走行性を与えるために微細な不活性微粒子を含有させて
、滑り性を付与する必要がある。又。
In order to provide runnability, it is necessary to include fine inert particles to provide slipperiness. or.

該不活性微粒子の平均粒径は、0,7〜10μm。The average particle size of the inert fine particles is 0.7 to 10 μm.

粒子量は0.01〜IO重量%である必要がある。The amount of particles should be between 0.01 and IO weight percent.

好ましくは1粒径は、0.3〜3μの範囲1粒子量は、
0.02〜0.121チ、更に好ましくは0、OJ〜0
.3重量%の範囲から選択される。粒径が0.7μmよ
り小さい場合もし、くは0.0重重量%以下では、フィ
ルムの表面粗度が小さすぎて滑り性に寄与しないので不
適である。一方10μmより大きい場合もしくは10重
−m%より多い場合にはフィルムの表面粗度が荒れすぎ
て、不適である。
Preferably, the particle size is in the range of 0.3 to 3μ, and the amount of particles is,
0.02 to 0.121 inches, more preferably 0, OJ to 0
.. It is selected from a range of 3% by weight. If the particle size is smaller than 0.7 μm or less than 0.0% by weight, the surface roughness of the film will be too small and will not contribute to slipperiness, which is unsuitable. On the other hand, if it is larger than 10 μm or larger than 10 wt-m %, the surface roughness of the film will be too rough, making it unsuitable.

かかる不活性微粒子をフィルム中に含有させる方法のひ
とつとして、ポリエチレンナフタレート製造時に反応系
内に溶存している金属化合物1例えばエステル交換反応
後系内に湿存し℃いる金属化合物にリン化合物を作用さ
せて微細な粒子を析出させる。いわゆる析出粒子法があ
る。該手法は、特に粗大粒子が少な(好ましい手法であ
るが、簡便な手法として今ひとつの手法いわゆる添加粒
子法がより好ましく用いられる。
One method for incorporating such inert fine particles into the film is to add a phosphorus compound to the metal compound dissolved in the reaction system during polyethylene naphthalate production, for example, to the metal compound that remains wet in the system after the transesterification reaction. act to precipitate fine particles. There is a so-called precipitated particle method. This method is particularly preferable because it uses fewer coarse particles, but as a simple method, another method, the so-called additive particle method, is more preferably used.

ここで添力ロ粒子法とは、ポリエチレンーー、6−ナフ
タレート製造工程から、fA腹膜前押出工程のいずれか
の工程でポリエチレンナフタレート重合体原料中に不活
性な微細粒子を配合させる方法であり、この不活性微粒
子としては1例えば、カオリン、ゼオライト、セライト
、タルク、炭酸マグネンウム、炭酸カルシウム、炭酸バ
リウム、硫酸カルシウム、リン酸リチウム。
Here, the added particle method is a method in which inert fine particles are blended into the polyethylene naphthalate polymer raw material in any step from the polyethylene-6-naphthalate manufacturing process to the fA preperitoneal extrusion process. Examples of the inert fine particles include kaolin, zeolite, celite, talc, magnesium carbonate, calcium carbonate, barium carbonate, calcium sulfate, and lithium phosphate.

リン酸カルシウム、リン酸マグネシウム、酸化アルミニ
ウム、r52化ケイ素、酸化チタン、フッ化リチウム、
ンユウ酸カルシウム及びOa、Ba。
Calcium phosphate, magnesium phosphate, aluminum oxide, silicon r52, titanium oxide, lithium fluoride,
Calcium oxalate and Oa, Ba.

Z n 、 M n 9のテレフタル酸塩等から選ばれ
た7種以上の金属化合物あるいはカーボンブラック丑を
挙げろことができる。この不活性化合物の形状は球状、
塊状、あるいは偏平状等のいずれであっても良(、又そ
の硬度、比重1色等についても特に制限はない。
Examples include seven or more metal compounds selected from terephthalates of Z n and M n 9, and carbon black. The shape of this inert compound is spherical,
It may be either lumpy or flat (and there are no particular restrictions on its hardness, specific gravity, color, etc.).

本発明において面配向度JPと平均屈折重石とは下記式
■及び■を満たさなければならない。
In the present invention, the plane orientation degree JP and the average refractometer must satisfy the following formulas (1) and (2).

JP≦1.弘3・n−コ、/36  ・・・・・・・・
・・・・■i、tt、go≦n≦/、1.7!0   
・・・・・・・・・・・・■ここで平均屈折重石は下記
式(イ)で表わされる量であり、一般に熱固定温度で決
まり、フィルムの密度と比例することが知られている。
JP≦1. Hiro 3・n-ko, /36 ・・・・・・・・・
...■i, tt, go≦n≦/, 1.7!0
・・・・・・・・・・・・■Here, the average refractometer is the amount expressed by the following formula (a), which is generally determined by the heat-setting temperature and is known to be proportional to the density of the film. .

五 = //J  (na +n7 + n、)   
    、・、、、、、、、、、、  (イ)netは
一軸配向熱固定後のフィルムの厚さ方向の屈折率s ”
rは同フィルムのフィルム面内での最大屈折率、nzは
フィルム面内にオ6いてr方向と直角方向の屈折率であ
る。五が/、61.、A;0未満の場合には、フィルム
の財熱性に劣り又熱収縮率が大きくなり不適である。−
万石が/、4り!0を超えるとフィルムの機械的強度が
低下するため不適である。
Five = //J (na + n7 + n,)
, , , , , , , , (a) net is the refractive index s in the thickness direction of the film after uniaxial orientation heat fixation
r is the maximum refractive index of the same film within the film plane, and nz is the refractive index in the direction perpendicular to the r direction within the film plane. Five /, 61. , A; if it is less than 0, the film will have poor thermal properties and a high thermal shrinkage rate, making it unsuitable. −
Mangokuga/, 4ri! If it exceeds 0, it is unsuitable because the mechanical strength of the film decreases.

一方面配向度ΔPは、下記式(ロ)で表わされろ量であ
って、一般にフィルム面内の配向の度合を示している。
One-sided orientation degree ΔP is a degree of orientation expressed by the following formula (b), and generally indicates the degree of orientation within the plane of the film.

つまりポリエチレン−,2,A −ナフタレートのナフ
タレン環が面内に平行に配向している度合いを示してい
る。
In other words, it indicates the degree to which the naphthalene rings of polyethylene-,2,A-naphthalate are oriented in parallel within the plane.

Δp  = //2  (ny +”/  )−−・・
・・・・・・・ (ロ)JPと五の関係が上記式のを満
足したフィルムは上記式■を満たさないフィルムに比べ
て。
Δp = //2 (ny +”/ )−−・・
(b) Films in which the relationship between JP and 5 satisfies the above formula are compared to films that do not satisfy the above formula (■).

平坦易滑性に優れろものである。It has excellent flatness and smoothness.

面配向度JPと平均屈折重石が上記式■を満足するフィ
ルムは種々の方法で得られる。例えば1通常の手法で二
軸延伸したフィルムを。
A film whose plane orientation degree JP and average refraction weight satisfy the above formula (2) can be obtained by various methods. For example, 1. A film biaxially stretched using a conventional method.

=60℃以上融点直下の温度で長時間熱固定することに
よっても得られる。又、二軸延伸後熱固定時幅方向に弛
緩させることによっても得られる。このような手法でJ
Pと五の関係が上記式■を満足するようにしたフィルム
においても。
It can also be obtained by heat setting for a long time at a temperature of 60° C. or higher and just below the melting point. It can also be obtained by relaxing in the width direction during heat setting after biaxial stretching. With this method, J
Even in a film in which the relationship between P and 5 satisfies the above formula (■).

若干の平坦易滑化を達成することが出来るが。Although some flattening can be achieved.

その効果を強く発揮させるには、縦横逐次二軸延伸にお
いて、縦方向の配向をつまり縦−軸延伸フィルムの複屈
折率を低(押さえることにより上記式■を満足させるこ
とが必要である。か(して得られたフィルムは、突起の
周囲に該突起を核とした窪からなる凹凸単位が生じる。
In order to strongly exhibit this effect, it is necessary to satisfy the above formula (2) by suppressing the longitudinal orientation, that is, the birefringence of the longitudinally-axially stretched film, to a low value in sequential biaxial stretching in the longitudinal and lateral directions. (In the film thus obtained, uneven units consisting of depressions with the protrusions as the core are formed around the protrusions.

それ故事発明においては突起と該突起を核とした長径が
少くともO9−μm以上の窪みとからなる凹凸単位のフ
ィルム表面積/xJ半りの数A(個1〜)が下記式[3
]を満足しなければならない。
Therefore, in the present invention, the number A (number of pieces 1 to 1) of the film surface area/xJ half of the uneven unit consisting of a protrusion and a depression whose major axis is at least O9-μm or more with the protrusion as the core is calculated by the following formula [3
] must be satisfied.

o < A≦/よOOO・・・・・・・・・・・・・・
・■Aが零個では平坦易滑の効果がなく 1soo。
o < A≦/yoOOO・・・・・・・・・・・・・・・
・■ If there are zero A, there is no flat smoothing effect and it is 1soo.

個を超えると、フィルムの耐摩耗性が悪化し不適である
。好ましくは3個以上5ooo個以下。
If it exceeds 1, the abrasion resistance of the film deteriorates and is unsuitable. Preferably 3 or more and 5ooo or less.

更に好ましくは3個以上2!;00個以下である。More preferably 3 or more 2! ;00 or less.

しかるに工業用素材特に磁気記録媒体素材として該フィ
ルムを用いる場合には、基本的特性として厚さ斑が良好
でなければならない。二軸延伸熱固定後のフィルムが満
足すべき厚さ斑としては、タテ、ヨコ共にx7Xでt%
以下好ましくは3%以下である。ここでRはjm&での
最大厚みと最小厚みの差、iは平均厚みである。
However, when the film is used as an industrial material, particularly as a material for a magnetic recording medium, the basic property is that the film must have good thickness unevenness. The thickness unevenness that should be satisfied for the film after biaxial stretching and heat setting is t% at x7X for both vertical and horizontal directions.
It is preferably 3% or less. Here, R is the difference between the maximum thickness and minimum thickness at jm&, and i is the average thickness.

さて上記■、■及び0式を満足するフィルムについて厚
さ斑を測定したところ、厚さ斑の良好なものと不良のも
のが混在した。それ故、厚さ斑の良好なものについて要
因を検討したところ。
When the thickness unevenness was measured for films satisfying the above formulas (1), (2), and 0, there was a mixture of good thickness unevenness and poor thickness unevenness. Therefore, we investigated the factors that lead to good thickness unevenness.

フィルムの200℃での///2結晶化時間カ強り影響
することが判明した。つまりフィルムの200℃での/
/2結晶化時間が6分以下であることが必須である。好
ましくは5分以下、更に好ましくはダ分以下である。
It has been found that the crystallization time of the film at 200°C has a strong influence. In other words, the temperature of the film at 200℃/
/2 It is essential that the crystallization time is 6 minutes or less. Preferably it is 5 minutes or less, more preferably da minute or less.

ここでフィルムの200℃での//2結晶化時間を匂か
くする方法としては釉々あるが、一般的な処方としては
、結晶化促進剤を含有させろことである。結晶化促進剤
としては局級脂肪族カルボン酸又はその金属塩(?lJ
えはモンタン酸ナトリウム、ステアリン敵ナトリウム)
、芳香族カルボン酸又はその金属塩(例えば安息香酸ナ
トリウム)、アルキルスルホン酸、アルキルベンゼンス
ルホン酸、アイオノマー、ポリアルキレングリコール等
公知のものを用いれば良い。
Here, there are various methods for increasing the crystallization time of the film at 200° C., but a common recipe is to include a crystallization accelerator. As a crystallization accelerator, local aliphatic carboxylic acids or metal salts thereof (?lJ
Sodium montanate, sodium stearin)
, aromatic carboxylic acids or metal salts thereof (eg, sodium benzoate), alkylsulfonic acids, alkylbenzenesulfonic acids, ionomers, polyalkylene glycols, and other known compounds may be used.

フィルム中の含有量は、コ00℃での//コ結晶化時間
が所定の範囲になるように含有させれば良いが一般には
0.01−!、0重−!1%である。しかしながら特に
磁気記録媒体用フィルムとして使用する際には、上記の
ごとき有機の結晶化促進剤は粗大プツの原因となったり
、ブリードアウトして接着性の低下をきたしたりするた
め。
The content in the film may be such that the co-crystallization time at 00°C falls within a predetermined range, but generally 0.01-! , 0 weight-! It is 1%. However, especially when used as a film for magnetic recording media, organic crystallization promoters such as those described above may cause coarse lumps or bleed out, resulting in a decrease in adhesion.

必要最小限に止めると共に不純物を出きるだけ除いた精
製品を使用することが野ましい。200℃での//2結
晶化速度を速(する手法としては好ましくは、ポリエチ
レンーコ、6−ナフタレート重合時の特別な1合処方を
行なうことと無接の結晶化核剤例えばカオリン、炭カル
等を併用することが好ましい。
It is best to use purified products that have been kept to the minimum necessary level and have as many impurities removed as possible. Preferably, the method for increasing the crystallization rate at 200°C is to carry out a special combination formulation during polyethylene co-6-naphthalate polymerization and to use a non-contact crystallization nucleating agent such as kaolin or charcoal. It is preferable to use Cal etc. in combination.

か(して、厚さ斑、平坦易滑性に優れた画期的ナポリエ
チレン一一、6−ナフタレードフイ、IL/ムを見い出
すことができたが、以下具体的に製膜処方について記述
する。
As a result, we were able to discover an innovative napolyethylene 11, 6-naphthalate film, IL/mu, which was excellent in thickness unevenness, flatness, and slipperiness.The film-forming recipe will be specifically described below.

重合時特殊なリンを用い不活性微粒子を所定量含有した
ポリエチレンーコ、6−ナフタレート重合体中に、有機
の結晶化促進剤を必要に応じて含有させた重合体組成物
を、公知の手段で乾燥し、弓融押出後冷却ドラム状にキ
ャストした実質的に無配向のポリエチレンーコ、6−ナ
フタレートの未延伸フィルムをまず縦方向に延伸する。
A polymer composition in which an organic crystallization accelerator is optionally contained in a polyethylene-co-6-naphthalate polymer containing a predetermined amount of inert fine particles using special phosphorus during polymerization is prepared by known means. A substantially non-oriented unstretched film of polyethylene, 6-naphthalate, which was dried and cast into a cooling drum shape after bow-melt extrusion, was first stretched in the longitudinal direction.

その際まず複屈折率Δnがo、oso以上o、oqo以
下となるよう延伸(前段延伸)する。
At that time, the film is first stretched (pre-stretching) so that the birefringence Δn is at least o, oso and at most o, oqo.

この前段延伸は、/段階で行なってもよいし多段階に分
けて行なってもよい。延伸温度はポリエチレンーコ、6
−ナフタレートの二次転移温度以上/10℃以下の湯度
でへg倍からa、O倍の範囲で延伸すれば良い。又、前
段延伸の途中又は前段延伸後に配向緩和のための熱緩和
工程を含めることも好ましい。熱緩和工程としてロール
で行なってもよいし、外部加熱で行なってもよいが、熱
緩和処理前の縦延伸温度以上でo、5〜3.0秒、/、
01倍以下で行なうのがよい。かくして得られたフィル
ムを更に縦方向に複屈折率Δnが0.090以上o、i
ao以下となるよう延伸(後段延伸)したのち、横延伸
し、/jθ℃以上コロ0℃以下の温度で熱固定して二軸
配向熱固定フィルムを製造する。フィルムの厚さ斑を所
定の範囲にするためには、上述のとと(縦延伸を多段延
伸とすることが必要である。又。
This pre-stretching may be performed in stages or in multiple stages. Stretching temperature is polyethyleneco, 6
- Stretching may be carried out at a hot water temperature of 10° C. or above the second-order transition temperature of naphthalate and in the range of 10 g to a, 0 times. It is also preferable to include a thermal relaxation step for orientation relaxation during or after the first-stage stretching. The thermal relaxation step may be carried out with a roll or by external heating, but at a temperature equal to or higher than the longitudinal stretching temperature before the thermal relaxation treatment, for 5 to 3.0 seconds, /
It is best to do this at a magnification of 0.01 times or less. The thus obtained film is further modified in the longitudinal direction to have a birefringence Δn of 0.090 or more o, i
After stretching (second stage stretching) so that the film temperature is below ao, it is laterally stretched and heat-set at a temperature of /jθ°C or more and 0°C or less to produce a biaxially oriented heat-set film. In order to keep the thickness unevenness of the film within a predetermined range, it is necessary to perform the above-mentioned longitudinal stretching in multiple stages.

フィルムの200℃での//コ結晶化時間が短い時にの
み厚さ斑が改良された理由としては、上記の後段延伸に
おいて、結晶化速度が速くなるため低倍率の延伸で配向
結晶化が進行し、厚さ斑の改良が行なわれたものと思わ
れる。
The reason why the thickness unevenness was improved only when the co-crystallization time of the film at 200°C was short is because the crystallization speed increases in the above-mentioned latter stage stretching, so oriented crystallization progresses with low stretching ratio. However, it seems that the thickness unevenness has been improved.

以上述べたごと(本発明によればポリ、エチレン−コツ
6−ナフタレートフィルムの面配向度を低下させても、
厚さ斑が良好でかつ平坦易滑性に優れたフィルムが得ら
れ、またポリエチレン一一、6−ナフタレートフィルム
が高品質のフィルム用途に適用可能となり、極めて工業
的価値に優れるものである。
As stated above (according to the present invention, even if the degree of plane orientation of the polyethylene-6-naphthalate film is reduced,
A film with good thickness unevenness and excellent flatness and smoothness can be obtained, and the polyethylene 1-1,6-naphthalate film can be applied to high-quality film applications, and has extremely excellent industrial value.

〔実施例〕〔Example〕

以下実施例により本発明を説明するが1本発明は、その
要旨を越えない限り以下の実施例によって限定されるも
のではない。なお、フィルムの諸物性の測定方法は次の
通りである。
The present invention will be explained below with reference to examples, but the present invention is not limited by the following examples unless it exceeds the gist thereof. The various physical properties of the film were measured as follows.

(1)厚さ斑 安立電気社製連続続フィルム厚さ測定器(を子マイクロ
メーター使用)により二軸延伸フィルムの縦及び横方向
に沿って測定し、3m長さについて次式により算出した
(1) Thickness The thickness was measured along the vertical and horizontal directions of the biaxially stretched film using a continuous film thickness measuring device (using a micrometer) manufactured by Madarasu Ritsu Denki Co., Ltd., and calculated using the following formula for a length of 3 m.

(2)複屈折率Δn カールツアイス社製偏光顕微鏡にて縦延伸フィルムのり
ターデーンヨンを測定し1次式により複屈折率Δnを求
めた。
(2) Birefringence Δn The thickness of the longitudinally stretched film was measured using a polarizing microscope manufactured by Carl Zeiss, and the birefringence Δn was determined using a linear equation.

Δn=R/a    R: リターデーンヨンd:フイ
ルム厚み (3)屈折率 アタゴ社製アツベ式屈折計にてコ5℃でγ方向、β方向
及び厚さ方向の屈折率を富法により測定した。
Δn=R/a R: Retardation: Film thickness (3) Refractive index The refractive index in the γ direction, β direction, and thickness direction was measured at 5° C. using an Atsabe type refractometer manufactured by Atago Co., Ltd. by the method. .

(4)平均突起高さRa JIB BOAO1〜/97A記載の方法により行なっ
た。測定は小坂研究所昨製表面粗さ測定機モデル8に−
jFを用いた。触針径コμ、触針圧30■、カットオフ
値o、og非、測定長はコ、juとした。測定は12点
行ない、最大値、最小値をカットし10点の平均値で示
した。
(4) Average protrusion height Ra It was performed by the method described in JIB BOAO1-/97A. The measurement was carried out using the surface roughness measuring machine model 8 manufactured by Kosaka Laboratory.
jF was used. The stylus diameter was μ, the stylus pressure was 30 cm, the cut-off value was o, og non-, and the measurement length was co, ju. Measurement was carried out at 12 points, the maximum value and minimum value were cut off, and the average value of the 10 points was shown.

(5)金属とのgdJ摩擦係数μd 固定した硬質クロムメッキ仕上げのビン(直径4 yx
x )に巻きつげ角/、3に°(θ)でフィルムを接触
させて、j−,71Tz)の荷重をフィルムの一端にか
げて、7m7分の速度で走行させ、他端の抵抗力(Tt
)を測定する。このときのマサツ係数を次式により求め
た。
(5) gdJ friction coefficient μd with metal Fixed hard chrome plated bottle (diameter 4 yx
The film is brought into contact with the winding angle /, 3° (θ), and a load of j-, 71Tz) is applied to one end of the film, and the film is run at a speed of 7m7, and the resistance force at the other end ( Tt
) to measure. The Masatsu coefficient at this time was determined using the following formula.

(6)突起を核としその周辺に窪を有する凹凸単位の数
A カールツアイス社友微分干渉顕微鏡でアルミニウムを蒸
着したフィルムの表面を7!rθ倍で写真撮影し1合計
1〜のフィルムの表面積当り、長径がOo、2μm以上
の凹凸単位の数A(個1〜)を数えた。
(6) Number A of uneven units having protrusions as cores and depressions around them.7! The surface of a film on which aluminum was deposited was measured using a Carl Zeiss differential interference microscope. Photographs were taken at a magnification of rθ, and the number A (1 to 1) of uneven units having a major axis of Oo and 2 μm or more was counted per surface area of the film, which had a total of 1 to 1.

(7)  フィルムの200℃での//2結晶化時間パ
ーキンエルマー社製D80 ニーBヲ用いた。
(7) Crystallization time of film at 200°C: D80 Knee B manufactured by PerkinElmer was used.

試料を16℃/mi nで300℃まで昇温し。The sample was heated to 300°C at 16°C/min.

300℃で5分間放置後A II ℃/minでコ00
℃まで急速降温させ、コ00℃で等温結晶化させたのち
、結晶化ピークまでの時間を測定した。
After leaving at 300℃ for 5 minutes, heat at AII℃/min.
After rapidly lowering the temperature to 0.degree. C. and performing isothermal crystallization at 00.degree. C., the time until the crystallization peak was measured.

比較例l ナフタレン−コツ6−ジカルボン酸ジメチル100部、
エチレングリコール10部及び酢酸カルシウム−水塩0
.7部及び酢[IJチウムニ水塩0.77部を反応器に
仕込み、刀口熱昇温すると共にメタノールを留出させて
エステル交換反応を行ない1反応開始後約弘時間を要し
てコ30℃に達せしめ、実質的にエステル交換を終了し
た。
Comparative Example 1 100 parts of dimethyl naphthalene-6-dicarboxylate,
10 parts of ethylene glycol and 0 calcium acetate hydrate
.. 7 parts of vinegar and 0.77 parts of IJ thiium dihydrate were charged into a reactor, heated at the tip of a knife, distilled off methanol, and carried out a transesterification reaction. The transesterification was substantially completed.

次にこの反応生成物にトリエチルホスフェートo、Js
部を添加し、更に重縮合触媒として三散化アンチモン0
.0!部を添加した後、常法に従ってポリエステルを得
た。この時の〔n〕=0.53であった。これを固相重
合して〔n〕=0.63の重合体組成物を得た。
Next, to this reaction product, triethyl phosphate o, Js
of antimony tridisperse as a polycondensation catalyst.
.. 0! After adding 1.0 parts, a polyester was obtained according to a conventional method. At this time, [n]=0.53. This was subjected to solid phase polymerization to obtain a polymer composition with [n]=0.63.

次に先の原料ポリエステルを乾燥後、浴融押出しを行い
、未延伸フィルムを得た。その際靜を密着法を採用した
。該未延伸フィルムをまず733℃でコ、グ倍延伸しΔ
m=0.010のフィルムとし更にtSO℃で/、2倍
延伸してΔn=0.200の縦−軸延伸フイルムを得た
。この時延伸ロールとしては弐面粗度/Sのセラミック
コートロールを使用した。次に該縦−軸延伸フイルムな
i!ro℃でテンターにて9.0倍延伸したのち、23
!T℃で熱固定して10μのフィルムを得た。か(して
得られたフィルムの物性を表/に示す。
Next, after drying the raw material polyester, bath melt extrusion was performed to obtain an unstretched film. At that time, we adopted the silent contact method. The unstretched film was first stretched at 733°C by a factor of Δ
The film with m=0.010 was further stretched 2 times at tSO°C to obtain a longitudinally-axially stretched film with Δn=0.200. At this time, as the stretching roll, a ceramic coated roll having an upper surface roughness of /S was used. Next, the longitudinally-axially stretched film i! After stretching 9.0 times with a tenter at ro℃,
! A 10μ film was obtained by heat setting at T°C. Table 1 shows the physical properties of the film obtained.

実施例/ ナフタレン−コツ6−ジカルボン酸ジメチル100部、
エチレングリコ−Al2O部及び酢酸カルシウム−水塩
0.11部を反応器に仕込み加熱昇温すると共にメタノ
ールを留去させて、エステル交換反応を行ない反応開始
後約ダ時間を要して230℃に達せしめ、実質的にエス
テル交換を終了させたのち酢酸リチウムニ水塩Q、77
部を添加した。次にこの反応生成物にトリメチルホスフ
ェート0.2g部添加し、更に重縮合触媒として二酸化
アンチモン0.05部を添加した後、常法に従ってポリ
エステルを得た。比較例1と同様に固相重合を行ない(
n) = o、t sとした。
Example/100 parts of dimethyl naphthalene-6-dicarboxylate,
Part of ethylene glyco-Al2O and 0.11 parts of calcium acetate hydrate were placed in a reactor and heated to raise the temperature, and methanol was distilled off to carry out the transesterification reaction. After the start of the reaction, the temperature was raised to 230°C over a period of about 1 hour. After achieving this and substantially completing the transesterification, lithium acetate dihydrate Q, 77
part was added. Next, 0.2 g part of trimethyl phosphate was added to this reaction product, and then 0.05 part of antimony dioxide was added as a polycondensation catalyst, and then a polyester was obtained according to a conventional method. Solid phase polymerization was carried out in the same manner as in Comparative Example 1 (
n) = o, ts.

製膜に関しては比較例1と同様に行ないサンプルを得た
Film formation was carried out in the same manner as in Comparative Example 1 to obtain a sample.

実施例コ 実施例/において、トリメチルホスフェートを添加した
のち、平均粒径/、2μの炭酸カルシウム、7 o o
 ppm添加する以外は実施例/と同様に重合し1重合
体組成物を得た。この重合体組成物な用い比較例/と同
様に製膜してフィルムを得た。
In Example/Example/, after addition of trimethyl phosphate, calcium carbonate of average particle size/, 2μ, 7 o o
Polymerization was carried out in the same manner as in Example except that ppm was added to obtain a single polymer composition. A film was obtained by forming a film using this polymer composition in the same manner as in Comparative Example.

実施例3 実施例コと同様の重合体組成物を用い、押出製膜時、高
級脂肪酸す) IJウムを!; 000 ppmトライ
ブレンドし、洛硼押出しを行った後、実施例コと同様に
延伸してフィルムを得た。これらの結果を表1に示す。
Example 3 Using the same polymer composition as in Example 3, higher fatty acids were added during extrusion film formation. ;000 ppm tri-blending and extrusion, followed by stretching in the same manner as in Example C to obtain a film. These results are shown in Table 1.

〔発明の効果〕〔Effect of the invention〕

本塁発明方法によれば、厚さ斑、平坦易滑性ともに優れ
たフィルムが得られる。
According to the method of the present invention, a film excellent in both thickness unevenness and flatness and smoothness can be obtained.

Claims (2)

【特許請求の範囲】[Claims] (1)平均粒径0.1〜10μの不活性微粒子を0.0
1〜10重量%含有するポリエチレン−2,6−ナフタ
レートフィルムであって、そのフィルムの200℃での
1/2結晶化時間が6.0分以下でありかつ面配向度Δ
Pと平均屈折率@n@が下記式[1]及び[2]を満た
すと共に突起と該突起を核とした長径が少くとも0.2
μm以上の窪みとからなる凹凸単位のフィルム表面積1
mm^2当りの数A(個/mm^2)が下記式[3]を
満たし、フィルムのタテ、ヨコの厚さ斑が共に8%以下
であることを特徴とする平坦易滑性、フィルムの厚さ斑
にすぐれたポリエチレン−2,6−ナフタレートフィル
ム。 ΔP≦1.43@n@−2.136…………[1]1.
6650≦@n@≦1.6750…………[2]0<A
≦15000…………[3]
(1) 0.0 inert fine particles with an average particle size of 0.1 to 10μ
A polyethylene-2,6-naphthalate film containing 1 to 10% by weight, the 1/2 crystallization time of the film at 200°C is 6.0 minutes or less, and the degree of plane orientation Δ
P and the average refractive index @n@ satisfy the following formulas [1] and [2], and the long axis of the protrusion and the protrusion as a core is at least 0.2
Film surface area of the unit of unevenness consisting of depressions of μm or more 1
A flat and slippery film characterized by the number A per mm^2 (pieces/mm^2) satisfying the following formula [3], and the thickness unevenness in both the vertical and horizontal directions of the film being 8% or less. Polyethylene-2,6-naphthalate film with excellent thickness unevenness. ΔP≦1.43@n@−2.136…………[1]1.
6650≦@n@≦1.6750……[2]0<A
≦15000…………[3]
(2)実質的に無配向のポリエチレン−2,6−ナフタ
レートの未延伸フィルムをまず縦方向に複屈折率Δnが
0.030以上0.090以下となるよう延伸(前段延
伸)し、更に縦方向に複屈折率Δnが0.090以上0
.140以下となるよう延伸(後段延伸)したのち、横
延伸する事を特徴とする特許請求の範囲第1項記載のポ
リエチレン−2,6−ナフタレートフィルム。
(2) A substantially unoriented unstretched film of polyethylene-2,6-naphthalate is first stretched in the longitudinal direction so that the birefringence Δn becomes 0.030 or more and 0.090 or less (pre-stretching), and then The birefringence Δn is 0.090 or more in the direction
.. 14. The polyethylene-2,6-naphthalate film according to claim 1, wherein the polyethylene-2,6-naphthalate film is stretched to a molecular weight of 140 or less (post-stage stretching) and then laterally stretched.
JP20628886A 1986-09-02 1986-09-02 Polyethylene-2,6-naphthalate film Pending JPS6360732A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP20628886A JPS6360732A (en) 1986-09-02 1986-09-02 Polyethylene-2,6-naphthalate film

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP20628886A JPS6360732A (en) 1986-09-02 1986-09-02 Polyethylene-2,6-naphthalate film

Publications (1)

Publication Number Publication Date
JPS6360732A true JPS6360732A (en) 1988-03-16

Family

ID=16520824

Family Applications (1)

Application Number Title Priority Date Filing Date
JP20628886A Pending JPS6360732A (en) 1986-09-02 1986-09-02 Polyethylene-2,6-naphthalate film

Country Status (1)

Country Link
JP (1) JPS6360732A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0325724A (en) * 1989-06-23 1991-02-04 Diafoil Co Ltd Oriented polyester film for magnetic disk
JPH05131538A (en) * 1991-11-13 1993-05-28 Teijin Ltd Polyethylene-2, 6-naphthalate film

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0325724A (en) * 1989-06-23 1991-02-04 Diafoil Co Ltd Oriented polyester film for magnetic disk
JPH05131538A (en) * 1991-11-13 1993-05-28 Teijin Ltd Polyethylene-2, 6-naphthalate film

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