JPH07238152A - Production of polyethylene naphthalate film - Google Patents
Production of polyethylene naphthalate filmInfo
- Publication number
- JPH07238152A JPH07238152A JP3043294A JP3043294A JPH07238152A JP H07238152 A JPH07238152 A JP H07238152A JP 3043294 A JP3043294 A JP 3043294A JP 3043294 A JP3043294 A JP 3043294A JP H07238152 A JPH07238152 A JP H07238152A
- Authority
- JP
- Japan
- Prior art keywords
- film
- polymer
- polyethylene naphthalate
- naphthalate
- hydroxyethyl
- 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.)
- Granted
Links
Landscapes
- Polyesters Or Polycarbonates (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ポリエチレンナフタレ
ートフィルムの製造方法に関する。FIELD OF THE INVENTION The present invention relates to a method for producing a polyethylene naphthalate film.
【０００２】さらに詳しくは、良好な生産性で表面欠点
の無いポリエチレンナフタレートフィルムを製造する方
法に関する。More specifically, it relates to a method for producing a polyethylene naphthalate film having good productivity and no surface defects.
【０００３】[0003]
【従来の技術】ポリエチレンナフタレートは、従来知ら
れているポリエステルの中でも機械的特質、耐熱性、耐
薬品性などに優れた性質を有しており、フィルム用途で
は、例えば磁気記録媒体、コンデンサー、電気絶縁、製
版、写真用フィルムなどの材料として好適である。2. Description of the Related Art Polyethylene naphthalate has excellent mechanical properties, heat resistance, chemical resistance and the like among conventionally known polyesters, and in film applications, for example, magnetic recording media, capacitors, It is suitable as a material for electrical insulation, plate making, photographic film and the like.
【０００４】しかしながら、ポリエチレンナフタレート
は、例えばポリエチレンテレフタレートと比較し、製膜
時において溶融ポリマをダイスリットを通して薄膜化す
る際、口金部にポリマの劣化物が付着することに起因す
る筋状の白濁部分（筋状欠点）がフィルムに発生しやす
く、また、ポリマの劣化物がフィルムに混入して粗大な
突起を形成し、その結果商品価値を著しく低下させる現
象が生じるため、表面に欠点の無いフィルムの生産性が
低いという問題がある。However, compared with polyethylene terephthalate, for example, polyethylene naphthalate has streaky white turbidity caused by the adherence of polymer deterioration products to the die when thinning a molten polymer through a die slit during film formation. Areas (streak defects) tend to occur on the film, and deterioration products of the polymer mix into the film to form coarse protrusions, resulting in a phenomenon that markedly reduces the commercial value, so there is no defect on the surface. There is a problem that the productivity of the film is low.
【０００５】これらのポリマの劣化物が口金部に付着す
ることによる生産性低下を抑制する方法として、口金部
分に油状物を塗り、ポリマ劣化物の離脱を容易にするこ
と、口金部の形状を最適化すること、口金部を定期的に
清掃することなどが行なわれているが、未だ生産性を十
分に向上させるに至っていない。As a method of suppressing the productivity deterioration due to the deterioration products of these polymers adhering to the die part, an oily substance is applied to the die part so as to facilitate the removal of the polymer deteriorated product, and the shape of the die part is changed. Although optimization and regular cleaning of the mouthpiece have been carried out, the productivity has not been sufficiently improved yet.
【０００６】また、生産性を低下させる原因になってい
るポリマの劣化物の発生を抑制するため、例えば特開昭
６２−１４３９３８号公報などに示されるように、回分
式重縮合法でポリマを製造時に熱安定剤として添加する
リン化合物の量や種類の最適化を図る検討が行なわれて
きたが未だ十分な効果を奏するに至っていない。Further, in order to suppress the generation of polymer deterioration products which cause a decrease in productivity, a polymer is produced by a batch polycondensation method as disclosed in, for example, JP-A-62-143938. Studies have been conducted to optimize the amount and type of phosphorus compound added as a heat stabilizer at the time of production, but it has not yet achieved sufficient effects.
【０００７】ポリエチレンナフタレートが上記の欠点が
生じやすいのは、ポリエチレンテレフタレートと比較
し、産業上有用な重合度のポリマとなるまで重縮合反応
を進行させると溶融粘度が高くなるため、回分式の製造
法においては重縮合缶からポリマを排出する際に長時間
を必要とする結果、排出初期に比べ末期ではカルボキシ
ル基末端濃度は増加し、分子量は小さくなるなどポリマ
の品質低下が原因になっている。さらに、ポリエチレン
ナフタレートは高粘度のために缶内に付着残留するポリ
マが多くなるため熱劣化が進行し、回分式重縮合法では
前述のごとく、１回の重縮合反応によって得られたポリ
マで重縮合缶からの排出初期と末期におけるポリマ特性
が異なるという問題点に加えて、さらに回を重ねて重縮
合反応を行なった場合、缶内に付着残留した熱劣化ポリ
マの影響のために回分毎に得られたポリマの特性の間に
さらに大きなバラツキが生じ、ポリマの分子量、カルボ
キシル基末端濃度やジエチレングリコール含量をさらに
大きく変動させる。この結果、回分式重縮合法で得たポ
リエチレンナフタレートを用いてフィルムを製造する
際、製膜時の破れや厚み斑が発生し、生産安定性を低下
させるという問題がある。[0007] Polyethylene naphthalate is apt to cause the above-mentioned drawbacks because, when compared with polyethylene terephthalate, the melt viscosity becomes high when the polycondensation reaction proceeds until a polymer having a polymerization degree industrially useful is obtained. In the manufacturing method, it takes a long time to discharge the polymer from the polycondensation can.As a result, the terminal concentration of the carboxyl group increases in the final stage compared to the initial stage of the discharge, and the molecular weight becomes small, which causes deterioration of the polymer quality. There is. Furthermore, since polyethylene naphthalate has a high viscosity, a large amount of polymer remains in the can because it adheres to and remains in the can. Therefore, in the batch polycondensation method, the polymer obtained by one polycondensation reaction as described above is used. In addition to the problem that the polymer properties at the beginning and the end of discharge from the polycondensation can are different, and when the polycondensation reaction is repeated more times, each batch is affected by the heat-degraded polymer remaining in the can. There is even greater variation in the properties of the polymer obtained, and the molecular weight of the polymer, the terminal carboxyl group concentration, and the diethylene glycol content are further varied. As a result, when a film is produced using the polyethylene naphthalate obtained by the batch polycondensation method, there is a problem that tearing and uneven thickness occur during film production, which lowers production stability.
【０００８】上記回分式の重縮合方式で製造したポリマ
から得たフィルムの筋状欠点、熱劣化物の微小の固まり
による粗大突起の生成は、表面の平滑性が高度に要求さ
れる磁気テープ用途、特に磁性金属を蒸着して磁性層を
形成する蒸着テープや金属磁性体とバインダーの混合物
を塗布して磁性層を形成するメタルテープの支持体、な
らびに写真用途、特に微小な欠点が画像の価値を著しく
低下させる高感度写真フィルムなどに用いるフィルムの
生産性を著しく低下させる。また、上記回分式の重縮合
方式で製造したポリエチレンナフタレートの分子量、カ
ルボキシル末端基濃度やジエチレングリコール含量の変
動ならびに熱劣化物の生成は、厚さが薄いフィルム、特
に厚さが０．５〜２０μｍ域のフィルムを製膜する際に
は、フィルム破れの多発や、厚み斑の原因になり、良好
なフィルムの生産性を極度に低下させる。The strip-like defects of the film produced from the polymer produced by the batch-type polycondensation method, and the formation of coarse projections due to minute lumps of heat-deteriorated products are used in magnetic tape applications where a high degree of surface smoothness is required. , Especially vapor deposition tape that deposits a magnetic metal to form a magnetic layer, a metal tape support that forms a magnetic layer by coating a mixture of a metal magnetic material and a binder, and photographic applications, especially when a minute defect is the value of an image. The productivity of a film used for a high-speed photographic film or the like is significantly reduced. In addition, fluctuations in the molecular weight, the concentration of carboxyl end groups and the content of diethylene glycol of polyethylene naphthalate produced by the batch polycondensation method and the generation of heat-deteriorated products are caused by a thin film, particularly a thickness of 0.5 to 20 μm. When a film in the area is formed, it often causes film breakage and uneven thickness, and extremely reduces the productivity of a good film.
【０００９】[0009]
【発明が解決しようとする課題】本発明者らは、前述の
ようなポリエチレンナフタレートの製膜時の筋状欠点や
熱劣化物による粗大突起の生成などによる表面欠点の無
く、厚み斑の小さいポリエチレンナフタレートフィルム
を良好な生産性で製造する方法を見出だすこと課題に鋭
意検討を重ね本発明に到達した。DISCLOSURE OF THE INVENTION The inventors of the present invention do not have the above-mentioned streak-like defects at the time of film formation of polyethylene naphthalate and surface defects due to the formation of coarse projections due to heat-degraded products, and have a small thickness unevenness. The inventors have earnestly studied to find a method for producing a polyethylene naphthalate film with good productivity, and arrived at the present invention.
【００１０】[0010]
【課題を解決するための手段】前記した本発明の課題
は、以下の構成によって達成される。 １．ビス（ヒドロキシエチル）ナフタレートを連続的に
重縮合して得たポリエチレンナフタレートを用いること
を特徴とする、ポリエチレンナフタレートフィルムの製
造方法。 ２．ビス（ヒドロキシエチル）ナフタレートを連続的に
重縮合して得たポリエチレンナフタレートを用いること
を特徴とする、表面突起の平均高さが５〜４００ｎｍで
あるポリエチレンナフタレートフィルムの製造方法。 ３．ビス（ヒドロキシエチル）ナフタレートを連続的に
重縮合して得たポリエチレンナフタレートを用いること
を特徴とする、カルボキシル末端基数が５〜４５当量／
１０6 ｇである上記１項または上記２項に記載のポリエ
チレンナフタレートフィルムの製造方法。The above-described object of the present invention can be achieved by the following constitution. 1. A method for producing a polyethylene naphthalate film, which comprises using polyethylene naphthalate obtained by continuously polycondensing bis (hydroxyethyl) naphthalate. 2. A method for producing a polyethylene naphthalate film having an average height of surface protrusions of 5 to 400 nm, which comprises using polyethylene naphthalate obtained by continuously polycondensing bis (hydroxyethyl) naphthalate. 3. A polyethylene naphthalate obtained by continuously polycondensing bis (hydroxyethyl) naphthalate is used, wherein the number of carboxyl terminal groups is 5 to 45 equivalents /
The method for producing a polyethylene naphthalate film according to the above item 1 or 2, wherein the amount is 10 6 g.
【００１１】本発明において、フィルムの製膜に用いる
ポリエチレンナフタレートは、ビス（ヒドロキシエチ
ル）ナフタレートを連続的に重縮合する方法によって製
造する。In the present invention, polyethylene naphthalate used for forming a film is produced by a method of continuously polycondensing bis (hydroxyethyl) naphthalate.
【００１２】本発明において、ビス（ヒドロキシエチ
ル）ナフタレートは、ナフタレンジカルボン酸とエチレ
ングリコールを直接エステル化する方法または、ジメチ
ルナフタレートとエチレングリコールを用いエステル交
換によって得る方法のいずれの方法により得られたもの
であってもよく、上記のエステル化反応またはエステル
交換反応を所望によって１槽または複数の槽に分け、連
続的に反応を行なうことによって得ることができる。In the present invention, bis (hydroxyethyl) naphthalate was obtained by either the method of directly esterifying naphthalenedicarboxylic acid and ethylene glycol or the method of obtaining it by transesterification using dimethyl naphthalate and ethylene glycol. The above esterification reaction or transesterification reaction can be obtained by dividing the above-mentioned esterification reaction or transesterification reaction into one tank or a plurality of tanks and carrying out the reaction continuously.
【００１３】本発明において、ビス（ヒドロキシエチ
ル）ナフタレートというのは、エステル交換反応または
エステル化反応によって得られたビス（ヒドロキシエチ
ル）ナフタレートならびにこの化合物の１０重量体以下
の低重合体の混合物をいう。In the present invention, bis (hydroxyethyl) naphthalate means a mixture of bis (hydroxyethyl) naphthalate obtained by a transesterification reaction or an esterification reaction and a low polymer of 10 weight parts or less of this compound. .
【００１４】また、エステル交換反応またはエステル化
反応は、触媒としてマグネシウム、リチウム、亜鉛、カ
ルシウム、マンガンなどの金属化合物を用いることによ
って、反応時間を短縮することができる。この場合、最
終的に得られたポリエチレンナフタレート中に触媒残渣
による不溶物を少なくすることができる点から、マグネ
シウム、マンガン、亜鉛化合物を用いるのが好ましく、
特に好ましいのはマグネシウム化合物である。In the transesterification reaction or the esterification reaction, the reaction time can be shortened by using a metal compound such as magnesium, lithium, zinc, calcium or manganese as a catalyst. In this case, it is preferable to use magnesium, manganese, and zinc compounds from the viewpoint that insoluble matters due to catalyst residues can be reduced in the finally obtained polyethylene naphthalate,
Particularly preferred is a magnesium compound.
【００１５】上記で得られたビス（ヒドロキシエチル）
ナフタレートを撹拌ならびに反応物を連続的に移動させ
る機能を備えた反応槽で２３０℃から３１０℃まで加熱
し、減圧下で重縮合反応を行なう。この際、所望に応じ
て重縮合工程を１槽または複数槽に分割して連続的に行
なうことができる。重縮合反応の触媒としては、アンチ
モン、ゲルマニウム、チタンなど重縮合触媒として公知
の金属化合物を用いることができるが、好ましくはアン
チモン、ゲルマニウム化合物で、特に好ましくはゲルマ
ニウム化合物である。Bis (hydroxyethyl) obtained above
The polycondensation reaction is performed under reduced pressure by heating from 230 ° C. to 310 ° C. in a reaction tank equipped with a function of stirring naphthalate and continuously moving the reaction product. At this time, the polycondensation step can be continuously performed by dividing it into one tank or a plurality of tanks, if desired. As the catalyst for the polycondensation reaction, metal compounds known as polycondensation catalysts such as antimony, germanium and titanium can be used, but antimony and germanium compounds are preferable, and germanium compounds are particularly preferable.
【００１６】本発明において用いるジカルボン酸は、
２，６−ナフタレンジカルボン酸を主成分とするが、そ
の一部（通常、全酸成分の３０モル％以下）を、例えば
シュウ酸、コハク酸、アジピン酸、セバチン酸、ダイマ
ー酸、ヘキサヒドロテレフタル酸、フタル酸、イソフタ
ル酸、テレフタル酸、２，７−ナフタレンジカルボン
酸、１，５−ナフタレンジカルボン酸、ジフェニルジカ
ルボン酸、ジフェニルエーテルジカルボン酸、ジフェノ
キシエタン−４，４′−ジカルボン酸、ジフェニルスル
ホンジカルボン酸、３，５−ジカルボキシベンゼンスル
ホン酸ナトリウム、グリコール酸、ｐ−オキシ安息香
酸、ｐ−オキシエトキシ安息香酸などの二官能性酸の１
種または２種以上でおきかえることができる。The dicarboxylic acid used in the present invention is
The main component is 2,6-naphthalenedicarboxylic acid, and a part of it (usually 30 mol% or less of the total acid component) is, for example, oxalic acid, succinic acid, adipic acid, sebacic acid, dimer acid, hexahydroterephthalate. Acid, phthalic acid, isophthalic acid, terephthalic acid, 2,7-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenyletherdicarboxylic acid, diphenoxyethane-4,4'-dicarboxylic acid, diphenylsulfonedicarboxylic acid Acid, sodium 3,5-dicarboxybenzenesulfonate, glycolic acid, p-oxybenzoic acid, bifunctional acid such as p-oxyethoxybenzoic acid 1
It can be replaced with one kind or two or more kinds.
【００１７】また、本発明において用いるグリコールは
エチレングリコールを主成分するが、その一部（通常、
全グリコール成分の３０モル％以下）を、例えばＨＯ
（ＣＨ2 ）ｎＯＨ（ここでｎは３〜１０の整数を示す）
で示される直鎖脂肪族グリコール、イソブチレングリコ
ール、ポリエチレングリコ−ル、ネオペンチルグリコー
ル、１，４−シクロヘキサンジオール、２，２−ビス−
４−ヒドロキシフェニルプロパン、ヒドロキノン、１，
５−ジヒドロキシナフタレン、２，６−ジヒドロキシナ
フタレンなどのジオキシ化合物の１種または２種以上で
おきかえることができる。The glycol used in the present invention contains ethylene glycol as a main component, but a part of it (usually,
30 mol% or less of the total glycol component), for example, HO
(CH 2 ) nOH (where n is an integer of 3 to 10)
A linear aliphatic glycol, isobutylene glycol, polyethylene glycol, neopentyl glycol, 1,4-cyclohexanediol, 2,2-bis-
4-hydroxyphenylpropane, hydroquinone, 1,
It can be replaced by one or more dioxy compounds such as 5-dihydroxynaphthalene and 2,6-dihydroxynaphthalene.
【００１８】本発明に用いるポリエチレンナフタレート
の固有粘度は０．５〜０．８が好ましく、さらには０．
５５〜０．７，特には０．５８〜０．６５が好ましい。
固有粘度が０．５以下の場合は得られたフィルムの機械
的強度が低く、０．８以上になると製膜時の溶融粘度が
高くなり過ぎる傾向がある。The intrinsic viscosity of the polyethylene naphthalate used in the present invention is preferably 0.5 to 0.8, more preferably 0.
55 to 0.7, particularly 0.58 to 0.65 is preferable.
When the intrinsic viscosity is 0.5 or less, the mechanical strength of the obtained film is low, and when it is 0.8 or more, the melt viscosity during film formation tends to be too high.
【００１９】本発明に用いるポリエチレンナフタレート
のカルボキシル末端基濃度は、得られるフィルムのカル
ボキシル末端基濃度が４５当量／１０6 ｇ以下になる範
囲のものがが好ましく、さらには４０当量／１０6 ｇ以
下、特に３５当量／１０6 ｇ以下になるものが好まし
い。なお、カルボキシル末端基濃度は低い方が好ましい
が、５当量／１０6 ｇ以下のフィルムが得られるポリマ
を工業的に経済性良く製造するのが困難になる。また、
カルボキシル末端基濃度が４５当量／１０6 ｇ以上にな
ると、製膜時の口金部分に劣化物の付着が増加し、良好
な表面を有するフィルムの収率の低下が相対的に大きく
なる。また、ジエチレングリコールの含量は１．５重量
％以下、特に１．３重量％以下が好ましい。ジエチレン
グリコールの含量が１．５重量％以上になると、得られ
るフィルムの軟化温度が低下し、製膜時やフィルムを加
工する際の巻取時にフィルム同士が粘着しやすくなり好
ましくない。The concentration of the carboxyl end groups of the polyethylene naphthalate used in the present invention is preferably such that the concentration of the carboxyl end groups of the obtained film is 45 equivalents / 10 6 g or less, more preferably 40 equivalents / 10 6 g. It is particularly preferable that the amount is 35 equivalents / 10 6 g or less. It is preferable that the carboxyl terminal group concentration is low, but it becomes difficult to industrially and economically produce a polymer capable of obtaining a film of 5 equivalents / 10 6 g or less. Also,
When the carboxyl terminal group concentration is 45 equivalents / 10 6 g or more, the adherence of deteriorated substances to the die portion during film formation increases, and the yield of a film having a good surface relatively decreases. Further, the content of diethylene glycol is preferably 1.5% by weight or less, particularly preferably 1.3% by weight or less. When the content of diethylene glycol is 1.5% by weight or more, the softening temperature of the obtained film is lowered, and the films tend to stick to each other during film formation or winding during processing of the film, which is not preferable.
【００２０】本発明のフィルムの製造方法は、上記の連
続重縮合で得たポリエチレンナフタレートを用い、製膜
用口金を備えた押出機でポリマを２９０〜３２０℃の溶
融状態で押出し、２０〜５０℃の冷却ロールで冷却して
未延伸フィルムを得る。この未延伸フィルムを縦方向に
３〜１０倍、横方向に３〜１０倍延伸し、所望によって
は、再度縦方向に１〜３倍延伸した後、１９０〜２３０
℃で熱処理して二軸延伸フィルムを得る。In the method for producing a film of the present invention, the polyethylene naphthalate obtained by the above-mentioned continuous polycondensation is used, and the polymer is extruded in a molten state at 290 to 320 ° C. with an extruder equipped with a die for film formation, and then 20 to 20 ° C. An unstretched film is obtained by cooling with a cooling roll at 50 ° C. This unstretched film is stretched 3 to 10 times in the machine direction and 3 to 10 times in the transverse direction, and if necessary, 1 to 3 times in the machine direction again, and then 190 to 230.
A biaxially stretched film is obtained by heat treatment at ℃.
【００２１】また、本発明のフィルムの製造方法は、２
〜３基の押出機と溶融ポリマの合流部ならびに溶融ポリ
マの分配装置を備えた製膜用の口金を用い、溶融状態で
２〜５層に積層し、上記と同様に冷却、縦ならびに横延
伸、熱処理をして２〜５層の積層フィルムを得ることが
できる。The method for producing the film of the present invention is 2
~ Using a spinneret for film formation equipped with three extruders, a confluent part of the molten polymer, and a distributor for the molten polymer, laminate 2 to 5 layers in a molten state, and perform cooling, longitudinal and transverse stretching in the same manner as above. Then, heat treatment can be performed to obtain a laminated film having 2 to 5 layers.
【００２２】また本発明において、ポリエチレンナフタ
レートに無機粒子、有機塩粒子、架橋性高分子粒子など
の公知の粒子を添加して製膜することによって、製膜
時、加工時、使用時の走行性やハンドリング性を向上す
ることができる。無機粒子としては、例えば炭酸カルシ
ウム、カオリン、タルク、炭酸マグネシウム、炭酸バリ
ウム、硫酸カルシウム、硫酸バリウム、リン酸リチウ
ム、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、酸化ケイ素、酸化チタン、フッ化リチウム、
シュウ酸カルシウム、Ｃａ、Ｂａ、Ｚｎ、Ｍｎなどのテ
レフタル酸塩などを挙げることができ、これらのうち１
種または２種以上を添加することができる。また、架橋
性高分子粒子としては、例えばジビニルベンゼン、スチ
レン、アクリル酸、メタクリル酸、アクリル酸もしくは
メタクリル酸のアルキルエステルなどのビニル系モノマ
の単独重合体または共重合体を挙げることができる。Further, in the present invention, known particles such as inorganic particles, organic salt particles and crosslinkable polymer particles are added to polyethylene naphthalate to form a film, so that running during film formation, processing and use can be achieved. It is possible to improve the property and the handling property. Examples of the inorganic particles include calcium carbonate, kaolin, talc, magnesium carbonate, barium carbonate, calcium sulfate, barium sulfate, lithium phosphate, calcium phosphate, magnesium phosphate, aluminum oxide, silicon oxide, titanium oxide, lithium fluoride,
Examples thereof include terephthalic acid salts such as calcium oxalate, Ca, Ba, Zn, and Mn.
One kind or two or more kinds can be added. Examples of the crosslinkable polymer particles include homopolymers or copolymers of vinyl-based monomers such as divinylbenzene, styrene, acrylic acid, methacrylic acid, and alkyl esters of acrylic acid or methacrylic acid.
【００２３】所望によって前記の粒子を添加して本発明
の方法で得たフィルムは、表面に筋状欠点や熱劣化物に
よる粗大突起が無く極めて良好な表面特性を有している
が、この特性が好ましく発揮されるのはフィルムの表面
突起の平均高さが４００ｎ以下であり、さらには２００
ｎｍ以下、特には８０ｎｍ以下である。なお、突起の平
均高さが５ｎｍ以下になると、フィルムの加工時、使用
時の走行性が著しく低下する傾向がある。The film obtained by the method of the present invention by adding the above-mentioned particles, if desired, has extremely good surface characteristics without streaky defects or coarse projections due to heat-deteriorated products. Is preferably exhibited when the average height of the surface protrusions of the film is 400 n or less, and further 200
nm or less, particularly 80 nm or less. When the average height of the protrusions is 5 nm or less, the running property of the film tends to be significantly reduced during processing and use.
【００２４】また、本発明の方法で得たフィルムは前記
の表面欠点が無いので、すべての厚みのフィルムで良好
な表面特性を有しているが、この特性が好ましく発揮さ
れるのは８０μｍ以下、さらには２０μｍ以下、特には
１０μｍ以下である。フィルム表面の突起の平均高さが
４００ｎｍを越える場合や、厚さが８０μｍを越える場
合は、前記の熱劣化物による粗大突起や筋状欠点が相対
的に目立たなくなる傾向が見られる。Further, since the film obtained by the method of the present invention does not have the above-mentioned surface defects, it has good surface properties for films of all thicknesses, but this property is preferably exhibited at 80 μm or less. Further, it is 20 μm or less, and particularly 10 μm or less. When the average height of the projections on the film surface exceeds 400 nm, or when the thickness exceeds 80 μm, the coarse projections and streak-like defects due to the heat-deteriorated product tend to be relatively inconspicuous.
【００２５】本発明の方法によって得られたフィルム
は、磁気記録媒体、フィルムコンデンサー、電気絶縁、
感光剤またはさらに磁気記録層を塗布した写真用フィル
ム、製版などの材料として好ましく使用できる。上記各
種用途の中でも、金属酸化物あるいは金属の磁性体を用
いたいずれの磁気記録媒体に使用するフィルム用途にも
好適であるが、特に好適な用途は、磁気記録媒体の中
で、支持体に高度の平滑性、無欠点性を要求される金属
蒸着タイプの磁気記録媒体、デジタル記録方式の磁気記
録媒体の支持体用のフィルムである。The film obtained by the method of the present invention is used for magnetic recording media, film capacitors, electrical insulation,
It can be preferably used as a material for a photographic film coated with a photosensitizer or a magnetic recording layer, a plate-making plate and the like. Among the above various uses, it is suitable for use as a film for any magnetic recording medium using a metal oxide or a magnetic material of metal, and a particularly preferable use is for a support in a magnetic recording medium. It is a film for a support of a metal vapor deposition type magnetic recording medium and a digital recording type magnetic recording medium which are required to have high smoothness and no defect.
【００２６】[0026]
【実施例】本発明をさらに具体的に説明するために、以
下実施例および比較例を挙げて説明するが、これら実施
例は、本発明を限定するものではない。なお、本発明に
おける種々の物性、特性の測定方法、定義は下記のとお
りである。また、本発明の実施例および比較例に示す触
媒、リン化合物の添加量は、ジカルボン酸成分１００重
量部に対する重量部数である。 １．固有粘度 ｏ−クロロフェノールを溶媒とし、２５℃で測定した。 ２．カルボキシル基濃度 Pohlらによる Analytical Chemistry 第２６巻１６１４
頁記載の方法で測定した。 ３．ジエチレングリコール含量の測定 ポリマチップ０．５ｇをモノエタノールアミン中でアミ
ン分解し、遊離したジエチレングリコールをガスクロマ
トグラフィーで測定した。なお、数値はポリマ中のジエ
チレングリコールの重量％である。 ４．平均突起高さ ４検出方式のフィールドエミション電子線三次元粗さ解
析装置（エリオニクス社製ＥＲＡ−８０００ＦＥ）を用
い、フィルム表面の平坦面の高さを０としたときの突起
高さを測定した。ここで、走査型電子顕微鏡の倍率は１
０００〜３００００倍の間を選択し、測定を１００視野
について行い、５ｎｍ以上の高さを有するものを突起と
し、その高さの平均値を用いた。なお、場合によって
は、原子間力顕微鏡（Ｄｉｇｉｔａｌ Ｉｎｓｔｒｕｍ
ｅｎｔ社製 Ｎａｎｏｓｃｏｐｅ２）をもちいて５μｍ
四方の視野を走査速度０．６９Ｈｚで走査することによ
って得られた高さ情報を、上記粗さ解析装置の値に読み
替えて用いた。EXAMPLES In order to more specifically describe the present invention, examples and comparative examples will be described below, but these examples do not limit the present invention. In addition, various physical properties in the present invention, measuring methods of properties, and definitions are as follows. Further, the addition amounts of the catalyst and the phosphorus compound shown in Examples and Comparative Examples of the present invention are parts by weight with respect to 100 parts by weight of the dicarboxylic acid component. 1. Intrinsic viscosity Using o-chlorophenol as a solvent, it was measured at 25 ° C. 2. Carboxyl group concentration Analytical Chemistry Vol. 26, 1614 by Pohl et al.
It was measured by the method described on the page. 3. Measurement of diethylene glycol content 0.5 g of polymer chips were subjected to amine decomposition in monoethanolamine, and the released diethylene glycol was measured by gas chromatography. The numerical value is the weight% of diethylene glycol in the polymer. 4. Average projection height 4 The projection height when the height of the flat surface of the film was set to 0 was measured using a field emission electron three-dimensional roughness analyzer (ERA-8000FE manufactured by Elionix Co., Ltd.) with a detection method. . Here, the magnification of the scanning electron microscope is 1
000 to 30,000 times was selected, measurement was performed for 100 fields of view, and those having a height of 5 nm or more were defined as protrusions, and the average value of the heights was used. In some cases, an atomic force microscope (Digital Instrument
5 μm using Nanoscope2) manufactured by ent
The height information obtained by scanning the four visual fields at a scanning speed of 0.69 Hz was used by replacing it with the value of the roughness analyzer.
【００２７】５．粗大突起 小坂研究所の非接触３次元表面粗さ計ＨＩＰＯＳＳ（Ｅ
Ｔ−３０ＨＫ）を用い、高さ４００ｎｍ以上の突起の数
をつぎの条件で２０回測定し、１ｍｍ2 当たりの個数に
換算して求めた。数が多いほど、粗大突起が多いことを
示す。 ・縦倍率：２００００倍 ・横倍率：５００倍 ・カットオフ：０．０８ｍｍ ・送りピッチ：０．５μｍ ・測定長 ：５００μｍ ・測定面積 ：０．０１９４ｍｍ2 ・走査速度 ：１００μｍ／秒5. Coarse protrusion Kosaka Laboratory's non-contact three-dimensional surface roughness meter HIPS (E
(T-30HK), the number of protrusions having a height of 400 nm or more was measured 20 times under the following conditions, and converted into the number per 1 mm 2 . The larger the number, the larger the number of coarse projections.・ Vertical magnification: 20000 times ・ Horizontal magnification: 500 times ・ Cutoff: 0.08 mm ・ Feed pitch: 0.5 μm ・ Measuring length: 500 μm ・ Measuring area: 0.0194 mm 2・ Scanning speed: 100 μm / sec
【００２８】６．筋状欠点 同一原料組成で３時間製膜した後、直後に得た５０ｃｍ
四方のフィルムを１０倍に拡大した視野で観察して筋状
欠点の個数を測定した。なお、次の基準で１、２級を合
格とした。 筋状欠点の個数 ０ 個 ：１級 １ 〃 ：２級 ２〜３〃 ：３級 ４個以上 ：４級6. Striped defect 50 cm obtained immediately after film formation with the same raw material composition for 3 hours
The number of streak-like defects was measured by observing the films on all sides with a field of view magnified 10 times. It should be noted that grades 1 and 2 were passed according to the following criteria. Number of streak defects 0: 1st grade 1〃: 2nd grade 2-3〃: 3rd grade 4 or more: 4th grade
【００２９】７．厚み斑 アンリツ社製フィルムシックネステスタＫＧ６０１Ａを
使用し、所定の方向に幅５０ｍｍ，長さ５０ｍ長の試料
を速度３ｍ／分で走行させフィルム厚みを測定した。ア
ンリツ社製広範囲電子マイクロメータＫ３０６Ｃでフィ
ルム厚みを読取り、次式から厚み斑を算出した。 厚み斑（％）＝（最大厚さ−最小厚さ）／平均厚さ×１
００7. Thickness Unevenness A film thickness tester KG601A manufactured by Anritsu Corporation was used to measure a film thickness by running a sample having a width of 50 mm and a length of 50 m in a predetermined direction at a speed of 3 m / min. The film thickness was read with a wide range electronic micrometer K306C manufactured by Anritsu Co., Ltd., and the thickness unevenness was calculated from the following equation. Thickness variation (%) = (maximum thickness-minimum thickness) / average thickness x 1
00
【００３０】（連続重縮合方法によるポリマの製造）精
留塔を備えた縦型の多段の流下式反応槽で上部から下部
に温度１９０℃から２３０℃に加熱できる第１エステル
交換反応槽へ、溶融した２，６−ナフタレンジカルボン
酸ジメチル１００部、予熱したエチレングリコール５１
部、酢酸マグネシウム０．０５部を連続的に供給し、エ
ステル交換反応率９５％の反応物を連続的に抜き出し
た。この反応物を精留塔、撹拌機を備えた第２エステル
交換反応槽に連続的に移行し、２３０℃で加熱してエス
テル交換反応率が９９．９％以上のビス（ヒドロキシエ
チル）ナフタレートを得た。上記ビス（ヒドキシエチ
ル）ナフタレートを次工程へ移行させる過程で、アルカ
リ水溶液にした二酸化ゲルマニウム０．０１部とリン酸
トリメチル０．０３部をラインミキサーを用いて各々別
の供給口から供給した。(Production of Polymer by Continuous Polycondensation Method) In a vertical multi-stage flow-down reaction tank equipped with a rectification column, a first transesterification reaction tank capable of heating from 190 ° C. to 230 ° C. from the upper part to the lower part, 100 parts of melted dimethyl 2,6-naphthalenedicarboxylate, preheated ethylene glycol 51
Parts and 0.05 parts of magnesium acetate were continuously supplied, and a reaction product having a transesterification reaction rate of 95% was continuously extracted. This reaction product was continuously transferred to a second transesterification reaction tank equipped with a rectification column and a stirrer, and heated at 230 ° C. to convert bis (hydroxyethyl) naphthalate having a transesterification reaction rate of 99.9% or more. Obtained. In the process of transferring the bis (hydroxyethyl) naphthalate to the next step, 0.01 parts of germanium dioxide and 0.03 parts of trimethyl phosphate made into an alkaline aqueous solution were supplied from separate supply ports using a line mixer.
【００３１】さらに、上記反応物を撹拌機、減圧系およ
び副生物の流出装置を備えた予備重縮合槽へ移行させ、
２６５℃、４０Ｔｏｒｒで１時間の滞留時間反応させ
た。次いで、横型の撹拌翼、減圧系および副生物の流出
装置およびスクリュー方式の反応物の系外への流出装置
を備えた横型反応槽へ上記反応物を連続的に移行させ、
流入口から流出装置の方向へ２７０℃から２９０℃の温
度勾配をつけた状態で反応を行ない、流出装置から連続
的にガット状で排出、冷却し、カッターで切断してチッ
プ状の固有粘度０．６３、ジエチレングリコール含量
１．０％、カルボキシル基末端濃度３０当量／１０6 ｇ
のポリエチレンナフタレート（ポリマＡ）を得た。Further, the above reaction product was transferred to a preliminary polycondensation tank equipped with a stirrer, a pressure reducing system and a by-product outflow device,
The reaction was carried out at 265 ° C. and 40 Torr for a residence time of 1 hour. Then, the reaction product was continuously transferred to a horizontal reaction tank equipped with a horizontal stirring blade, a decompression system and a by-product outflow device, and a screw-type reaction product outflow device.
The reaction is carried out with a temperature gradient of 270 ° C. to 290 ° C. from the inflow port toward the outflow device, and is continuously discharged from the outflow device in the form of a gut, cooled, and cut with a cutter to obtain a chip-shaped intrinsic viscosity of 0. .63, diethylene glycol content 1.0%, carboxyl group terminal concentration 30 equivalents / 10 6 g
Polyethylene naphthalate (Polymer A) was obtained.
【００３２】（回分式重縮合方法によるポリマの製造）
精留塔、撹拌機を備えたオートクレーブに、２，６−ナ
フタレンジカルボン酸ジメチル１００部、エチレングリ
コール５１部を仕込み、さらに０．０５部の酢酸マグネ
シウムを加え、２００℃から２３５℃へ加熱昇温し、生
成するメタノールを排出しながら３．５時間反応して、
エステル交換反応率が９９．９％のビス（ヒドロキシエ
チル）ナフタレートを得た。得られた反応生成物にアル
カリ水溶液にした二酸化ゲルマニウム０．０１部を加
え、さらにリン酸トリメチルエステル０．０３部を加え
て、２３５℃から２９０℃まで昇温しながら徐々に減圧
し、１Ｔｏｒｒ以下で２９０℃、２時間維持して重縮合
反応を完結させた。その後、缶内のポリマをガット状で
排出したものを冷却、切断してチップ状の固有粘度は
０．６２、ジエチレングリコール含量１．３％カルボキ
シル基末端濃度５０当量／１０6 ｇのポリエチレンナフ
タレート（ポリマＢ）を得た。(Production of Polymer by Batch Polycondensation Method)
An autoclave equipped with a rectification column and a stirrer was charged with 100 parts of dimethyl 2,6-naphthalenedicarboxylate and 51 parts of ethylene glycol, and 0.05 part of magnesium acetate was further added, and heated from 200 ° C to 235 ° C. And reacting for 3.5 hours while discharging the produced methanol,
Bis (hydroxyethyl) naphthalate having a transesterification rate of 99.9% was obtained. To the obtained reaction product, 0.01 part of germanium dioxide made into an alkaline aqueous solution was added, and 0.03 part of phosphoric acid trimethyl ester was further added, and the pressure was gradually reduced while increasing the temperature from 235 ° C. to 290 ° C. to 1 Torr or less. The temperature was maintained at 290 ° C. for 2 hours to complete the polycondensation reaction. Then, the polymer discharged from the can in the form of a gut was cooled and cut to obtain a chip-shaped intrinsic viscosity of 0.62, a diethylene glycol content of 1.3%, a carboxyl group terminal concentration of 50 equivalents / 10 6 g of polyethylene naphthalate ( Polymer B) was obtained.
【００３３】（粒子マスタポリマの製造）前記の回分式
重縮合方法によるポリマの製造の方法を用い、ビス（ヒ
ドロキシエチル）ナフタレートを得た段階で、エチレン
グリコールへ均一に分散させた平均径０．４μｍの炭酸
カルシウム粒子、平均径０．２μｍの球形ポリジビニル
ベンゼン粒子、平均径０．０５μｍの球形酸化ケイ素粒
子の各スラリを別々の反応系に添加し、その後は同様に
して重縮合反応を行い、前記粒子を２重量％含有した３
種類の粒子マスタポリマを得た。(Production of Particle Master Polymer) Using the method for producing a polymer by the batchwise polycondensation method described above, when bis (hydroxyethyl) naphthalate is obtained, an average diameter of 0.4 μm uniformly dispersed in ethylene glycol is obtained. Calcium carbonate particles, spherical polydivinylbenzene particles having an average diameter of 0.2 μm, and spherical silicon oxide particles having an average diameter of 0.05 μm were added to separate reaction systems, and then polycondensation reaction was carried out in the same manner. 3 containing 2% by weight of the particles
A kind of particle master polymer was obtained.
【００３４】実施例１ 溶融押出機、Ｔ型の製膜用口金、冷却ドラム、縦延伸装
置、横延伸装置ならびに熱処理装置を備えた通常の二軸
延伸製膜機を用い、前記の連続式重縮合反応で得たポリ
マＡ８０重量％、ジビニルベンゼン粒子マスタポリマ１
５重量％ならびに炭酸カルシウム粒子マスタポリマ５重
量％をチップ状態で混合して押出機に供給し、３００℃
で溶融押出して３５℃の冷却ドラムで冷却し、厚さ３７
５μｍの未延伸フィルムを得た。このフィルムを再度１
３５℃に加熱して縦方向に５倍、横方向に５倍延伸し、
続いて２１０℃で熱処理して厚さ１５μｍのフィルムを
得た。Example 1 A continuous biaxially stretched film forming machine equipped with a melt extruder, a T-type film forming die, a cooling drum, a longitudinal stretching device, a transverse stretching device and a heat treatment device was used, and the above continuous heavy 80% by weight of polymer A obtained by condensation reaction, divinylbenzene particle master polymer 1
5% by weight and 5% by weight of calcium carbonate particle master polymer are mixed in a chip state and supplied to an extruder at 300 ° C.
Melt extruded and cooled in a cooling drum at 35 ° C to a thickness of 37
An unstretched film of 5 μm was obtained. This film again 1
Heat to 35 ° C and stretch 5 times in the machine direction and 5 times in the transverse direction,
Then, it heat-processed at 210 degreeC and obtained the film with a thickness of 15 micrometers.
【００３５】比較例１ 実施例１において、ポリマＡに替えて前記の回分式重縮
合反応で得たポリマＢを用いる以外は実施例１と同様に
して、厚さ１５μｍのフィルムを得た。Comparative Example 1 A film having a thickness of 15 μm was obtained in the same manner as in Example 1 except that the polymer A obtained in the batch polycondensation reaction was used instead of the polymer A.
【００３６】実施例２ ２基の押出機と溶融ポリマの合流部ならびに表裏が同じ
で中層が異なる溶融ポリマにすることができる分配装置
を備えた３層複合製膜用口金を用いる以外は、実施例１
と同様の二軸延伸製膜機を用い、一方の押出機にポリマ
Ａのみを、他方の押出機にポリマＡ８５重量％とジビル
ベンゼン粒子マスタポリマ１５重量％の混合物を供給
し、口金部の溶融ポリマの分配装置を調節して、中層が
ポリマＡのみからなる３００μｍの層、表裏がポリマＡ
と粒子マスタの混合物からなる各３０μｍの層からなる
複合状態で溶融押出して３５℃の冷却ドラムで冷却し、
厚さ３６０μｍの未延伸フィルムを得た。この未延伸フ
ィルムを再度１３５℃に加熱して縦方向に６倍、横方向
に５倍延伸し、ひきつずき２１５℃で熱処理して、中層
がポリマＡのみからなる１０μｍの層、表裏がポリマＡ
と粒子マスタの混合物である各１μｍの層からなり、全
厚みが１２μｍのフィルムを得た。Example 2 Except for using a three-layer composite film-forming die having two extruders and a confluence of molten polymers and a distributor capable of forming molten polymers having the same front and back and different middle layers. Example 1
The same biaxially stretched film forming machine was used, and only one polymer A was supplied to one extruder and a mixture of 85% by weight of the polymer A and 15% by weight of divinylbenzene particle master polymer was supplied to the other extruder to melt the die. Adjusting the polymer distributor, the middle layer is a layer of 300 μm consisting only of polymer A, the front and back are polymer A
Melt-extruded in a composite state consisting of 30 μm layers each consisting of a mixture of
An unstretched film having a thickness of 360 μm was obtained. This unstretched film was heated again to 135 ° C., stretched 6 times in the longitudinal direction and 5 times in the transverse direction, and heat treated at 215 ° C. in Tsuzuki, and the middle layer was a layer of 10 μm consisting of only polymer A. Polymer A
And a particle master, each layer having a thickness of 1 μm, and having a total thickness of 12 μm.
【００３７】比較例２ 実施例２において、ポリマＡに替えてポリマＢを用いる
以外は実施例２と同様にして、中層がポリマＢのみから
なる１０μｍの層、表裏がポリマＢと粒子マスタの混合
物である各１μｍの層からなり、全厚みが１２μｍのフ
ィルムを得た。Comparative Example 2 The procedure of Example 2 was repeated, except that the polymer A was replaced by the polymer B, the middle layer was a layer of 10 μm composed of only the polymer B, and the front and back surfaces were a mixture of the polymer B and the particle master. And a total thickness of 12 μm was obtained.
【００３８】実施例３ ３基の押出機（押出機イ、ロ、ハ）と溶融ポリマの合流
部ならびに各層が異なる溶融ポリマにすることができる
分配装置を備えた３層複合製膜用口金を用いる以外は、
実施例１と同様の二軸延伸製膜機を用い、押出機イにポ
リマＡ７０重量％と前記球形酸化ケイ素粒子マスタポリ
マ３０重量％の混合物を、押出機ロにポリマＡのみを、
押出機ハにはポリマＡ８５重量％とポリジビニルベンゼ
ン粒子マスタポリマ１５重量％の混合物を各々供給し、
口金部の溶融ポリマの分配装置を調節して、第１層がポ
リマＡと酸化ケイ素粒子マスタポリマの混合物からなる
０．９μｍの層、第２層がポリマＡのみからなる２０
４．６μｍの層、第３層がポリマＡとポリジビニルベン
ゼン粒子マスタの混合物からなる４．５μｍの層からな
る複合状態で溶融押出して、３５℃の冷却ドラムで冷却
し、厚さ２１０μｍの未延伸フィルムを得た。この未延
伸フィルムを再度１３５℃に加熱して縦方向に６倍、横
方向に５倍延伸し、ひきつずき２１５℃で熱処理して、
第１層がポリマＡと酸化ケイ素粒子マスタポリマの混合
物からなる０．０３μｍの層、第２層がポリマＡのみか
らなる６．８２μｍの層、第３層がポリマＡとポリジビ
ニルベンゼン粒子マスタの混合物からなる０．１５μｍ
の層からなり、全厚みが７μｍの３層複合フィルムを得
た。Example 3 A three-layer composite film-forming spinneret equipped with three extruders (extruders a, b, and c) and a confluent part of molten polymer and a distributor for allowing each layer to be a different molten polymer. Other than using
Using the same biaxially stretched film forming machine as in Example 1, a mixture of 70% by weight of Polymer A and 30% by weight of the spherical silicon oxide particle master polymer was used in Extruder A, and only Polymer A was added in Extruder B.
The extruder c was fed with a mixture of 85% by weight of polymer A and 15% by weight of polydivinylbenzene particle master polymer,
The molten polymer distributor of the die was adjusted so that the first layer was a 0.9 μm layer made of a mixture of polymer A and silicon oxide particle master polymer, and the second layer was made of polymer A only.
4.6 μm layer, the third layer is melt-extruded in a composite state consisting of 4.5 μm layer consisting of a mixture of polymer A and polydivinylbenzene particle master, cooled by cooling drum at 35 ° C. A stretched film was obtained. This unstretched film is heated again to 135 ° C., stretched 6 times in the longitudinal direction and 5 times in the transverse direction, and heat treated at 215 ° C.
The first layer is a 0.03 μm layer made of a mixture of polymer A and silicon oxide particle master polymer, the second layer is a 6.82 μm layer made of only polymer A, and the third layer is a mixture of polymer A and polydivinylbenzene particle master. Consisting of 0.15 μm
A three-layer composite film having a total thickness of 7 μm was obtained.
【００３９】比較例３ 実施例３において、ポリマＡに替えてポリマＢを用いる
以外は実施例３と同様にして、第１層がポリマＢと酸化
ケイ素粒子マスタポリマの混合物からなる０．０３μｍ
の層、第２層がポリマＢのみからなる６．８２μｍの
層、第３層がポリマＢとポリジビニルベンゼン粒子マス
タの混合物からなる０．１５μｍの層からなり、全厚み
が７μｍの３層複合フィルムを得た。Comparative Example 3 In the same manner as in Example 3 except that the polymer B was used in place of the polymer A, the first layer was 0.03 μm in which the first layer was a mixture of the polymer B and the silicon oxide particle master polymer.
Layer, the second layer is a 6.82 μm layer consisting only of polymer B, the third layer is a 0.15 μm layer consisting of a mixture of polymer B and polydivinylbenzene particle master, and the total thickness is 7 μm. I got a film.
【００４０】上記で得られた二軸延伸フィルムの性質を
測定し、結果を表１に示す。The properties of the biaxially stretched film obtained above were measured, and the results are shown in Table 1.
【００４１】[0041]
【表１】 表１に示す通り、ビス（ヒドロキシエチル）ナフタレー
トを連続的に重縮合して得たポリエチレンナフタレート
を用いたフィルムは、表面に粗大突起や筋状欠点がほと
んど無く、さらに厚み斑が著しく少なく良好な特性を有
している。これに対し、従来の回分式重縮合方法で得た
ポリエチレンナフタレートを用いたフィルムは、上記の
各特性で劣っている。[Table 1] As shown in Table 1, the film using polyethylene naphthalate obtained by continuously polycondensing bis (hydroxyethyl) naphthalate has almost no coarse projections or streak-like defects on the surface, and furthermore, thickness unevenness is significantly small and good. It has various characteristics. On the other hand, the film using polyethylene naphthalate obtained by the conventional batch polycondensation method is inferior in each of the above properties.
【００４２】[0042]
【発明の効果】本発明の方法で得たポリエチレンナフタ
レートフィルムは、表面に粗大突起や筋状欠点がほとん
ど無く、さらに厚み斑が著しく少なく良好な特性を有し
ているので、表面欠点や厚み斑によって性能に著しく影
響を受ける磁気記録媒体、フィルムコンデンサー、電気
絶縁、感光剤またはさらに磁気記録層を塗布した写真用
フィルム、製版などの材料として好適であり、これらの
性能向上に寄与する。EFFECT OF THE INVENTION The polyethylene naphthalate film obtained by the method of the present invention has few rough projections and streak-like defects on the surface and further has good characteristics with few thickness irregularities. It is suitable as a material for magnetic recording media, film capacitors, electrical insulation, photosensitizers or photographic films coated with a magnetic recording layer, plate making, etc., whose performance is significantly affected by unevenness, and contributes to the improvement of these properties.
Claims (3)
連続的に重縮合して得たポリエチレンナフタレートを用
いる（ことを特徴とする）、ポリエチレンナフタレート
フィルムの製造方法。1. A method for producing a polyethylene naphthalate film, which comprises (is characterized in) using polyethylene naphthalate obtained by continuously polycondensing bis (hydroxyethyl) naphthalate.
連続的に重縮合して得たポリエチレンナフタレートを用
いる（ことを特徴とする）、表面突起の平均高さが５〜
４００ｎｍであるポリエチレンナフタレートフィルムの
製造方法。2. A polyethylene naphthalate obtained by continuously polycondensing bis (hydroxyethyl) naphthalate is used (characterized in that), and the average height of surface protrusions is 5 to 5.
A method for producing a polyethylene naphthalate film having a thickness of 400 nm.
連続的に重縮合して得たポリエチレンナフタレートを用
いる（ことを特徴とする）、カルボキシル末端基数が５
〜４５当量／１０6 ｇである請求項１または請求項２に
記載のポリエチレンナフタレートフィルムの製造方法。3. A polyethylene naphthalate obtained by continuously polycondensing bis (hydroxyethyl) naphthalate is used (characterized in that), and has 5 carboxyl end groups.
It is-45 equivalent / 10 < 6 > g, The manufacturing method of the polyethylene naphthalate film of Claim 1 or Claim 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3043294A JP3291891B2 (en) | 1994-02-28 | 1994-02-28 | Method for producing polyethylene naphthalate film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3043294A JP3291891B2 (en) | 1994-02-28 | 1994-02-28 | Method for producing polyethylene naphthalate film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07238152A true JPH07238152A (en) | 1995-09-12 |
| JP3291891B2 JP3291891B2 (en) | 2002-06-17 |
Family
ID=12303791
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3043294A Expired - Fee Related JP3291891B2 (en) | 1994-02-28 | 1994-02-28 | Method for producing polyethylene naphthalate film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3291891B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09302113A (en) * | 1996-05-16 | 1997-11-25 | Toray Ind Inc | Biaxially oriented polyester film for molding container |
| KR20040017023A (en) * | 2002-08-20 | 2004-02-26 | 에스케이씨 주식회사 | Biaxially oriented polyethylenenaphthalate film for an electric insulation and method for the preparation thereof |
| KR100816414B1 (en) * | 2006-10-31 | 2008-03-25 | 에스케이씨 주식회사 | Biaxially oriented polyethylenenaphthalate film and the preparation thereof |
-
1994
- 1994-02-28 JP JP3043294A patent/JP3291891B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09302113A (en) * | 1996-05-16 | 1997-11-25 | Toray Ind Inc | Biaxially oriented polyester film for molding container |
| KR20040017023A (en) * | 2002-08-20 | 2004-02-26 | 에스케이씨 주식회사 | Biaxially oriented polyethylenenaphthalate film for an electric insulation and method for the preparation thereof |
| KR100816414B1 (en) * | 2006-10-31 | 2008-03-25 | 에스케이씨 주식회사 | Biaxially oriented polyethylenenaphthalate film and the preparation thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3291891B2 (en) | 2002-06-17 |
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