JPS6098524A - Polyester film for magnetic tape - Google Patents
Polyester film for magnetic tapeInfo
- Publication number
- JPS6098524A JPS6098524A JP20725683A JP20725683A JPS6098524A JP S6098524 A JPS6098524 A JP S6098524A JP 20725683 A JP20725683 A JP 20725683A JP 20725683 A JP20725683 A JP 20725683A JP S6098524 A JPS6098524 A JP S6098524A
- Authority
- JP
- Japan
- Prior art keywords
- film
- particles
- polyester
- shrinkage rate
- magnetic tape
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Magnetic Record Carriers (AREA)
Abstract
Description
【発明の詳細な説明】
本発明はオーディオ磁気テープ用ポリエステルフィルム
に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyester film for audio magnetic tape.
更に詳しくはフィルム製造時の巻き特性に優れ、且つ磁
気テープとした時の走行性および電磁気特性に優れた二
軸延伸ポリエステルフィルムに関する。More specifically, the present invention relates to a biaxially oriented polyester film that has excellent winding properties during film production and excellent running properties and electromagnetic properties when made into a magnetic tape.
現在、磁気テープのペース材料としては、機械的特性、
熱的特性および価格等の諸点からポリエステルフィルム
が広く用いられている。Currently, magnetic tape paste materials have mechanical properties,
Polyester films are widely used due to their thermal properties and cost.
磁気テープ分野の中では、近年ビデオテープ用途におけ
る伸びが著しいが、一方オーディオテープ用途の需要も
着実に増加している。In the magnetic tape field, demand for videotape applications has been growing rapidly in recent years, while demand for audio tape applications has also been steadily increasing.
このオーディオテープも近年屋外における苛酷な東件下
、例えば高温多湿下で使用されるケースが増加している
が、かかる糸件下においてもその機能の低下を来たさな
いこと、即ち優れたテープ走行性や電磁気特性を維持す
ることが熱望されている。In recent years, this audio tape has been increasingly used outdoors under harsh conditions, such as high temperature and humidity, but it is an excellent tape that does not deteriorate in its functionality even under such conditions. There is a strong desire to maintain running performance and electromagnetic properties.
即ち、通常高温においてはテープの変形が著しく々るた
め、走行性自体が不安定になるばかりでなく、記録信号
の歪み即ちいわゆるワウフラッタ−現象が起り易くなる
。That is, at high temperatures, the tape usually deforms significantly, which not only makes the running performance unstable, but also tends to cause distortion of the recording signal, that is, the so-called wow and flutter phenomenon.
走行性を改良するためには一般にポリエステルに対し不
活性な微粒子全添加しフィルム表面を粗面化すればよい
ことが知られているが、オーディオテープはビデオテー
プに比ベテープの送シ速度が速いこと、また固定ヘッド
を用いていること等の理由から特に優れた走行性が要求
される。一方電磁変換特性全良好に保つためにはテープ
表面はなるべく平滑であることが好ましく、両者を同時
に満足することは困難である。It is generally known that in order to improve running properties, it is sufficient to roughen the film surface by adding all inert fine particles to polyester, but audio tape has a faster tape feeding speed than video tape. In addition, because a fixed head is used, particularly excellent running performance is required. On the other hand, in order to maintain good electromagnetic conversion characteristics, it is preferable that the tape surface be as smooth as possible, but it is difficult to satisfy both requirements at the same time.
ところで、かかる磁気テープのベースフィルムであるポ
リエステルフィルムは原料ポリエステルを溶融押出して
/−ト化した後、縦、横二軸方向に延伸しロール状に巻
き取る工程により製造されるが、この場合フィルム表面
が平滑であるとしばしば巻き取り工程でトラブルが発生
する。例えばロールの端面が不揃いとなったり、表面あ
るいは内部にしわやキズが発生しタシする。By the way, polyester film, which is the base film of such magnetic tapes, is manufactured by a process of melt-extruding raw polyester, converting it into a sheet, stretching it biaxially and horizontally, and winding it into a roll. Smooth surfaces often cause problems during the winding process. For example, the end face of the roll may become uneven, or wrinkles or scratches may occur on the surface or inside.
本発明者らは、かかる実情に鑑み、フィルム製造時の巻
き特性に優れ、且つオーディオテープとした時苛酷な使
用条件にもかかわらず、電磁気的な特性を損ねることな
くしかも走行性に優れたポリエステルフィルムについて
検討した結果、ある特定の粒子を含有し、且つ表面粗度
および収縮率がある特定の条件を満すフィルムの場合に
初めてこれらの特性が茜度に達成されること全知得し本
発明を完成するに至った。In view of these circumstances, the present inventors have developed a polyester that has excellent winding properties during film production, does not impair electromagnetic properties and has excellent running properties when used as an audio tape despite harsh usage conditions. As a result of studying the film, it was discovered that these characteristics can only be achieved with a degree of madness when the film contains certain particles and satisfies certain conditions for surface roughness and shrinkage rate. I was able to complete it.
即ち、本発明は、平均粒径0./〜Sμの粒子を0,1
〜7重量%含有してなるポリエステルフィルムであって
、フィルム表面の多重干渉法によるn次の干渉縞の個数
Hn(個/−)、平均線中心粗さRα(μ)、iih′
cで60分間保持した時の熱収縮率α(%)およびフィ
ルムの縦方向のF−を値(Ky / ml )が下記式
(1) 〜t6) ’に同時に満足すること全特徴とす
るオーディオ磁気テープ用ホIJ−Zステルフィルム
に存する。That is, in the present invention, the average particle size is 0. /~Sμ particles 0,1
A polyester film containing ~7% by weight, the number of n-th interference fringes on the film surface measured by multiple interference method Hn (pieces/-), the average line center roughness Rα (μ), iih'
Audio having all the characteristics that the heat shrinkage rate α (%) and F- value (Ky / ml) in the longitudinal direction of the film when held at c for 60 minutes simultaneously satisfy the following formula (1) ~ t6) ' Ho IJ-Z stell film for magnetic tape
exists in
100≦H2≦500 ・・・・・・・・・・・・・・
・(1)!≦H8≦100 ・・・・・・・・・・・・
・・・(2)H4≦30 ・・・・・・・・・・・・・
・・(3)0.0+2k ≦Ra ≦θ、Og ・・・
・・・・・・・・・・・・(すα≦八へ ・・・・・・
・・・・・・・・・(5)F−5≧lユ ・・・・・・
・・・・・・・・・(6)本発明におけるポリエステル
フィルムは、ポリエチレンテレフタレートヲ主体とする
ポリマー、例えばポリエチレンテレフタレートホモポリ
マー、エチレンテレフタレート単位が少くともざOモル
係以上であるコポリマー、ブロックコポリマー等を溶融
フィルム化し、延伸して得られるものが好ましいが、本
発明の特徴の一つはそのポリエステル中の不活性物質粒
子にある。100≦H2≦500 ・・・・・・・・・・・・・・・
・(1)! ≦H8≦100 ・・・・・・・・・・・・
・・・(2) H4≦30 ・・・・・・・・・・・・・・・
... (3) 0.0+2k ≦Ra ≦θ, Og ...
・・・・・・・・・・・・(to α≦8 ・・・・・・
・・・・・・・・・(5) F-5≧lyu ・・・・・・
(6) The polyester film in the present invention is a polymer mainly composed of polyethylene terephthalate, such as a polyethylene terephthalate homopolymer, a copolymer or a block copolymer containing at least 0 moles of ethylene terephthalate units. It is preferable to melt the polyester into a film and stretch it, but one of the features of the present invention lies in the inert material particles in the polyester.
即ち、よく知られているように、ポリエステルフィルム
の走行性を改良するためにはフィルム中にポリエステル
に対して不活性な微粒子を存在させれば良いが、本発明
者らは本発明で必要なフィルム表面粗度を得るためには
、かかる粒子を平均粒径が0./〜5μ、月つポリエス
テルに対する含有量が0./〜/ M 社%の範囲から
選択すれば良いことを知得した。That is, as is well known, in order to improve the runnability of a polyester film, it is sufficient to include fine particles inactive to polyester in the film, but the present inventors have developed In order to obtain the film surface roughness, such particles have an average particle size of 0. /~5μ, the content relative to the polyester is 0. I learned that it is sufficient to select from the range of /~/ Company M%.
この場合、より好捷しくに、かかる粒子が異なる性質含
有する。2種類の粒子群から構成されていることが望ま
しい。In this case, more preferably such particles contain different properties. It is desirable that the particle group is composed of two types of particle groups.
即ち、本発明において;まポリエステ、へ製造工程中で
析出せしめた粒子、いわゆる析出粒子と、ポリエステル
製造工程に外部から添加した粒子、いわゆる添加粒子の
2種類の粒子を併用する場合に最もその効果が奏せられ
る。That is, in the present invention, the effect is most effective when two types of particles are used together: particles precipitated during the polyester manufacturing process, so-called precipitated particles, and particles added externally to the polyester manufacturing process, so-called additive particles. is played.
即ち、析出粒子は一般にポリエステルとの頴1剥離する
ことはほとんどなく、かかる摩耗粉が原因上なるフィル
ム面上の粗大)【物や磁性層の塗布抜は効Vま生成し難
い。しかしながら相当粒子のみてはオーディオ用途にお
いてはしH゛シげ所望の表面粗度に1で到遠しイ1すな
(ろことがある。That is, the precipitated particles generally rarely separate from the polyester, and it is difficult to form coarse particles on the film surface caused by such abrasion particles. However, when considering only the corresponding particles, it may be difficult to achieve the desired surface roughness for audio applications.
仮に析出粒子量を増し例えば平均線中心粗さを望みの値
に調節したとしても、との場合性々にして粒子相互の凝
集による極めて粗大な突起、例えば多重干渉法で測定し
た時り次の干渉縞全 て市与える突起が存在し磁気テー
プ止した時記録信 ホ1゜号の欠落、即ちドロップアウ
トを引き起してし 粒ヨまう。 用し
一方、添加粒子は一般にポリエステルとの親 あ2和性
に欠けるためフィルムの摩擦、摩耗にょる し粒子の脱
落が生じ易いが、粒径、添加量を任意 0・/iCi
:y ) o−ルすることができるため、フィル ボリ
ム表面粗度の調節が容易であり、また滑シ性に Mfj
優れるという特徴を有する。 0・/
?ニーhら、2種類の粒子の両者を併せ用いるなら i
84は各々の欠点が大幅に改良されそれぞれの長所 の
学が充分生かされる。 平角
本発明においては析出粒子と添加粒子とを併 kN用す
る場合には、両者の使用割合f /7.20〜 るこ、
20// (粒子の重量比)、好ましくはi/7o〜
化し10// 、更に好ましくは//S; −!//の
範囲から に力選択するのが良い。 力
勿論、所望の走行性や表面粗度を満たすこと リ、iが
できればポリエステルフィルム中の粒子とし び/1出
粒子のみを用いることもできるし、またエステルに対す
る親和性の改良された添加−1例えば表面処理等金施し
た添加粒子lをする場合には該添加粒子のみで足シる場
合も・ずれにしてもこれらの粒子の平均粒径は〜左μで
なければならない。i fcこれらのエステルに対する
含有量の総和は0.7〜/チの範囲内から選択される。Even if the amount of precipitated particles is increased and, for example, the average line center roughness is adjusted to a desired value, in some cases extremely coarse protrusions due to mutual agglomeration of particles, such as the following when measured by multiple interference method, may occur. There are protrusions that give rise to interference fringes, and when magnetic tape is attached, they cause dropouts, or dropouts, in the recorded signal. On the other hand, since additive particles generally lack affinity with polyester, they tend to fall off due to friction and abrasion of the film, but the particle size and amount added can be adjusted as desired.
:y) Since it can be o-rolled, it is easy to adjust the fill volume surface roughness, and it also improves lubricity.
It has the characteristics of being excellent. 0/? Nih et al., if both types of particles are used together, i
In the 84, each of its shortcomings has been greatly improved and the strengths of each have been fully utilized. Rectangular In the present invention, when both precipitated particles and additive particles are used, the ratio of both used is f/7.20~ruko,
20// (weight ratio of particles), preferably i/7o~
10//, more preferably //S; -! It is better to select a force from the range of //. Of course, if it is possible to satisfy the desired runnability and surface roughness, it is also possible to use only the particles in the polyester film and the grains/single particles, or addition of particles with improved affinity for esters. For example, in the case of using additive particles 1 which have been subjected to surface treatment or the like, the average particle size of these particles must be ~μ on the left, whether or not the additive particles alone are sufficient. i fc The total content of these esters is selected within the range of 0.7 to 1/h.
平均粒径がμ未満あるいは含有量がo、i重fI:%未
満のにはフィルム表面が平滑に過ぎ、フィルムき特性や
走行性が悪化してしまうし、また粒径がSμを越えたり
、含有量が7重童剣、える場合にはこれらの特性は更に
改良されとはないばかシか、逆に電63i変換特性が悪
た9ドロツプアウトが増加したりするようる。If the average particle size is less than μ or the content is less than o, i weight fI:%, the film surface will be too smooth and the film properties and runnability will deteriorate, and if the particle size exceeds Sμ, If the content is higher than 7, these characteristics will not be improved further, or conversely, the 9 dropout, which has poor electric 63i conversion characteristics, will increase.
お、本発明でいう析出粒子とは、一般にボスチル製造工
程中でカルシウム化合物お上またはリチウム化合物と燐
化合物との反応により生成した粒子を指すが、具体的に
は例え コば次のような方法によって得ることができる
。The precipitated particles in the present invention generally refer to particles generated by the reaction between a calcium compound or a lithium compound and a phosphorus compound during the production process of Bostyl, but specifically, the following method is used: can be obtained by
■ カルシウム化合物あるいはリチウム化合 ム物の7
種以上を用いであるいは用いずして をエステル化また
はエステル交換反応を行な たい、反応終了後必要に応
じて更に上記金属 特化合物と回復または異種の金属化
合物を添 訓諭する。 散
■ 重縮合反応開始前の任意の時点におい−C性燐化合
物を添加する。■ Calcium or lithium compounds 7
The esterification or transesterification reaction is carried out with or without the use of more than one species, and after the reaction is completed, the above-mentioned metal compound is further recovered or added with a different metal compound as necessary. ③ Add the -C phosphorus compound at any time before the start of the polycondensation reaction.
燐化合物としでは上記金属化合物と反応して 反その一
部または全部をポリエステルとの親和性 好に優れた燐
酸塩または亜燐酸塩の誘導体に転化できるものならば如
何なる化合物でも良いが、 ム特に燐酸、燐酸のトリア
ルキルエステル、燐酸 後の部分アルキルエステル、亜
燐酸、亜@酸のト スリアルキルエステル、亜燐酸の部
分アルキルエ まステルの7種以上が好ましく用いられ
る。 ルこれら燐化合物の添加力1は該金属化合物の合
ム・倍当量用いられる。The phosphorus compound may be any compound as long as it reacts with the above metal compound and converts part or all of it into a phosphate or phosphite derivative having excellent affinity with polyester, but especially phosphoric acid. Seven or more of the following are preferably used: , trialkyl ester of phosphoric acid, partial alkyl ester after phosphorous acid, trialkyl ester of phosphorous acid, trisulfurous acid, and partial alkyl ester of phosphorous acid. The addition power of these phosphorus compounds is equivalent to the total amount of the metal compound.
以上のようにカルシウム化合物t 7jはリチウム合物
あるいはその双方全使用し、燐化合物併用することによ
シ、本発明で用いるに適し析出粒子を得ることができる
が、その中でもにカルシウム化合物と3佃1の燐化合物
及びSの燐化合物とから得られる析(f3粒子が/Lr
に分注に優れ、粗大粒子が少く、また保れた易滑を有す
ることから好適である。As described above, precipitated particles suitable for use in the present invention can be obtained by using a lithium compound or both together with a phosphorus compound for the calcium compound t7j. The analysis obtained from the phosphorus compound of Tsukuda 1 and the phosphorus compound of S (if the f3 particles are /Lr
It is suitable because it is excellent in dispensing, has few coarse particles, and maintains easy slippage.
このカルシウム化合物と複数の燐化合物との芯による析
出粒子全台むポリエステルの特にましい製造法の具体例
を以下に示す。A specific example of a particularly preferred method for producing a polyester in which all the precipitated particles are based on a core of a calcium compound and a plurality of phosphorus compounds will be shown below.
Jllち、まずエステル交換触媒としてカルシラ[ヒ合
物を用い、次いでエステル交換反応終了、反応系のカル
シウム化合物の総量がボリエ戸ル涼料全酸成分に対し0
..3〜1モル渠、好しくは0.3 A;〜0.6モル
φとなるようp)度力/ウム化合物を添加する。これら
のカルシウム化合物としては、反応系に可溶なカルシラ
ノ、カルボン酸のカルシウム塩、芳香族カルボン酸のカ
ルシウム塩、アルコラード等を挙げることができ、なか
でも酢酸カルシウムが好適である。First, Calcilla [Hymonide compound] was used as a transesterification catalyst, and then the transesterification reaction was completed, and the total amount of calcium compounds in the reaction system was 0 relative to the total acid component of the Bolibutol coolant.
.. .. Add the p) power/um compound to give 3 to 1 mole, preferably 0.3 A; ~0.6 mole φ. Examples of these calcium compounds include calcyrano, calcium salts of carboxylic acids, calcium salts of aromatic carboxylic acids, and alcolades that are soluble in the reaction system, with calcium acetate being particularly preferred.
次に、3価及びよ価の燐化合物からなる複数の燐化合物
ケ添加する。この場合使用される燐化合物としては、燐
酸、亜燐酸およびこれらのトリアルキルエステルまたは
部分アルキルエステルを挙げることができる。燐化合物
を添加した後、常法に従って重縮合反応全行なうことに
よシポリエステルを製造するが、この場合従来公知の重
縮合触媒5例えばアンチモン化合物、ゲルマニウム化合
物等を使用できる。Next, a plurality of phosphorus compounds consisting of trivalent and high valent phosphorus compounds are added. The phosphorus compounds used in this case include phosphoric acid, phosphorous acid, and trialkyl esters or partial alkyl esters thereof. After adding the phosphorus compound, a polyester is produced by carrying out a complete polycondensation reaction according to a conventional method. In this case, conventionally known polycondensation catalysts 5 such as antimony compounds and germanium compounds can be used.
本発明においてはこのようにして得られたポリエステル
との親和性に優れた析出粒子を用いるが、一方添加粒子
としては必要に応じて粉砕、分級処理を施した、カオリ
ン、炭酸カルシウム、シリカ、タルク、燐酸リチウム、
燐酸カルシウムおよびフッ化リチウム等の粒子を使用す
る。In the present invention, precipitated particles having excellent affinity with the polyester obtained in this way are used, but additive particles include kaolin, calcium carbonate, silica, talc, etc., which have been subjected to crushing and classification treatment as necessary. , lithium phosphate,
Particles such as calcium phosphate and lithium fluoride are used.
これらの粒子は通常ポリエステル製造工程中に添加され
るが、分散性さえ許されれば、生成ポリエステルに直接
ブレンドして使用することもできる。These particles are usually added during the polyester manufacturing process, but if dispersibility is permitted, they can also be used by directly blending them into the polyester produced.
本発明においては、このようにしである特定の平均粒径
を有する粒子を特定量含むポリエステルを原料として常
法により二軸延伸フィルムを得るが、この時得られるフ
ィルムの表面構造はある特定の条件を満足しなければな
らない。In the present invention, a biaxially stretched film is obtained by a conventional method using polyester containing a specific amount of particles having a specific average particle size as a raw material, but the surface structure of the film obtained at this time is determined under certain specific conditions. must be satisfied.
即ち、多重干渉法による2次の干渉縞の個数H2が10
0〜soo、好ましくはioo〜300(個1myり、
3次の干渉縞の個数H9が5〜100゜好ましくは10
〜10O(個/ md )、グ次の干渉縞の個数H4が
30(個/7π71)以下であって、且つ平均線中心粗
さRaが0.0.2 、t −0,θg(μ)好−まし
くけ0,0.7〜0.0 ? (μ)でなければならな
い。That is, the number H2 of secondary interference fringes by multiple interferometry is 10.
0~soo, preferably ioo~300 (pieces 1 my,
The number H9 of third-order interference fringes is 5 to 100°, preferably 10
~10O (pieces/md), the number H4 of G-order interference fringes is 30 (pieces/7π71) or less, and the average line center roughness Ra is 0.0.2, t -0, θg (μ) Preferably 0.0.7~0.0? Must be (μ).
H3が100未満の場合にはフィルムの摩擦係数が大き
く、磁性層塗布前後におけるフィルムの走行性が悪化す
るし、またこの値がSOOを越えるようになると電磁変
換特性、即ちシグナルとノイズとの比(S/N )が悪
化するようになる。If H3 is less than 100, the friction coefficient of the film will be large, and the running properties of the film before and after applying the magnetic layer will deteriorate, and if this value exceeds SOO, the electromagnetic conversion characteristics, that is, the ratio of signal to noise, will deteriorate. (S/N) becomes worse.
またHs が5未満であるとフィルムの耐摩耗性が劣シ
、フィルム同志あるいはフィルムと基材との摩耗により
しばしば白粉状物質が生成するようになる。一方H8が
/ 00f越えるようになると耐摩耗性は更に改良され
ない一方で逆にドロップアウトが多発する欠点が生じる
ようになる。この現象はH4か30を越えた場合に特に
顕著となる。If Hs is less than 5, the abrasion resistance of the film will be poor, and white powdery substances will often be produced due to abrasion between the films or between the film and the substrate. On the other hand, if H8 exceeds /00f, the abrasion resistance will not be further improved, but on the contrary, the drawback of frequent dropouts will occur. This phenomenon becomes particularly noticeable when the temperature exceeds H4 or 30.
Hnはフィルム表面粗度のうち各突起の高さに着目した
指標であシ本発明においては各々がある特定範囲内にな
ければならないが、更に本発明においてはフィルム表面
の凹凸の程度を示す平均線中心粗さRaがO1θコ3〜
θ、og(μ)の範囲になければならない。Hn is an index that focuses on the height of each protrusion in the film surface roughness, and in the present invention, each must be within a certain range, but in the present invention, Hn is an index that focuses on the height of each protrusion. Line center roughness Ra is O1θko3~
It must be in the range of θ, og(μ).
Raが0.0λ5未満であるとフィルム製造時ロール状
に高速度で巻き取る際ロール端面が不揃いになる等のト
ラブルが発生するし、また磁性層塗布前後の走行性が悪
化する。特に磁気テープを高温で使用する場合の走行性
が不安定となシ易い。一般にRaが大きいほど走行性は
改良されるがあまシVCRaが大きくなると例えば高域
出力、S/Nなどの電磁変換特性が悪化するのでこの値
は0.θgを越えないようにするのが良い。If Ra is less than 0.0λ5, troubles such as uneven roll end surfaces occur when the film is wound up into a roll at high speed during film production, and runnability before and after applying the magnetic layer deteriorates. In particular, when a magnetic tape is used at high temperatures, its running properties tend to be unstable. In general, the larger Ra is, the better the running performance is, but as VCRa becomes larger, electromagnetic conversion characteristics such as high-frequency output and S/N deteriorate, so this value should be 0. It is better not to exceed θg.
次に本発明のフィルムにおいては、//!;T::で1
0分間保持した時の熱収縮率αが7.3%以下であると
いう要件が同時に満たされてい々ければならない。Next, in the film of the present invention, //! ;T::1
At the same time, the requirement that the heat shrinkage rate α when held for 0 minutes must be 7.3% or less must be met.
オーディオテープの音響特性は磁気テープの伸縮の程度
にも左右されるのでこれを改良するためにはベースフィ
ルムの熱収縮率を小さくすることが好ましい。特に苛酷
な条件、例えばよ00以上の高温で使用される場合全想
定すればかかる熱収縮率αがへ3%以下であることが好
ましい。Since the acoustic characteristics of an audio tape depend on the degree of expansion and contraction of the magnetic tape, in order to improve this, it is preferable to reduce the heat shrinkage rate of the base film. In particular, when used under severe conditions, for example, at high temperatures of 0.000 C or higher, it is preferable that the thermal shrinkage rate α is 3% or less.
本発明において必要な熱収縮率を得るためには例えば次
のような方法を採用しうる。In order to obtain the necessary heat shrinkage rate in the present invention, for example, the following method can be adopted.
即ち、特にオーディオテープ用ベースフィルムとしては
、特に縦方向の熱収縮率が低いことが肝要であシ、この
ためには製膜工程中で通常よシ高い熱固定温度を与えた
p1実質的にフィルムに対し縦方向の弛緩処理を与える
際のフィルム温度は左O〜/!rOCが望ましく、二軸
延伸後フィルムがこの温度範囲にある間に、縦方向を無
張力txは低張力に維持することによって、所望の熱収
縮性を有するフィルムを得ることができる。That is, especially as a base film for audio tapes, it is important that the heat shrinkage rate is particularly low in the longitudinal direction. The film temperature when applying longitudinal relaxation treatment to the film is O~/! rOC is desirable, and by maintaining no tension tx in the longitudinal direction while the film is in this temperature range after biaxial stretching, a film having desired heat shrinkability can be obtained.
次に本発明フィルムの縦方向のF−j値、即ち!r%伸
長時の引張応力は/ 2 Kg / v+−以上、好ま
しくは/2.5〜.20に9/ynd、更に好ましくは
/コ、5〜1sKy/−である。長時間録音を達成する
ためには厚みの薄い高強度化フィルム、例えば縦方向の
F−,1−値が/ 、2 Kg / m4以上のフィル
ムが要求される。一般に縦方向のF−5値を大きくする
と熱収縮率も大きくなるため両者を所望の範囲内に保つ
ことは極めて難しいことであるが、本発明においては縦
方向の弛緩処理を行う等の方法を採用することニーよシ
これを達成する。Next, the F-j value in the longitudinal direction of the film of the present invention, ie! The tensile stress at r% elongation is /2 Kg/v+- or more, preferably /2.5~. 20 to 9/ynd, more preferably /, 5 to 1 sKy/-. In order to achieve long-term recording, a thin, high-strength film is required, for example, a film with a longitudinal F-,1-value of /2 Kg/m4 or more. Generally, as the F-5 value in the longitudinal direction increases, the thermal shrinkage rate also increases, so it is extremely difficult to maintain both within the desired range.However, in the present invention, methods such as longitudinal relaxation treatment are used. You can achieve this by recruiting.
以上詳述した如く、本発明はある特定の粒子を含有する
ポリエステルを原料として得られた、フィルムの表面粗
度、熱収縮率及び機械的強度がある特定の条件を潤すよ
うなオーディオテープ用ポリエステルフィルムに関する
ものであシ、その特徴は次に示す通シである。As detailed above, the present invention is a polyester for audio tapes that is obtained from a polyester containing specific particles and satisfies specific conditions for film surface roughness, heat shrinkage rate, and mechanical strength. It is related to film, and its characteristics are as follows.
■ フィルム表面には均一で微細な突起が数多く存在し
、優れた易滑性を与え、フィルム及び磁気テープとした
時安定した走行性を発揮しうる。(2) There are many uniform and fine protrusions on the surface of the film, which gives it excellent slipperiness and enables it to exhibit stable running properties when used as a film or magnetic tape.
■ また平均線中心粗さで表わされるフィルムの表面粗
度が特定範囲にあるときj!!!膜工程におけるロール
状への巻き取りが極めてスムースに進行する。■ Also, when the surface roughness of the film, expressed as the average line center roughness, is within a specific range, j! ! ! Winding into a roll in the membrane process proceeds extremely smoothly.
■ ベースフィルムの熱収縮率をある特定範囲とするこ
とによシ、オーディオテープ全苛酷な条件で使用したと
しても優れた音響特性を維持することができる。- By setting the heat shrinkage rate of the base film within a certain range, it is possible to maintain excellent acoustic properties even when the audio tape is used under severe conditions.
■ 更に、フィルムの縦方向の機械的な強度が強化され
ておシ、いわゆるバランスフィルムと異なシ、磁気テー
プの厚みを薄くすることが可能で長時間録音に適してい
る。■ Furthermore, the mechanical strength of the film in the vertical direction has been strengthened, making it possible to reduce the thickness of the magnetic tape and making it suitable for long-term recording, unlike so-called balanced films.
以下実施例及び比較例により本発明を更に詳細に説明す
るが、本発明はその要旨を越えない限シ以下の実施例に
限定されるものではない。The present invention will be explained in more detail with reference to Examples and Comparative Examples below, but the present invention is not limited to the following Examples unless the gist thereof is exceeded.
なお実施例および比較例中「部」とあるは「重量部」を
示す。また以下の実施例で用いた測定法を次に示す。In the Examples and Comparative Examples, "parts" indicate "parts by weight." Further, the measurement method used in the following examples is shown below.
(1)析出粒子量の測定;ポリエステル100?に0−
クロルフェノール/、07 fc加え/2θCで3時間
加熱した後、日立工機■製超遠心機&jP−7−を用い
30.00 Orpmでyo分間遠心分離を行ない得ら
れた粒子f100Cで真空乾燥する。該粒子を走査型差
動熱量計にて測定した時、ポリマーに相当する融解ピー
クが認められる場合には該粒子に0−クロルフェノール
を加熱冷却後再び遠心分離操作を行なう。融解ピークが
認められなくなった特販粒子を析出粒子とする。通常遠
心分離操作は2回で足りる。(1) Measurement of amount of precipitated particles; polyester 100? ni0-
After adding chlorphenol/, 07 fc and heating at 2θC for 3 hours, centrifugation was performed at 30.00 Orpm for yo minutes using a Hitachi Koki ultracentrifuge &jP-7-, and the resulting particles were vacuum dried with f100C. . When the particles are measured using a scanning differential calorimeter, if a melting peak corresponding to the polymer is observed, the particles are heated and cooled with 0-chlorophenol, and then centrifuged again. Specially sold particles whose melting peak is no longer observed are defined as precipitated particles. Normally, two centrifugation operations are sufficient.
(2)粒子の平均粒径の測定;顕微鏡法によった。(2) Measurement of average particle size of particles; by microscopy.
即ち粒子を含むポリエステル少量をカバーグラスにはさ
んで溶融急冷後、写真撮影後最大粒径を測定した。平均
粒径は最大径を直径とする球群の重量分布を算出するこ
とによシ重貴分率SO%の点の直径で表わされた粒径を
指す。That is, a small amount of polyester containing particles was sandwiched between cover glasses, melted and rapidly cooled, and a photograph was taken, after which the maximum particle size was measured. The average particle size refers to the particle size expressed by the diameter at the point where the precious fraction is SO% by calculating the weight distribution of a group of spheres with the maximum diameter as the diameter.
(3) 多重干渉法によるフィルム表面の突起個数の測
定;日本光学(イ)1サーフエイス・フィニツシユ−マ
イクロスコープを用いアルミニウム蒸着したフィルムに
ついて干渉縞を観察し一次、3次及びダ次の干渉縞の個
数を数え/ml当りの個数に換算する。用いタミラーの
反射率は65%であシ顕微鏡倍率Fi200倍であゝる
。1だ測定波長はO,S弘μである。(3) Measuring the number of protrusions on the film surface using multiple interference method; Nippon Kogaku (a) 1 Surf-Ace Finish Microscope was used to observe the interference fringes on the aluminum-deposited film, and the first-, third-, and second-order interference fringes were measured. Count the number of pieces/convert to number per ml. The reflectance of the mirror used was 65%, and the microscope magnification Fi was 200 times. 1. The measurement wavelength is O, S Hong μ.
(4)平均線中心粗さRa (μ)の測定; JISB
otθ/−/974記載の方法によった。測定は小板研
究所a者製解析装置(AY−一)付3次元粗さ測定器を
用いて行ない、カットオフは1↑
o、o g調、測定長iaS覇とした。(4) Measurement of average line center roughness Ra (μ); JISB
The method described in otθ/-/974 was used. The measurement was carried out using a three-dimensional roughness measuring device equipped with an analysis device (AY-1) manufactured by Koita Research Institute, and the cutoff was 1↑ o, o g, and the measurement length was iaS.
(5) フィルム巻き特性の評価;直径lりαの紙管に
ラインスピード約/り0m7分で製造されるフィルムを
tooom巻き取り、端面の状態を観察し、次の3ラン
クに分けた。 −A:端面が全て完全に揃っている。(5) Evaluation of film winding characteristics: A film produced at a line speed of about 0 m/7 minutes was wound around a paper tube with a diameter of 1/alpha, and the condition of the end surface was observed and divided into the following three ranks. -A: All end faces are completely aligned.
B:端面の一部が不揃いである。B: Part of the end face is irregular.
C:端面のかなりの部分が不揃いである。C: A considerable portion of the end face is irregular.
(6)磁気テープの製法;
紹 成 部(重量)
γ−Fe2O3100
ポリ(塩化ビニル−酢酸ビニル)共重合体 、23ニト
リルゴム 7
メチルエチルケトン 100
トルエン 100
上記組成物をボールミルで241時間混練した後、ポリ
イソシアネート化合物を5部加え、更に7時間分散処理
を行ない磁性塗料とし、これを乾燥厚3μとなるようフ
ィルムに塗布し、磁気配向させた後乾燥しオーディオ用
テープとした。(6) Manufacturing method for magnetic tape; Introduction Parts (weight) γ-Fe2O3 100 Poly(vinyl chloride-vinyl acetate) copolymer, 23 Nitrile rubber 7 Methyl ethyl ketone 100 Toluene 100 After kneading the above composition in a ball mill for 241 hours, Five parts of an isocyanate compound was added, and a dispersion treatment was further carried out for 7 hours to obtain a magnetic paint. This was coated on a film to a dry thickness of 3 μm, and after magnetic orientation, it was dried to obtain an audio tape.
(7)走行性;磁気テープの走向安定性の尺度として反
磁性層面の静摩擦係数全ASTM D/g9’l−4,
7の方法により測定した。(7) Running properties: As a measure of the running stability of the magnetic tape, the static friction coefficient of the diamagnetic layer surface total ASTM D/g9'l-4,
Measured by method No. 7.
但し測定時の温湿度を各々yoC160%RHとした。However, the temperature and humidity at the time of measurement were yoC160%RH.
(8)耐摩耗性
長さ777m1幅3.75−の磁気テープを巻取機にか
け、−qm1分の速度で繰り返し走行させ中間に設置し
たA mmφの硬質クロム固定ピンに付着した摩耗量を
目視評価し次に示すランクに分けた。(8) Wear resistance A magnetic tape with a length of 777 m and a width of 3.75 mm was placed on a winder and repeatedly run at a speed of -q m 1 minute, and the amount of wear attached to a hard chrome fixing pin of A mmφ installed in the middle was visually observed. It was evaluated and divided into the following ranks.
ランクA:全く付着しない。Rank A: No adhesion at all.
ランクB:若干付着するが実用上支障はない。Rank B: Slight adhesion, but no practical problem.
ランクC:付着量が多く実用上支障がち第(6)項の方
法で製造したオーディオテープに10キロヘルツで録音
を行ない、t/!;Cで10分間熱処理を施した後再生
音の周波数変化を測定した。Rank C: Recording is performed at 10 kilohertz on an audio tape manufactured by the method in item (6), which tends to have a large amount of adhesion and poses a practical problem, and t/! After heat treatment at C for 10 minutes, the frequency change of the reproduced sound was measured.
OQ 熱収縮率の測定
長さ1ooo調、幅、20rranのフィルムを無荷重
で/75C%60分間エアーオーブン中で熱処理したの
ち熱収縮率を測定した。OQ Measurement of Heat Shrinkage A film with a length of 100mm and a width of 20rran was heat treated in an air oven at 75C% for 60 minutes without any load, and then the heat shrinkage was measured.
(ロ) F−5値の測定
東洋ボールドウィン■社製テンシロンUTM−m型を用
い室温で測定した。F−1値は3チ伸長時に加えられた
力を、フィルムの単位断面積尚シに加えられた力(Ic
g7vrl)で表わしたものである。(b) Measurement of F-5 value Measurement was carried out at room temperature using Tensilon UTM-m model manufactured by Toyo Baldwin. The F-1 value is calculated by calculating the force applied during 3-inch elongation by the force applied to the unit cross-sectional area of the film (Ic
g7vrl).
実施例/
(ポリエステルの製造)
ジメチルテレフタシー8フ00部、エチレングリコール
6S部及び酢酸カルシウム−水塩o、o y部(ジメチ
ルテレフタレートに対し0,1モル%)をエステル交換
反応槽に取シ、反応開始後弘時間かけてコλ0Cに到達
させ、実質的にエステル交換反応を終了させた。Example/ (Manufacture of polyester) 800 parts of dimethyl terephthalate, 6S parts of ethylene glycol, and o, oy parts of calcium acetate hydrate (0.1 mol % based on dimethyl terephthalate) were placed in a transesterification reaction tank. After the start of the reaction, a temperature of λ0C was reached over a period of time, and the transesterification reaction was substantially completed.
次に酢酸カルシウム−水塩0..27部(0,3モル%
)及ヒドリエチルホスフェ−) 0.J 0部を添加し
1後、10分後にトリエチルホスファイ) 0.07部
(カルシウム化合物の合計量に対する燐化合物の合計量
は1.0倍当量)全添加し、更に三酸化アンチモンO,
OS部を加え常法に従って重合を行なった。7時間後反
応を停止し固有粘度O2乙グのポリエステル(A)を得
た。Next, calcium acetate-hydrate salt 0. .. 27 parts (0.3 mol%
) and hydrethylphosphate) 0. 0 parts of J was added, and 10 minutes later, 0.07 parts of triethylphosphite (total amount of phosphorus compounds relative to the total amount of calcium compounds is 1.0 times equivalent) was added, and further antimony trioxide O,
The OS portion was added and polymerization was carried out according to a conventional method. After 7 hours, the reaction was stopped and a polyester (A) having an intrinsic viscosity of O2 was obtained.
該ポリエステル中には平均粒径約/μの析出粒子が認め
られ、その量はポリエステルに対しo3M量チであった
。In the polyester, precipitated particles with an average particle diameter of about /μ were observed, and the amount of precipitated particles was about 03M based on the polyester.
一方、ポリエステ、−(A)の製造においてエステル交
換反応終了後、酢酸カルシウム−水塩及び2種類の燐化
合物を添加する代シに、平均粒径/、!rμの炭酸カル
シウムo3部、及び燐酸θ、o4を部を添加する他はポ
リエステル(A)の製造と同様にして添加粒子を含むポ
リエステル(B)を得た。On the other hand, in the production of polyester (A), after the transesterification reaction is completed, calcium acetate hydrate and two types of phosphorus compounds are added to the average particle size /,! Polyester (B) containing additive particles was obtained in the same manner as in the production of polyester (A), except that 3 parts of rμ of calcium carbonate and 4 parts of phosphoric acid θ and o were added.
(ポリエステルフィルムの製造)
ポリエステル(蜀とポリエステル(B)と全り/3(重
量比)にブレンドし2?0Cで押出機よりシート状に押
出し未延伸シートを得た。次いで縦方向にg夕Cで79
.2倍、横方向に9!r’Cで3.7倍延伸し、−一3
Cで3秒間熱固定を行なった。(Manufacture of polyester film) Polyester (Shu) and polyester (B) were blended at a total weight ratio of 3/3 (weight ratio) and extruded into a sheet form from an extruder at 2-0C to obtain an unstretched sheet. 79 in C
.. 2x horizontally 9! Stretched 3.7 times at r'C, -13
Heat fixation was performed at C for 3 seconds.
この場合熱固定の前の昇温過程と熱固定の後の室温まで
の冷却過程で、極力フィルムを低張力に保ち、実施例1
に該当するポリエステルフィルムft得た。In this case, the tension of the film was kept as low as possible during the temperature raising process before heat setting and the cooling process to room temperature after heat setting.
A polyester film ft corresponding to the above was obtained.
該フィルムの多重干渉法による表面突起の個数、平均線
中心粗さ、熱収縮率及び機械的強度の測定結果を第1表
に示す。Table 1 shows the results of measuring the number of surface protrusions, average line center roughness, thermal shrinkage rate, and mechanical strength of the film by multiple interference method.
なおフィルムの巻き取シ工程における観察結果も合わせ
て第1表に示す。Table 1 also shows the observation results during the film winding process.
(オーディオテープとしての評価)
このようにして得られたフィルムに(6)の方法で磁性
層′fr、塗布、乾燥後、y、tsmm幅にスリットし
てテープ化した。該テープの走行性、耐摩耗性及び録音
−再生時の周波数変化を第1表に示す。(Evaluation as an audio tape) A magnetic layer 'fr was coated on the film thus obtained by the method (6), and after drying, it was slit into a tape having a width of y, ts mm. Table 1 shows the running properties, abrasion resistance, and frequency changes during recording and reproduction of the tape.
比較例/
実施例1のポリエステルフィルムの製造において、ポリ
エステル(A)のみ’lci料として用いる他は実施例
/と同様にしてポリエステルフィルム全製造し、更に磁
気テープを得た。Comparative Example: In the production of the polyester film of Example 1, a polyester film was entirely produced in the same manner as in Example, except that only polyester (A) was used as the lci material, and a magnetic tape was also obtained.
これらの特性を第1表に示す。These properties are shown in Table 1.
比較例コ
11[例/のポリエステルフィルム
いて、ポリエステル(B)のみを原料として用いる他は
実施例/と同様にしてポリエステルフィルムを製造し、
更に磁気テープを得た。これらの特性を第1表に示す。Comparative Example 11 A polyester film was produced in the same manner as in Example, except that only polyester (B) was used as a raw material.
Furthermore, magnetic tape was obtained. These properties are shown in Table 1.
比較例3
笑m?+lzのポリエステルフィルムの熱収縮率を/.
ぶーとした。即ち実施例1と同様にして未延伸フィルム
を得、次いで縦方向にgS′cで9.1倍、横方向に9
5υで3.3倍延伸し、277Cで3秒間熱固定全行な
い比較例3のポリエステルフィルム金得た。Comparative example 3 lol? The heat shrinkage rate of the polyester film of +lz is /.
It was blurry. That is, an unstretched film was obtained in the same manner as in Example 1, and then gS'c was increased by 9.1 times in the machine direction and 9 times in the transverse direction.
The polyester film of Comparative Example 3 was obtained by stretching 3.3 times at 5υ and heat-setting at 277C for 3 seconds.
実施例コ
実施例1のポリエステル(蜀の製造において、エステル
交換反応終了後酢酸カル7ウムー水塩の代シに酢酸リチ
ウムニ水塩0./左部を,また二種類の燐化合物の代り
にトリメチルホスフェ− ) 0,/り部(カルシウム
化合物及びリチウム化合物の合計量に対し/.θ倍尚量
)を添加する他は実施例/と同様にして重合を行ないポ
リエステル(C)を得た。Example 1 In the production of the polyester of Example 1 (Shu), after the transesterification reaction was completed, lithium acetate dihydrate was added in place of calcium acetate hydrate, and trimethyl was added in place of the two types of phosphorus compounds. Polyester (C) was obtained by polymerization in the same manner as in Example 1, except that 0./part (/.θ times the amount of the total amount of the calcium compound and lithium compound) was added.
ポリエステル(C)中には平均粒径約/μの析出粒子が
認められ、その量はポリエステルに対しO.ダ重量%で
あった。In the polyester (C), precipitated particles with an average particle size of about /μ are observed, and the amount is O. % by weight.
次ニポリエステル(C)とポリエステル(B)とをX/
4t(重楚比)にブレンドし、実施例/と同様にして二
軸延伸フィルムを製造し、更に6′妖気テープを得た。Next, polyester (C) and polyester (B) are
A biaxially oriented film was produced in the same manner as in Example 1 by blending the mixture to 4t (heavy weight ratio), and a 6' Yoki tape was also obtained.
これらの特性全第1訟に示す。All of these characteristics are shown in the first case.
Claims (1)
含有してなるポリエステルフィルムであって、フィルム
表面の多重干渉法によるn次の干渉縞の個数Hn (個
/−)、平均線中心粗さRa、 (μ)、/ / &
?、″″cA O分間保持シタトキノ熱収縮率α(%)
およびフィルムの縦方向のF−3値(Kグ/−)が下記
式(1)〜(6)を同時に満足することを特徴とするオ
ーディオ磁気テープ用ポリエステルフィルム。 100≦馬≦soo ・・・・・曲・・曲(1)S≦H
8≦ioo ・・曲・1曲(2)H4≦30 ・・・・
・−・・・・曲(3)0.023≦Ra≦O1og・・
凹曲・曲(4)α≦/、3 ・・凹曲・凹(5) F−&≧/コ ・・・・・山・・・・・・・(6)(1) 0.7 to 1% by weight of particles with average particle diameters o, i to Sμ
A polyester film containing: the number of n-th interference fringes measured by multiple interference method on the film surface Hn (pieces/-), the average line center roughness Ra, (μ), / / &
? ,''cA O minute retention heat shrinkage rate α (%)
and a polyester film for an audio magnetic tape, characterized in that the longitudinal F-3 value (Kg/-) of the film simultaneously satisfies the following formulas (1) to (6). 100≦Horse≦soo...Song...Song (1) S≦H
8≦ioo...Song/1 song (2) H4≦30...
・-・・Song (3) 0.023≦Ra≦O1og・・
Concave curve/curve (4) α≦/, 3... Concave curve/concave (5) F-&≧/ko...Mountain......(6)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP20725683A JPS6098524A (en) | 1983-11-04 | 1983-11-04 | Polyester film for magnetic tape |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP20725683A JPS6098524A (en) | 1983-11-04 | 1983-11-04 | Polyester film for magnetic tape |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS6098524A true JPS6098524A (en) | 1985-06-01 |
Family
ID=16536782
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP20725683A Pending JPS6098524A (en) | 1983-11-04 | 1983-11-04 | Polyester film for magnetic tape |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6098524A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6381022A (en) * | 1986-09-25 | 1988-04-11 | Teijin Ltd | Biaxially oriented polyester film |
US6275350B1 (en) * | 1998-04-03 | 2001-08-14 | Hewlett-Packard Company | Magnetic head and method for compensating for magnetic tape dimensional instability |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS51115571A (en) * | 1975-04-04 | 1976-10-12 | Asahi Chemical Ind | Method of manufacturing polyester film |
JPS51146573A (en) * | 1975-06-10 | 1976-12-16 | Asahi Chemical Ind | Method of producing film excellent in dimensional stability |
JPS53106783A (en) * | 1977-03-01 | 1978-09-18 | Teijin Ltd | Polyester film with improved travelling property |
JPS5415978A (en) * | 1977-06-28 | 1979-02-06 | Teijin Ltd | Polyester film |
JPS5434207A (en) * | 1977-08-23 | 1979-03-13 | Teijin Ltd | Polyester film |
JPS5434206A (en) * | 1977-08-23 | 1979-03-13 | Teijin Ltd | Polyester film |
JPS5522915A (en) * | 1978-08-07 | 1980-02-19 | Toray Ind Inc | Manufacture of polyester film |
JPS563430A (en) * | 1979-06-20 | 1981-01-14 | Diafoil Co Ltd | Biaxially oriented polyester film for magnetic tape |
-
1983
- 1983-11-04 JP JP20725683A patent/JPS6098524A/en active Pending
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS51115571A (en) * | 1975-04-04 | 1976-10-12 | Asahi Chemical Ind | Method of manufacturing polyester film |
JPS51146573A (en) * | 1975-06-10 | 1976-12-16 | Asahi Chemical Ind | Method of producing film excellent in dimensional stability |
JPS53106783A (en) * | 1977-03-01 | 1978-09-18 | Teijin Ltd | Polyester film with improved travelling property |
JPS5415978A (en) * | 1977-06-28 | 1979-02-06 | Teijin Ltd | Polyester film |
JPS5434207A (en) * | 1977-08-23 | 1979-03-13 | Teijin Ltd | Polyester film |
JPS5434206A (en) * | 1977-08-23 | 1979-03-13 | Teijin Ltd | Polyester film |
JPS5522915A (en) * | 1978-08-07 | 1980-02-19 | Toray Ind Inc | Manufacture of polyester film |
JPS563430A (en) * | 1979-06-20 | 1981-01-14 | Diafoil Co Ltd | Biaxially oriented polyester film for magnetic tape |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6381022A (en) * | 1986-09-25 | 1988-04-11 | Teijin Ltd | Biaxially oriented polyester film |
JPH0455583B2 (en) * | 1986-09-25 | 1992-09-03 | Teijin Ltd | |
US6275350B1 (en) * | 1998-04-03 | 2001-08-14 | Hewlett-Packard Company | Magnetic head and method for compensating for magnetic tape dimensional instability |
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