JP2010250910A - Support for magnetic recording medium and data storage using the same - Google Patents
Support for magnetic recording medium and data storage using the same Download PDFInfo
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- JP2010250910A JP2010250910A JP2009101080A JP2009101080A JP2010250910A JP 2010250910 A JP2010250910 A JP 2010250910A JP 2009101080 A JP2009101080 A JP 2009101080A JP 2009101080 A JP2009101080 A JP 2009101080A JP 2010250910 A JP2010250910 A JP 2010250910A
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- magnetic
- recording medium
- magnetic recording
- support
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- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Magnetic Record Carriers (AREA)
Abstract
Description
本発明は、記憶容量が０．８ＴＢ以上であるデータストレージのベースフィルムに用いる磁気記録媒体用支持体に関する。 The present invention relates to a support for a magnetic recording medium used for a data storage base film having a storage capacity of 0.8 TB or more.
２軸配向ポリエステルフィルムを用いた磁気記録媒体用支持体は、デジタルビデオ用テープや、コンピュータのバックアップ用テープ（以後、データテープという）などに用いられている。近年、磁気テープ、特に高密度に磁気記録を行うデータテープにおいては、トラックが非常に小型化したことによって、テープ走行・保存時のわずかな熱的・力学的寸法変化や、データを記録する際と読み取る際の温湿度環境の違いが、データの再生不良を引き起こす問題点が生じてきた。従って、高密度記録に対応する磁気記録媒体には、温湿度環境変化や熱およびテープ張力などの応力に対して高い寸法安定性が要求される。リニア記録方式のデータテープにおいては、特にテープ幅方向の高い寸法安定性が必要となる。 Supports for magnetic recording media using a biaxially oriented polyester film are used for digital video tapes, computer backup tapes (hereinafter referred to as data tapes), and the like. In recent years, in magnetic tapes, especially data tapes that perform magnetic recording at high density, the track has become very small, which can cause slight thermal and mechanical dimensional changes during tape running and storage, and data recording. The difference in the temperature and humidity environment at the time of reading has caused a problem that causes poor data reproduction. Therefore, a magnetic recording medium compatible with high-density recording is required to have high dimensional stability against stresses such as changes in temperature and humidity environment and heat and tape tension. In a linear recording type data tape, high dimensional stability in the tape width direction is particularly required.
従来、磁気テープの素材としては、ポリエチレンテレフタレート（以下、ＰＥＴと称することがある。）とならんで、ポリエチレン−２，６−ナフタレンジカルボキシレート（以下、ＰＥＮと称することがある。）が用いられてきたが、高密度記録の磁気テープのベースフィルムに求められる寸法安定性の要求はますます厳しくなってきており、それだけでは不十分であった。そこで、上記の寸法安定性の要求に応え得るベースフィルムとして、ポリエステルフィルムに金属、半金属のなどの金属材料からなる強化膜を設けた磁気記録媒体用支持体やこの支持体を用いた磁気記録媒体が知られている（特許文献１および２）。 Conventionally, as a material for magnetic tape, polyethylene-2,6-naphthalenedicarboxylate (hereinafter sometimes referred to as PEN) is used in addition to polyethylene terephthalate (hereinafter sometimes referred to as PET). However, the requirements for dimensional stability required for the base film of magnetic tapes for high-density recording have become increasingly severe, and that alone has been insufficient. Therefore, as a base film that can meet the above dimensional stability requirements, a magnetic recording medium support in which a reinforcing film made of a metal material such as a metal or a semimetal is provided on a polyester film, or a magnetic recording using this support. Medium is known (Patent Documents 1 and 2).
また、特許文献３〜７には、粗大突起を低減するために触媒種を特定のものにしたり、フィルム中に含有させる粒子として粗大粒子の少ないものを用いること、およびそのような処理を行った粗大突起の少ないフィルムも提案されている。しかしながら、近年の高密度記録の要求はすさまじく、特に記録容量が１巻あたり１ＧＢを超えるようなデータストレージでは、前述の特許文献３〜７で粗大突起がないとされたフィルムを、前述の特許文献１および２の磁気記録媒体用支持体に用いても十分に応えられなくなってきた。 Further, in Patent Documents 3 to 7, a specific catalyst species is used to reduce coarse protrusions, or particles having few coarse particles are used as particles to be contained in the film, and such treatment is performed. A film with few coarse protrusions has also been proposed. However, the demand for high-density recording in recent years is tremendous. Especially in the data storage in which the recording capacity exceeds 1 GB per volume, the film which has no coarse protrusion in the above-mentioned Patent Documents 3 to 7 is used. Even if it is used as the support for magnetic recording media 1 and 2, it has not been able to respond sufficiently.
本発明の目的は、記憶容量が０．８ＴＢ以上であるデータストレージのベースフィルムに用いても優れた電磁変換特性を発現できるポリエステルフィルムを提供することにある。 An object of the present invention is to provide a polyester film that can exhibit excellent electromagnetic characteristics even when used as a base film for data storage having a storage capacity of 0.8 TB or more.
本発明者らは上記課題を解決しようと鋭意研究するにあたって、前述の特許文献３〜６では長径が１５μｍ以上の粗大突起しか見ておらず、他方前述の特許文献７では測定波長が５８０ｎｍであるため高さが２９０ｎｍ以上の粗大突起しか見ておらず、それらで確認することができていない微小な粗大突起が影響しているのではないかと考えた。そこで、まずどのような粗大突起が影響するのか検討したところ、粗大突起については長径よりも高さが影響し、高さ１３０ｎｍの粗大突起を８００個／１００ｃｍ２以下にしたとき、記憶容量が０．８ＴＢ以上であるデータストレージのベースフィルムに用いても優れた電磁変換特性を発現できることを見出し、本発明に到達した。 In order to solve the above-mentioned problems, the inventors of the present invention have only seen a coarse protrusion having a major axis of 15 μm or more in the above-mentioned Patent Documents 3 to 6, while the above-mentioned Patent Document 7 has a measurement wavelength of 580 nm. For this reason, only coarse protrusions having a height of 290 nm or more were seen, and it was thought that minute coarse protrusions that could not be confirmed by them had an influence. Therefore, first, what kind of coarse protrusions are affected is examined. As for the coarse protrusions, the height influences more than the major axis, and when the number of coarse protrusions having a height of 130 nm is 800 pieces / 100 cm 2 or less, the storage capacity is 0. The present inventors have found that excellent electromagnetic conversion characteristics can be exhibited even when used for a data storage base film of .8 TB or more, and have reached the present invention.
かくして本発明によれば、二軸配向ポリエステルフィルム層（Ｆ層）の少なくとも磁性層を形成する側の面に金属類または金属系無機化合物からなる層（Ｍ層）が設けられた磁気記録媒体用支持体であって、Ｆ層の磁性層を形成する側の表面は、波長２６０ｎｍの光の干渉によって測定される粗大突起の数が、８００個／１００ｃｍ２以下であること、Ｍ層の厚みが５〜１３０ｎｍの範囲にあること、そして、記憶容量が０．８ＴＢ以上であるデータストレージに用いる磁気記録媒体用支持体が提供される。 Thus, according to the present invention, for a magnetic recording medium, a layer (M layer) made of a metal or a metal-based inorganic compound is provided on at least the surface of the biaxially oriented polyester film layer (F layer) on which the magnetic layer is formed. The surface of the support on the side of forming the magnetic layer of the F layer has a number of coarse protrusions measured by interference of light having a wavelength of 260 nm of 800/100 cm 2 or less, and the thickness of the M layer is Provided is a support for a magnetic recording medium that is in the range of 5 to 130 nm and is used for data storage having a storage capacity of 0.8 TB or more.
また、本発明によれば、本発明の好ましい磁気記録媒体用支持体の態様として、Ｆ層のポリエステルがポリエチレンテレフタレートまたはポリエチレン−２，６−ナフタレンジカルボキシレートであること、Ｆ層の磁性層を形成する側の表面が、表面粗さ（ＲａＡ）１〜５ｎｍの範囲であること、Ｆ層の磁性層を形成しない側の表面が、表面粗さ（ＲａＢ）３〜１０ｎｍの範囲にあることの少なくともいずれか一つを具備する磁気記録媒体用支持体も提供される。 According to the present invention, as a preferred embodiment of the support for a magnetic recording medium of the present invention, the polyester of the F layer is polyethylene terephthalate or polyethylene-2,6-naphthalenedicarboxylate, and the magnetic layer of the F layer is The surface to be formed has a surface roughness (RaA) in the range of 1 to 5 nm, and the surface of the F layer on which the magnetic layer is not formed has a surface roughness (RaB) in the range of 3 to 10 nm. There is also provided a support for a magnetic recording medium comprising at least one of them.
さらにまた、本発明によれば、本発明の磁気記録媒体用支持体と、その一方の表面に形成された磁性層とからなる記憶容量が０．８ＴＢ以上であるデータストレージ、さらに磁性層が塗布によって形成され、記録方式がリニア記録方式であるデータストレージも提供される。 Furthermore, according to the present invention, a data storage comprising the support for a magnetic recording medium of the present invention and a magnetic layer formed on one surface thereof has a storage capacity of 0.8 TB or more, and further a magnetic layer is applied. A data storage is also provided which has a linear recording method.
本発明の磁気記録媒体用支持体を用いれば、記憶容量が０．８ＴＢ以上であるデータストレージのベースフィルムに用いたときにエラーとなる微小な粗大突起までも低減されていることから、寸法安定性だけでなく、電磁変換特性にも優れたデータストレージを提供することができる。 The use of the magnetic recording medium support of the present invention reduces the size of microscopic protrusions that cause errors when used in a data storage base film with a storage capacity of 0.8 TB or more. It is possible to provide data storage that is excellent in electromagnetic conversion characteristics as well as performance.
以下、本発明について、詳述する。
本発明の磁気記録媒体用支持体は、二軸配向ポリエステルフィルム層（Ｆ層）の少なくとも磁性層を形成する側の面に金属類または金属系無機化合物からなる層（Ｍ層）が設けられている。本発明の磁気記録媒体用支持体の特徴の一つは、Ｆ層の磁性層を形成する側の表面は、波長２６０ｎｍの光の干渉によって測定される粗大突起の数が、８００個／１００ｃｍ２以下ということにある。好ましい粗大突起数は６００個／１００ｃｍ２以下、さらに５００個／１００ｃｍ２以下である。このような小さな突起はこれまで問題とならなかったが、記憶容量が０．８ＴＢ以上であるデータストレージに用いると、このような小さな突起も問題となり、その問題を解消したのが本発明である。そのため、粗大突起数が上限を超えると、データストレージとしたときにエラーが多発してしまう。
Hereinafter, the present invention will be described in detail.
The support for a magnetic recording medium of the present invention has a biaxially oriented polyester film layer (F layer) provided with a layer (M layer) made of a metal or a metal-based inorganic compound on at least the surface on which the magnetic layer is formed. Yes. One of the features of the support for a magnetic recording medium of the present invention is that the surface of the F layer on the side where the magnetic layer is formed has a number of coarse protrusions measured by interference of light having a wavelength of 260 nm of 800/100 cm 2. It is in the following. A preferable number of coarse protrusions is 600/100 cm 2 or less, and further 500/100 cm 2 or less. Such a small protrusion has not been a problem until now, but when used for data storage with a storage capacity of 0.8 TB or more, such a small protrusion also becomes a problem, and the present invention has solved the problem. . Therefore, if the number of coarse protrusions exceeds the upper limit, errors occur frequently when data storage is used.
ところで、このような粗大突起は、特許文献７に記載された粗大突起の測定と基本的な測定原理は同じで、特徴は波長２６０ｎｍという非常に波長の短い光を用いたことにある。具体的には、フィルムを平坦な面に重ね合わせると、フィルムの表面に突起があることから両者の間に空間ができる。そして、そこに光を当てると、光の波長（λ：ｎｍ）に対して、λ／２になる間隔の部分は反射光が打ち消しあい、その結果、突起を中心に黒い点もしくは黒いリング状の模様が発現する。そのような観点から、理論的には、本発明における粗大突起は高さが１３０ｎｍ以上の高さを有する突起を意味する。なお、特許文献７では、測定するフィルム同士を重ね合わせて測定するが、波長２６０ｎｍではポリエステル自体が光を吸収することから、平坦なガラスプレートなどに貼り付けて、ガラスプレート側から光を照射し、ガラスプレートと空間の境界と空間とフィルム表面の境界とで反射される反射光（ポリエステルフィルムを通過しない光）による干渉の縞を観察すればよい。 By the way, such a coarse protrusion has the same basic measurement principle as the measurement of the coarse protrusion described in Patent Document 7, and is characterized in that light having a very short wavelength of 260 nm is used. Specifically, when the film is superimposed on a flat surface, there is a projection on the surface of the film, so that there is a space between the two. Then, when light is applied to the light wavelength (λ: nm), the reflected light cancels out at the interval of λ / 2, and as a result, a black dot or a black ring shape centering on the protrusion A pattern appears. From such a viewpoint, theoretically, the coarse protrusion in the present invention means a protrusion having a height of 130 nm or more. In Patent Document 7, measurement is performed by superimposing films to be measured. Since the polyester itself absorbs light at a wavelength of 260 nm, it is attached to a flat glass plate or the like and irradiated with light from the glass plate side. What is necessary is just to observe the fringe of the interference by the reflected light (light which does not pass through the polyester film) reflected by the boundary between the glass plate and the space and the boundary between the space and the film surface.
また、本発明の好ましい対応として、Ｆ層は、突起を中心に黒い点と黒いリング状の模様の両方もしくは突起を中心に複数の黒いリング状の模様が観察される極大突起数が１００個／１００ｃｍ２以下、さらに８０個／１００ｃｍ２以下であることが好ましい。なお、理論的には、本発明における極大突起は高さが２６０ｎｍ以上の高さを有する突起を意味する。 In addition, as a preferable correspondence of the present invention, the F layer has a maximum number of protrusions of 100 at which both a black dot and a black ring-shaped pattern centering on the protrusion or a plurality of black ring-shaped patterns centered on the protrusion are observed. It is preferably 100 cm 2 or less, more preferably 80 pieces / 100 cm 2 or less. Theoretically, the maximum protrusion in the present invention means a protrusion having a height of 260 nm or more.
本発明におけるＦ層を構成するポリエステルは、フィルムへの製膜が可能なものであれば、それ自体公知のものを採用できる。例えば、ジオール成分と芳香族ジカルボン酸成分との重縮合によって得られる芳香族ポリエステルが好ましく、かかる芳香族ジカルボン酸成分として、例えばテレフタル酸、イソフタル酸、２，６-ナフタレンジカルボン酸、４，４’−ジフェニルジカルボン酸、６，６’−（エチレンジオキシ）ジ−２−ナフトエ酸などの６，６’−（アルキレンジオキシ）ジ−２−ナフトエ酸が挙げられ、またジオール成分として、例えばエチレングリコール、１，４-ブタンジオール、１，４-シクロヘキサンジメタノール、１，６-ヘキサンジオールが挙げられる。 As the polyester constituting the F layer in the present invention, a polyester known per se can be adopted as long as it can be formed into a film. For example, an aromatic polyester obtained by polycondensation of a diol component and an aromatic dicarboxylic acid component is preferable. Examples of the aromatic dicarboxylic acid component include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4 ′ -Diphenyldicarboxylic acid, 6,6 '-(alkylenedioxy) di-2-naphthoic acid such as 6,6'-(ethylenedioxy) di-2-naphthoic acid, and the diol component include, for example, ethylene Examples include glycol, 1,4-butanediol, 1,4-cyclohexanedimethanol, and 1,6-hexanediol.
これらの中でも、高温での加工時の寸法安定性の点からは、エチレンテレフタレートまたはエチレン−２，６−ナフタレンジカルボキシレートを主たる繰り返し単位とするものが好ましく、特にエチレン−２，６−ナフタレンジカルボキシレートを主たる繰り返し単位とするものが好ましい。 Among these, ethylene terephthalate or ethylene-2,6-naphthalenedicarboxylate is the main repeating unit from the viewpoint of dimensional stability during processing at high temperature, and ethylene-2,6-naphthalene is particularly preferable. Those having carboxylate as the main repeating unit are preferred.
また、より環境変化に対する寸法安定性を向上させる観点から、国際公開２００８／０９６６１２号パンフレットに記載された６，６’−（エチレンジオキシ）ジ−２−ナフトエ酸成分、６，６’−（トリメチレンジオキシ）ジ−２−ナフトエ酸成分および６，６’−（ブチレンジオキシ）ジ−２−ナフトエ酸成分などを共重合したものも挙げられる。 Further, from the viewpoint of further improving the dimensional stability against environmental changes, the 6,6 ′-(ethylenedioxy) di-2-naphthoic acid component described in International Publication No. 2008/096612 pamphlet, 6,6 ′-( Examples include those obtained by copolymerizing a trimethylenedioxy) di-2-naphthoic acid component and a 6,6 ′-(butylenedioxy) di-2-naphthoic acid component.
ところで、本発明におけるポリエステルは、含有する不溶性粗大異物が、少ないことが好ましい。不溶性粗大異物を少なくするには、ポリエステルの製造に用いる芳香族ジカルボン酸成分やジオール成分を蒸留などの精製工程を繰り返して不純物を減らし、後述の重合工程で用いる触媒や安定剤として析出しにくい物を選択することなどが挙げられる。 By the way, it is preferable that the polyester in this invention contains few insoluble coarse foreign materials. In order to reduce insoluble coarse particles, repeat the purification process such as distillation of aromatic dicarboxylic acid components and diol components used in the production of polyester to reduce impurities, and to prevent precipitation as a catalyst or stabilizer used in the polymerization step described later And so on.
本発明におけるポリエステルは、ｏ-クロロフェノール中で３５℃の雰囲気下で測定したときの固有粘度が、０．４０ｄｌ／ｇ以上であることが好ましく、０．４０〜１．０ｄｌ／ｇであることがさらに好ましい。固有粘度が０．４ｄｌ／ｇ未満ではフィルム製膜時に切断が多発したり、成形加工後の製品の強度が不足することがある。一方固有粘度が１．０ｄｌ／ｇを超える場合は重合時の生産性が低下する。 The polyester according to the present invention preferably has an intrinsic viscosity of 0.40 dl / g or more when measured in o-chlorophenol at 35 ° C. in an atmosphere of 0.40 to 1.0 dl / g. Is more preferable. If the intrinsic viscosity is less than 0.4 dl / g, cutting may occur frequently during film formation, or the strength of the product after forming may be insufficient. On the other hand, when the intrinsic viscosity exceeds 1.0 dl / g, productivity during polymerization is lowered.
なお、本発明におけるポリエステルは、本発明の効果を損なわない範囲で、それ自体公知の他の共重合成分をさらに共重合、例えば繰り返し単位のモル数に対して１０モル％以下、さらに５モル％以下の範囲で共重合していてもよいし、他の熱可塑性樹脂などを、例えば２０重量％以下、さらに１０重量％以下の範囲でブレンドしても良い。 The polyester in the present invention is further copolymerized with other copolymer components known per se within a range not impairing the effects of the present invention, for example, 10 mol% or less, further 5 mol% with respect to the number of moles of repeating units. The copolymer may be copolymerized in the following range, or may be blended with another thermoplastic resin or the like in a range of, for example, 20% by weight or less, and further 10% by weight or less.
ところで、本発明におけるＦ層は、上述のポリエステルから製造できるが、搬送や巻取りなどの特性を実用上問題ない範囲で維持しつつ、データストレージにしたときの電磁変換特性を高度に維持させる観点から、磁性層を形成する側の表面は、表面粗さ（ＲａＡ）が１〜５ｎｍの範囲にあることが好ましい。好ましいＲａＡは、１〜４ｎｍ、さらに２〜４ｎｍの範囲である。 By the way, although F layer in this invention can be manufactured from the above-mentioned polyester, while maintaining characteristics, such as conveyance and winding, in the range which is practically satisfactory, the viewpoint which maintains the electromagnetic conversion characteristic when it is set as data storage highly. Therefore, the surface on the side on which the magnetic layer is formed preferably has a surface roughness (RaA) in the range of 1 to 5 nm. Preferred RaA is in the range of 1 to 4 nm, more preferably 2 to 4 nm.
このような表面粗さ（ＲａＡ）を具備させる観点から、磁性層を形成する側の表面を形成するポリエステルは、不活性粒子を含有しないか、含有するとしても、平均粒径０．０５〜０．１５μｍ、さらに０．０７〜０．１４μｍの不活性粒子を、該表面を形成するポリエステルの重量を基準として、０．００５〜０．２重量％、さらに０．００７〜０．１８重量％の範囲で含有することが好ましい。なお、ここでいう不活性粒子を含有しないとは、平均粒径０．０５μｍ以上の不活性粒子の含有量が０．００５重量％未満であることを意味する。 From the viewpoint of providing such surface roughness (RaA), the polyester that forms the surface on the side of forming the magnetic layer does not contain or contains inert particles, but has an average particle size of 0.05 to 0. 0.15 μm, further 0.07 to 0.14 μm of inert particles, based on the weight of the polyester forming the surface, 0.005 to 0.2% by weight, further 0.007 to 0.18% by weight. It is preferable to contain in the range. The term “not containing inert particles” as used herein means that the content of inert particles having an average particle size of 0.05 μm or more is less than 0.005% by weight.
不活性粒子を含有させる場合、含有させる不活性粒子は粗大粒子を含まないか含有するとしても極めて含有量が少ない不活性粒子が好ましい。また、ポリエステル中で、一次粒子の大半が、一次粒子のままポリマー中に分散している単独分散型粒子が好ましい。このような粒子としては、シリコーン樹脂、架橋アクリル樹脂、架橋ポリエステル、架橋ポリスチレンなどの有機高分子粒子および球状シリカなどが好ましく、特にシリコーン樹脂、架橋ポリスチレンおよび球状シリカが好ましい。もちろん、これらの不活性粒子を含有させる場合でも、さらに粗大粒子をなくすため、フィルターでのろ過を行ったり、分散剤で不活性粒子の表面を処理したり、押出機での混練を強化することが好ましい。 When the inert particles are contained, the inert particles to be contained are preferably inert particles that contain no coarse particles or have a very small content even if they are contained. Moreover, the single dispersion type particle | grains in which most primary particles are disperse | distributing in the polymer with primary particles are preferable in polyester. As such particles, organic polymer particles such as silicone resin, crosslinked acrylic resin, crosslinked polyester, crosslinked polystyrene, and spherical silica are preferable, and silicone resin, crosslinked polystyrene, and spherical silica are particularly preferable. Of course, even when these inert particles are contained, in order to eliminate further coarse particles, filtration with a filter, treatment of the surface of the inert particles with a dispersant, and strengthening of kneading with an extruder Is preferred.
本発明におけるＦ層は、前述の表面粗さを有するものであれば特に制限されず、単層フィルムでも２層以上のポリエステル層からなる積層フィルムであっても良い。ただ、磁性層側が同じ表面粗さなら、より搬送性や巻取り性を向上させやすく、同じ搬送性や巻取り性なら、より磁性層側の表面粗さを平坦にすることができることから、２層以上のポリエステル層からなり、非磁性層側の表面粗さが磁性層側の表面粗さよりも１ｎｍ以上大きい積層フィルムが好ましい。 The F layer in the present invention is not particularly limited as long as it has the above-mentioned surface roughness, and may be a single layer film or a laminated film composed of two or more polyester layers. However, if the magnetic layer side has the same surface roughness, it is easier to improve the transportability and winding property, and if the same transportability and winding property, the surface roughness on the magnetic layer side can be made flatter. A laminated film composed of at least a polyester layer and having a surface roughness on the nonmagnetic layer side that is 1 nm or more larger than the surface roughness on the magnetic layer side is preferable.
そのような観点から、磁性層を形成しない側のＦ層の表面は、表面粗さ（ＲａＢ）が磁性層側の表面粗さ（ＲａＡ）よりも１ｎｍ以上大きく、３〜１０ｎｍの範囲にあることが好ましい。好ましいＲａＢは、４〜９ｎｍ、さらに５〜９ｎｍの範囲である。ＲａＢが下限未満もしくはＲａＡよりも小さいと、搬送性や巻取り性の向上効果が発現されがたく、他方上限を超えると、磁性層側の表面を突き上げや転写によって粗くすることがある。 From such a viewpoint, the surface of the F layer on the side where the magnetic layer is not formed has a surface roughness (RaB) that is 1 nm or more larger than the surface roughness (RaA) on the magnetic layer side and is in the range of 3 to 10 nm. Is preferred. Preferred RaB is in the range of 4-9 nm, more preferably 5-9 nm. When RaB is less than the lower limit or smaller than RaA, the effect of improving the transportability and the winding property is hardly exhibited, and when the other upper limit is exceeded, the surface on the magnetic layer side may be roughened by pushing up or transferring.
磁性層を形成しない側の表面に上述のような表面粗さを具備させるには、平均粒径が０．２〜０．５μｍ、さらに０．２〜０．４μｍの不活性粒子（以下、不活性粒子Ｉと称することがある）を、該表面を形成するポリエステルの重量を基準として、０．０１〜０．２重量％、さらに０．０２〜０．２重量％の範囲で含有させることが好ましい。さらに、磁性層を形成しない側の表面は、平均粒径が０．０５〜０．１５μｍ、さらに０．０６〜０．１４μｍの不活性粒子（以下、不活性粒子ＩＩと称することがある）を、０．０５〜０．３重量％、さらに０．０６〜０．２５重量％の範囲で含有することが好ましい。このような２種類以上の不活性粒子を併用することで、より搬送性と巻取り性を高めつつ、磁性層側の表面を平坦に維持しやすい。 In order to provide the above-mentioned surface roughness on the surface on which the magnetic layer is not formed, inert particles having an average particle size of 0.2 to 0.5 μm, and further 0.2 to 0.4 μm (hereinafter referred to as non-conductive particles). Active particles I) may be contained in the range of 0.01 to 0.2% by weight, more preferably 0.02 to 0.2% by weight, based on the weight of the polyester forming the surface. preferable. Furthermore, the surface on the side where the magnetic layer is not formed is an inert particle having an average particle diameter of 0.05 to 0.15 μm, more preferably 0.06 to 0.14 μm (hereinafter sometimes referred to as inert particle II). 0.05 to 0.3% by weight, and more preferably 0.06 to 0.25% by weight. By using such two or more kinds of inert particles in combination, it is easy to keep the surface on the magnetic layer side flat while further improving the transportability and the winding property.
上述の磁性層を形成しない側の表面に含有させる不活性粒子としては、ポリマー中で安定的に存在できるものであれば特に制限されず、それ自体公知のものを採用でき、好ましくは前述の磁性層を形成する側の表面で説明したのと同様な不活性粒子である。 The inert particles to be contained on the surface on the side where the magnetic layer is not formed are not particularly limited as long as they can be stably present in the polymer, and those known per se can be adopted, and preferably the above-mentioned magnetic particles are used. Inactive particles similar to those described for the surface on the layer-forming side.
つぎに、Ｆ層の製造方法について説明する。まず、本発明におけるポリエステルの製造方法は、例えば芳香族ジカルボン酸もしくはそのエステル形成性誘導体とアルキレングリコールとをエステル化反応もしくはエステル交換反応させてポリエステルの前駆体を合成する第一反応と、該前駆体を重縮合反応させる第二反応とからなり、それ自体公知の方法を採用できる。前述のとおり、原料由来の異物を低減するために、芳香族ジカルボン酸もしくはそのエステル形成性誘導体とアルキレングリコールなどの原料は、精製を繰り返して、異物を低減しておくのが好ましい。ここでの異物が多いと、後述のろ過によっても異物が取りきれず、粗大突起が増えてしまうことがある。 Next, a method for manufacturing the F layer will be described. First, the polyester production method of the present invention includes, for example, a first reaction in which an aromatic dicarboxylic acid or an ester-forming derivative thereof and an alkylene glycol are esterified or transesterified to synthesize a polyester precursor, and the precursor It consists of a second reaction in which the product is polycondensed, and a method known per se can be adopted. As described above, in order to reduce foreign substances derived from raw materials, it is preferable to repeat purification of the raw materials such as aromatic dicarboxylic acid or its ester-forming derivative and alkylene glycol to reduce foreign substances. If there are many foreign substances here, foreign substances may not be removed even by filtration described later, and coarse protrusions may increase.
このように精製された原料は、前述の第一反応によってポリエステル前駆体となる。ここで重要なことは、このポリエステル前駆体を、第二反応を開始する前に、９５％ろ過精度が１０μｍ以下の第１フィルターでろ過を行ない、この段階でも不溶性粗大異物を減らすことであり、それによって後述の第二反応後のろ過で、さらに不溶性粗大異物量を減らしやすくなる。なお、第１フィルターでのろ過は一度に限定されず、必要であればさらにろ過を繰り返したり、フィルターを多重に使用しても良い。したがって、第一反応と第二反応の間で行なう第１フィルターのろ過精度は、フライスペック低減の観点からは小さいほど好ましく、９５％ろ過精度がさらに８μｍ以下、さらに５μｍ以下であることが好ましい。一方、第１フィルターの９５％ろ過精度の下限は特に制限されないが、小さくしていくとそれだけ詰まりやすく交換周期が短くなるので、生産性などの観点から３μｍ以上、さらに４μｍ以上であることが好ましい。また、第１フィルターは、金属繊維の不織布を積層した構造のもので、積層された金属不織布の空隙率は通常４０〜８０％の範囲にあることが、ろ過速度を維持しつつ、ろ過圧力に耐えられるので好ましい。なお、このような不溶性粗大異物量は、原料段階から極力減らすことが好ましいが、前述のとおり難しく、第一反応後のフィルターろ過によって取り除くことが、簡便で且つ極めて有効である。 The raw material thus purified becomes a polyester precursor by the first reaction described above. What is important here is that the polyester precursor is filtered through a first filter having a 95% filtration accuracy of 10 μm or less before the second reaction is started, and at this stage, insoluble coarse particles are reduced. This makes it easier to reduce the amount of insoluble coarse foreign matter by filtration after the second reaction described below. The filtration with the first filter is not limited to one time. If necessary, the filtration may be repeated further, or the filters may be used in multiple layers. Therefore, the filtration accuracy of the first filter performed between the first reaction and the second reaction is preferably as small as possible from the viewpoint of fly spec reduction, and the 95% filtration accuracy is preferably 8 μm or less, and more preferably 5 μm or less. On the other hand, the lower limit of the 95% filtration accuracy of the first filter is not particularly limited. However, since the replacement cycle becomes shorter as the filter becomes smaller as it is reduced, it is preferably 3 μm or more, and more preferably 4 μm or more from the viewpoint of productivity. . The first filter has a structure in which a nonwoven fabric of metal fibers is laminated, and the porosity of the laminated metal nonwoven fabric is usually in the range of 40 to 80%, while maintaining the filtration speed, It is preferable because it can withstand. Although it is preferable to reduce the amount of such insoluble coarse foreign matter as much as possible from the raw material stage, it is difficult as described above, and it is simple and extremely effective to remove it by filter filtration after the first reaction.
さらに好ましい第一反応の条件について説明する。第一反応は、常圧下で行ってもよいが、０．０５ＭＰａ〜０．５ＭＰａの加圧下で行うことが反応速度をより速めやすいことから好ましい。また、第一反応の温度は、２１０℃〜２７０℃の範囲で行うことが好ましい。反応圧力を上記範囲内とすることで反応の進行を進みやすくしつつ、ジアルキレングリコールに代表される副生物の発生を抑制できる。このとき、アルキレングリコール成分は、第一反応を行う反応系に存在する酸成分に対し１．１〜６モル倍用いることが、反応速度及び樹脂の物性維持の点から好ましい。より好ましくは２〜５モル倍、さらに好ましくは３〜５モル倍である。 Further preferable conditions for the first reaction will be described. The first reaction may be performed under normal pressure, but is preferably performed under a pressure of 0.05 MPa to 0.5 MPa because the reaction rate can be easily increased. Moreover, it is preferable to perform the temperature of 1st reaction in the range of 210 to 270 degreeC. By making the reaction pressure within the above range, it is possible to suppress the generation of by-products typified by dialkylene glycol while facilitating the progress of the reaction. At this time, the alkylene glycol component is preferably used in an amount of 1.1 to 6 moles relative to the acid component present in the reaction system in which the first reaction is carried out from the viewpoint of maintaining the reaction rate and the physical properties of the resin. More preferably, it is 2-5 mol times, More preferably, it is 3-5 mol times.
また、第一反応の反応速度をより早くするには、それ自体公知の触媒を用いることが好ましく、たとえばＬｉ，Ｎａ，Ｋ，Ｍｇ，Ｃａ，Ｍｎ、Ｃｏ、Ｔｉなどの金属成分を有する金属化合物が好ましく挙げられ、これらの中でも加圧下で行う場合は、反応の進みやすさの点からＭｎやＴｉ化合物が好ましい。特にＴｉ化合物は、さらに重縮合反応触媒としても使用でき、かつ触媒残渣の析出も少ないことから好ましい。本発明で用いるチタン化合物としては、触媒残渣の析出による不溶性粗大異物の発生を抑制する観点からポリエステル中に可溶な有機チタン化合物が好ましい。特に好ましいチタン化合物としては、チタンテトライソプロポキシド、チタンテトラプロポキシド、チタンテトラブトキシド、チタンテトラエトキシド、チタンテトラフェノキシド、トリメリット酸チタンなどを好ましく例示できる。 Further, in order to increase the reaction rate of the first reaction, it is preferable to use a catalyst known per se, for example, a metal compound having a metal component such as Li, Na, K, Mg, Ca, Mn, Co, and Ti. Among these, when performing under pressure, Mn and Ti compounds are preferable from the viewpoint of easy progress of the reaction. In particular, a Ti compound is preferable because it can be used as a polycondensation reaction catalyst, and the catalyst residue is less precipitated. The titanium compound used in the present invention is preferably an organic titanium compound that is soluble in polyester from the viewpoint of suppressing the generation of insoluble coarse particles due to precipitation of catalyst residues. Particularly preferable examples of the titanium compound include titanium tetraisopropoxide, titanium tetrapropoxide, titanium tetrabutoxide, titanium tetraethoxide, titanium tetraphenoxide, and trimellitic acid titanium.
添加する触媒量は、第一反応中に存在する全酸成分のモル数を基準として、金属元素換算で、１０〜１５０ミリモル％の範囲にあることが好ましく、さらに２０〜１００ミリモル％、特に３０〜７０ミリモル％の範囲にあることが反応速度を促進しつつ、触媒起因の粗大不溶性異物の生成を抑制でき、さらに得られる共重合芳香族ポリエステルの耐熱性を高度に維持できることから好ましい。なお、チタン化合物を添加する場合の添加時期は、第一反応のエステル化反応開始時から存在するように添加し、前述のとおり、引き続き重縮合反応触媒として使用することが好ましい。もちろん、重縮合反応速度をコントロールする目的で２回以上に分けて添加してもよい。 The amount of catalyst to be added is preferably in the range of 10 to 150 mmol%, more preferably 20 to 100 mmol%, especially 30, in terms of metal elements, based on the number of moles of all acid components present in the first reaction. It is preferable to be in the range of ˜70 mmol% because the reaction rate can be promoted, the formation of coarse insoluble foreign matters due to the catalyst can be suppressed, and the heat resistance of the resulting copolymerized aromatic polyester can be maintained at a high level. In addition, when adding a titanium compound, it is preferable to add so that it may exist from the time of the esterification reaction start of a 1st reaction, and as above-mentioned, it uses continuously as a polycondensation reaction catalyst. Of course, it may be added in two or more times for the purpose of controlling the polycondensation reaction rate.
つぎに、第一反応で得られた前駆体を重縮合反応させる第二反応について説明する。
本発明では、得られるポリエステルに、高度の熱安定性を付与させる目的で、第二反応における重縮合反応の開始以前に、反応系にリン化合物からなる熱安定剤を添加することが好ましい。具体的なリン化合物としては、化合物中にリン元素を有するものであれば特に限定されず、例えば、リン酸、亜リン酸、リン酸トリメチルエステル、リン酸トリブチルエステル、リン酸トリフェニルエステル、リン酸モノメチルエステル、リン酸ジメチルエステル、フェニルホスホン酸、フェニルホスホン酸ジメチルエステル、フェニルホスホン酸ジエチルエステル、リン酸アンモニウム、トリエチルホスホノアセテート、メチルジエチルホスホノアセテートなどを挙げることができ、これらのリン化合物は二種以上を併用してもよい。なお、リン化合物の添加時期は、第一反応が実質的に終了してから第二反応である重縮合反応初期の間に行なうことが好ましく、添加は一度に行ってもよいし、２回以上に分割して行ってもよい。
Next, the second reaction in which the precursor obtained in the first reaction is polycondensed will be described.
In the present invention, for the purpose of imparting a high degree of thermal stability to the obtained polyester, it is preferable to add a thermal stabilizer composed of a phosphorus compound to the reaction system before the start of the polycondensation reaction in the second reaction. The specific phosphorus compound is not particularly limited as long as it has a phosphorus element in the compound. For example, phosphoric acid, phosphorous acid, phosphoric acid trimethyl ester, phosphoric acid tributyl ester, phosphoric acid triphenyl ester, phosphorus Acid monomethyl ester, phosphoric acid dimethyl ester, phenylphosphonic acid, phenylphosphonic acid dimethyl ester, phenylphosphonic acid diethyl ester, ammonium phosphate, triethylphosphonoacetate, methyldiethylphosphonoacetate, etc., and these phosphorus compounds May use 2 or more types together. The phosphorus compound is preferably added during the initial stage of the polycondensation reaction, which is the second reaction, after the first reaction is substantially completed. The addition may be performed at one time or two or more times. You may divide into.
ところで、重縮合反応の温度は２７０℃〜３００℃の範囲で行い、重縮合反応中の圧力は５０Ｐａ以下の減圧下で行うのが好ましい。重縮合反応中の圧力が上限より高いと重縮合反応に要する時間が長くなり且つ重合度の高い共重合芳香族ポリエステルを得ることが困難になる。重縮合触媒としては、それ自体公知のＴｉ，Ａｌ，Ｓｂ，Ｇｅなどの金属化合物を好適に使用でき、それらの中でもエステル化反応時に添加されたチタン化合物を引き続き使用することが触媒残渣による不溶性粗大異物の発生を抑制できることから好ましい。 By the way, the polycondensation reaction is preferably performed at a temperature in the range of 270 ° C. to 300 ° C., and the pressure during the polycondensation reaction is preferably performed under a reduced pressure of 50 Pa or less. If the pressure during the polycondensation reaction is higher than the upper limit, the time required for the polycondensation reaction becomes long and it becomes difficult to obtain a copolymerized aromatic polyester having a high degree of polymerization. As the polycondensation catalyst, metal compounds such as Ti, Al, Sb and Ge known per se can be preferably used. Among them, the titanium compound added during the esterification reaction can be used continuously so that insoluble coarse particles due to catalyst residues can be used. It is preferable because the generation of foreign matter can be suppressed.
ところで、前述のとおり、さらに粗大突起を低減する観点から、重縮合反応によって得られる所望の分子量を有するポリエステルを、溶融状態で９５％ろ過精度がさらに１．５μｍ以下の第２フィルターでろ過することがこのましい。このようなろ過により、前述の第一反応と第二反応の間で行なうろ過では取りきれなかった、またはその後に生成された不溶性粗大異物を取り除くことが出来る。好ましい第２フィルターの９５％ろ過精度は、１μｍ以下であり、小さければ小さいほどフライスペックの点では好ましいが、生産性などの点から０．２μｍ以上、さらに０．３μｍ以上であることが好ましい。また、第２フィルターは、金属不織布メディアを積層した構造のもので、積層された金属不織布の空隙率は通常４０〜８０％の範囲にあることが、ろ過速度を維持しつつ、ろ過圧力に耐えられるので好ましい。 By the way, as described above, from the viewpoint of further reducing the coarse protrusion, the polyester having a desired molecular weight obtained by the polycondensation reaction is filtered with a second filter having a 95% filtration accuracy of 1.5 μm or less in a molten state. Is this. By such filtration, it is possible to remove insoluble coarse particles that could not be removed by the filtration performed between the first reaction and the second reaction described above, or that were generated thereafter. The 95% filtration accuracy of the preferred second filter is 1 μm or less, and the smaller the value, the more preferable in terms of fly specs, but from the viewpoint of productivity, it is preferably 0.2 μm or more, and more preferably 0.3 μm or more. In addition, the second filter has a structure in which metal nonwoven fabric media is laminated, and the porosity of the laminated metal nonwoven fabric is usually in the range of 40 to 80% so that it can withstand the filtration pressure while maintaining the filtration speed. This is preferable.
また、不活性粒子を含有させる方法については、前述のような粗大粒子の低減を行ったものを選択し、それをアルキレングリコールのスラリー状態として、さらにフィルターなどによって粗大粒子を低減し、それを重合工程で添加して粒子含有量が０．０２〜１．０重量％の粒子含有マスターポリエステルを作成し、該マスターポリエステルを粒子を含有しないポリエステルで希釈するのが、不活性粒子の凝集による粗大突起を低減する上で好ましい。 In addition, for the method of containing inert particles, select the one that has reduced the coarse particles as described above, make it an alkylene glycol slurry, further reduce the coarse particles with a filter, etc., and polymerize it. It is a coarse protrusion due to agglomeration of inert particles that is added in the process to prepare a particle-containing master polyester having a particle content of 0.02 to 1.0% by weight, and the master polyester is diluted with a polyester not containing particles. It is preferable in reducing the amount.
このようにして得られるポリエステルは、本発明の効果を阻害しない範囲で、紫外線吸収剤等の安定剤、酸化防止剤、可塑剤、滑剤、難燃剤、離型剤、核剤、を必要に応じて配合しても良いが、少なくとも磁性層を形成する側の表面に用いるポリエステルは、粗大突起を形成しやすい他の熱可塑性ポリマー、顔料、充填剤あるいはガラス繊維、炭素繊維、層状ケイ酸塩などは含有させないことが好ましい。 The polyester thus obtained contains a stabilizer such as an ultraviolet absorber, an antioxidant, a plasticizer, a lubricant, a flame retardant, a release agent, and a nucleating agent as necessary, as long as the effects of the present invention are not impaired. However, the polyester used on at least the surface on which the magnetic layer is formed may be other thermoplastic polymer, pigment, filler or glass fiber, carbon fiber, layered silicate, etc. Is preferably not contained.
本発明におけるＦ層は、データストレージのベースフィルムに用いることから、二軸配向フィルムである。二軸配向フィルムは、上述のポリエステルを溶融状態で押出し、二軸方向に延伸することで製造でき、製膜方法などはそれ自体公知のものを採用することができる。なお、前述の第２フィルターのろ過は、製膜直前であるほど、再凝集などによって後から生成される不溶性粗大異物の影響を低減できることから、製膜する際の溶融押出工程で用いるのが好ましい。 The F layer in the present invention is a biaxially oriented film because it is used as a base film for data storage. The biaxially oriented film can be produced by extruding the polyester described above in a molten state and stretching in the biaxial direction, and a film forming method or the like can be employed. The filtration of the second filter described above is preferably used in the melt extrusion step during film formation because the influence of insoluble coarse particles generated later by reaggregation or the like can be reduced as it is immediately before film formation. .
例えば、二軸配向積層ポリエステルフィルムで説明すると、押出し口金内または口金以前（一般に、前者はマルチマニホールド方式、後者はフィードブロック方式と呼ぶ）で、不活性粒子を含有させたポリエステルＢと、必要に応じて不活性粒子を含有させたポリエステルＡとを、それぞれさらに前述のような高精度のフィルターでろ過したのち、溶融状態にて積層複合し、上記好適な厚み比の積層構造となし、次いで口金よりポリエステルの融点（Ｔｍ）〜（Ｔｍ＋７０）℃の温度でフィルム状に共押出ししたのち、３０〜７０℃の冷却ロールで急冷固化し、未延伸積層フィルムを得る。その後、上記未延伸積層フィルムを常法に従い、一軸方向（縦方向または横方向）に（ポリエステルのガラス転移温度（Ｔｇ）−１０）〜（Ｔｇ＋７０）℃の温度で２．５〜８．０倍の倍率で、好ましくは３．０〜７．５倍の倍率で延伸し、次いで上記延伸方向とは直角方向（一段目延伸が縦方向の場合には、二段目延伸は横方向となる）に（Ｔｇ）〜（Ｔｇ＋７０）℃の温度で２．５〜８．０倍の倍率で、好ましくは３．０〜７．５倍の倍率で延伸する。さらに、必要に応じて、縦方向および／または横方向に再度延伸してもよい。すなわち、２段、３段、４段あるいは多段の延伸を行うとよい。全延伸倍率としては、通常９倍以上、好ましくは１０〜３５倍、さらに好ましくは１２〜３０倍である。 For example, in the case of a biaxially oriented laminated polyester film, polyester B containing inert particles in the extrusion die or before the die (generally, the former is called a multi-manifold method and the latter is called a feed block method) and necessary The polyester A containing the inert particles is further filtered through a high-precision filter as described above, and then laminated in a molten state to form a laminated structure with the above preferred thickness ratio, and then the die After co-extruding into a film at a temperature of the melting point (Tm) to (Tm + 70) ° C. of the polyester, it is rapidly cooled and solidified with a cooling roll of 30 to 70 ° C. to obtain an unstretched laminated film. Thereafter, the unstretched laminated film is 2.5 to 8.0 times in a uniaxial direction (longitudinal direction or transverse direction) at a temperature of (polyester glass transition temperature (Tg) -10) to (Tg + 70) ° C. according to a conventional method. The film is stretched at a magnification of 3.0 to 7.5, and preferably in a direction perpendicular to the stretching direction (when the first-stage stretching is the longitudinal direction, the second-stage stretching is the transverse direction). (Tg) to (Tg + 70) at a temperature of 2.5 to 8.0 times, preferably 3.0 to 7.5 times. Furthermore, you may extend | stretch again in the vertical direction and / or a horizontal direction as needed. That is, it is good to perform 2 steps, 3 steps, 4 steps, or multi-stage stretching. The total draw ratio is usually 9 times or more, preferably 10 to 35 times, and more preferably 12 to 30 times.
さらに、前記二軸配向フィルムは（Ｔｇ＋７０）〜（Ｔｍ−１０）℃の温度、例えば、ポリエチレンテレフタレートフィルムの場合、１８０〜２５０℃で熱固定結晶化することによって、優れた寸法安定性が付与される。その際、熱固定時間は１〜６０秒が好ましい。 Further, the biaxially oriented film is imparted with excellent dimensional stability by heat-set crystallization at a temperature of (Tg + 70) to (Tm-10) ° C., for example, 180 to 250 ° C. in the case of a polyethylene terephthalate film. The At that time, the heat setting time is preferably 1 to 60 seconds.
このようにして得られたＦ層は、前述のとおり、波長２６０ｎｍの光の干渉によって測定される粗大突起の数を測定し、上限以下になるように原料や不活性粒子の精製を強化したり、各段階でのフィルターによるろ過を強化したりすることで、製造することができる。 As described above, the F layer thus obtained measures the number of coarse protrusions measured by the interference of light having a wavelength of 260 nm, and enhances the purification of raw materials and inert particles so as to be below the upper limit. It can be manufactured by strengthening filtration with a filter at each stage.
そして、波長２６０ｎｍの光の干渉によって測定される粗大突起の数が前述の上限以下の表面にＭ層を設け、その上に磁性層を形成することで、記憶容量が０．８ＴＢ以上であるデータストレージとすることができ、そのときのエラーが非常に低減されたものとなる。なお、磁性層については、波長２６０ｎｍの光の干渉によって測定される粗大突起による影響を緩和しやすいことから、強磁性金属を含有する塗剤を塗布して形成する塗布型磁性層が好ましく、塗布型磁性層による走行性を利用できる観点から、記録方式がリニア記録方式であるデータストレージが好ましい。 Data having a storage capacity of 0.8 TB or more is obtained by providing an M layer on the surface where the number of coarse protrusions measured by interference of light having a wavelength of 260 nm is not more than the above-mentioned upper limit, and forming a magnetic layer thereon. Storage can be achieved, and errors at that time are greatly reduced. As for the magnetic layer, a coating type magnetic layer formed by applying a coating containing a ferromagnetic metal is preferable because the influence of coarse protrusions measured by interference of light having a wavelength of 260 nm is easily mitigated. From the viewpoint that the traveling property by the mold magnetic layer can be utilized, a data storage in which the recording method is a linear recording method is preferable.
本発明の磁気記録媒体用支持体は、Ｆ層の少なくとも一方に金属類または金属系無機化合物からなる層（Ｍ層）を有する。Ｍ層を有することで、Ｆ層のみからなる磁気記録媒体用支持体に比べ、温湿度環境変化および荷重による寸法変化の好ましい範囲を両立することが容易となる。ここで、金属類とは、いわゆる単体金属、半金属、合金、金属間化合物を表し、具体的には、例えば単体金属ではＭｇ、Ａｌ、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ｚｒ、Ｍｏ、Ｐｄ、Ａｇ、Ｓｎ、Ｐｔ、Ａｕ、Ｐｂ、半金属ではＣ、Ｓｉ、Ｇｅ、Ｓｂ、Ｔｅなどが挙げられ、これらの金属の数種を混ぜ合わせて合金や金属間化合物としてもよい。また、金属系無機化合物としては、例えば、上記金属類の酸化物や窒化物、炭化物、ホウ化物、硫化物などを用いることができる。具体的には、例えば、ＣｕＯ、ＺｎＯ、Ａｌ２Ｏ３、ＳｉＯ２、Ｆｅ２Ｏ３、Ｆｅ３Ｏ４、Ａｇ２Ｏ、ＴｉＯ２、ＭｇＯ、ＳｎＯ２、ＺｒＯ２、ＩｎＯ３などの酸化物、Ｓｉ４Ｎ３、ＴｉＮ、ＺｒＮ、ＧａＮ、ＴａＮ、ＡｌＮなどの窒化物、ＴｉＣ、ＷＣ、ＳｉＣ、ＮｂＣ、ＺｒＣ、Ｆｅ３Ｃなどの炭化物が挙げられる。また、上記の金属系無機化合物はそれぞれ単独で用いてもよく、もちろん複数種を混合して用いても構わない。中でも、Ｍ層を構成する金属材料は経済性の観点からアルミニウムや珪素を含むことが好ましい。 The support for magnetic recording media of the present invention has a layer (M layer) made of a metal or a metal-based inorganic compound on at least one of the F layers. By having the M layer, it becomes easy to achieve both a preferable range of temperature and humidity environment changes and a dimensional change due to a load, as compared with a magnetic recording medium support composed of only the F layer. Here, the metals represent so-called simple metals, metalloids, alloys, and intermetallic compounds. Specifically, for example, simple metals such as Mg, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Mo, Pd, Ag, Sn, Pt, Au, Pb, and semi-metals include C, Si, Ge, Sb, Te, etc. It may be an intercalation compound. As the metal-based inorganic compound, for example, oxides, nitrides, carbides, borides, sulfides, and the like of the above metals can be used. Specifically, for example, oxides such as CuO, ZnO, Al 2 O 3 , SiO 2 , Fe 2 O 3 , Fe 3 O 4 , Ag 2 O, TiO 2 , MgO, SnO 2 , ZrO 2 and InO 3 And nitrides such as Si 4 N 3 , TiN, ZrN, GaN, TaN, and AlN, and carbides such as TiC, WC, SiC, NbC, ZrC, and Fe 3 C. Moreover, said metal type inorganic compound may be used individually, respectively, and of course, multiple types may be mixed and used. Especially, it is preferable that the metal material which comprises M layer contains aluminum and silicon from an economical viewpoint.
Ｍ層の形成方法としては物理蒸着法や化学蒸着法を用いることができる。物理蒸着法には真空蒸着法、スパッタリング法があり、真空蒸着法が一般的である。特にＭ層の結晶粒径を小さく緻密にするためには蒸着物の運動エネルギーを高める必要がある。そのため電子ビーム蒸着やスパッタリング法が好ましい。 As a method for forming the M layer, physical vapor deposition or chemical vapor deposition can be used. Physical vapor deposition methods include vacuum vapor deposition and sputtering, and vacuum vapor deposition is common. In particular, in order to make the crystal grain size of the M layer small and precise, it is necessary to increase the kinetic energy of the deposited material. Therefore, electron beam evaporation or sputtering is preferable.
Ｍ層の厚みは５〜１３０ｎｍが好ましく、より好ましくは１０〜１２０ｎｍ、最も好ましくは１５〜１１０ｎｍである。この範囲にすることでＭ層の金属の結晶粒径を細かくすることができ、補強効果の向上と、表面平滑性への悪影響がないなどの条件を満足し易いため好ましい。厚みが下限よりも薄い場合、Ｍ層の金属の結晶形成が不完全となるため、強度を増加させる効果が小さくなるため、本発明の寸法安定性向上の効果が小さくなることがある。他方上限よりも厚い場合はクラックや粒界ができやすく、磁気記録媒体の表面が粗くなって電磁変換特性が悪化したり、Ｍ層が製造工程や、走行を繰り返す際に剥離や脱落が起こり易く、生産性が低下することがある。なお、本発明によれば、高さが１３０ｎｍ以上の粗大突起が極めて低減されていることから、このように薄いＭ層にしても平坦性に優れるという利点も有する。 The thickness of the M layer is preferably 5 to 130 nm, more preferably 10 to 120 nm, and most preferably 15 to 110 nm. By setting it in this range, the crystal grain size of the metal of the M layer can be made fine, and it is easy to satisfy the conditions such as improvement of the reinforcing effect and no adverse effect on the surface smoothness, which is preferable. When the thickness is less than the lower limit, the metal crystal formation of the M layer is incomplete, and the effect of increasing the strength is reduced, so that the effect of improving the dimensional stability of the present invention may be reduced. On the other hand, if it is thicker than the upper limit, cracks and grain boundaries are likely to occur, the surface of the magnetic recording medium becomes rough and electromagnetic conversion characteristics deteriorate, and the M layer is prone to peeling and dropping when the manufacturing process and running are repeated. , Productivity may decrease. According to the present invention, since the coarse protrusions having a height of 130 nm or more are extremely reduced, there is an advantage that even a thin M layer is excellent in flatness.
本発明の磁気記録媒体用支持体において、Ｍ層はＦ層の磁性層形成側にのみ設けても良いし、さらに両側に設けても良い。なお、磁気記録テープとしたときのカッピングやカールを抑制する観点から、Ｆ層の両側にＭ層を設けることが好ましい。また、上記好ましいＭ層の厚みは、Ｆ層の両面に設けた場合は、それぞれのＭ層が上記の範囲内にあることが好ましい。 In the magnetic recording medium support of the present invention, the M layer may be provided only on the magnetic layer forming side of the F layer, or may be provided on both sides. From the viewpoint of suppressing cupping and curling when a magnetic recording tape is used, it is preferable to provide M layers on both sides of the F layer. Moreover, when the thickness of said preferable M layer is provided in both surfaces of F layer, it is preferable that each M layer exists in said range.
本発明におけるＦ層は、Ｍ層と組み合わせて高密度磁気記録媒体の支持体として用いた際に優れた寸法安定性を発現するために、長手方向のヤング率が３〜１０ＧＰａ、さらに３．５〜９ＧＰａ、特に４〜８ＧＰａであることが好ましい。一方、幅方向のヤング率は、支持体としたときの温度膨張係数を前述の範囲とさせやすい観点から、４〜１５ＧＰａ、さらに５〜１４ＧＰａ、特に６〜１３ＧＰａ、もっとも好ましくは７〜１１ＧＰａの範囲であることが好ましい。Ｆ層の幅方向のヤング率が下限未満では、支持体としたときの温度膨張係数をマイナス側にすることが困難となり、他方上限を超えると、支持体としたときの温度膨張係数が過度にマイナス側となってしまう。 The F layer in the present invention has a Young's modulus in the longitudinal direction of 3 to 10 GPa, and further 3.5, in order to exhibit excellent dimensional stability when used as a support for a high-density magnetic recording medium in combination with the M layer. ˜9 GPa, particularly 4-8 GPa. On the other hand, the Young's modulus in the width direction is 4 to 15 GPa, more preferably 5 to 14 GPa, particularly 6 to 13 GPa, and most preferably 7 to 11 GPa, from the viewpoint that the temperature expansion coefficient when used as a support is easily in the above range. It is preferable that If the Young's modulus in the width direction of the F layer is less than the lower limit, it is difficult to make the temperature expansion coefficient negative when it is used as a support, while if it exceeds the upper limit, the temperature expansion coefficient when used as a support is excessive. It becomes the minus side.
本発明の磁気記録媒体用支持体は、長手方向のヤング率は５〜２０ＧＰａ、幅方向のヤング率は８〜２０ＧＰａであることが好ましい。支持体の長手方向のヤング率はさらに好ましくは５．５〜１８ＧＰａ、特に好ましくは６．０〜１５ＧＰａである。長手方向のヤング率が下限未満の時には磁気記録媒体を使用する際に張力の変動があった際に長手方向に変形しやすくなり、結果として、ポアソン比による幅方向の寸法変化が引き起こされやすくなる。長手方向のヤング率が上限を超える際には、幅方向のヤング率を範囲内に維持することが困難となり、ヘッドとの接触状態を安定に保つのが困難となる。支持体の幅方向のさらに好ましいヤング率は９〜１８ＧＰａ、特に好ましくは１０〜１６ＧＰａである。支持体の幅方向のヤング率が下限未満の場合、磁気ヘッドとの接触状態が不安定化するため電磁変換特性が悪化しやすくなる。支持体の幅方向のヤング率が上限を超える場合には、上記の好ましい支持体長手方向のヤング率範囲を達成することが困難となる。 The support for a magnetic recording medium of the present invention preferably has a Young's modulus in the longitudinal direction of 5 to 20 GPa and a Young's modulus in the width direction of 8 to 20 GPa. The Young's modulus in the longitudinal direction of the support is more preferably 5.5 to 18 GPa, and particularly preferably 6.0 to 15 GPa. When the Young's modulus in the longitudinal direction is less than the lower limit, it tends to be deformed in the longitudinal direction when there is a change in tension when using a magnetic recording medium, and as a result, a dimensional change in the width direction due to Poisson's ratio is likely to be caused. . When the Young's modulus in the longitudinal direction exceeds the upper limit, it is difficult to maintain the Young's modulus in the width direction within the range, and it becomes difficult to keep the contact state with the head stable. The more preferable Young's modulus in the width direction of the support is 9 to 18 GPa, particularly preferably 10 to 16 GPa. When the Young's modulus in the width direction of the support is less than the lower limit, the contact state with the magnetic head becomes unstable, and the electromagnetic conversion characteristics are likely to deteriorate. When the Young's modulus in the width direction of the support exceeds the upper limit, it is difficult to achieve the preferable Young's modulus range in the longitudinal direction of the support.
支持体の長手方向のヤング率（ＹＭＤ）と幅方向のヤング率（ＹＴＤ）の比、ＹＭＤ／ＹＴＤは０．５〜１．０であることが、上述のヘッドとの安定接触と、張力変動による長手方向の変形抑制を両立できる点から好ましい。より好ましいＹＭＤ／ＹＴＤの範囲は０．５５〜０．９、特に好ましくは０．６〜０．８である。 The ratio of the Young's modulus (YMD) in the longitudinal direction of the support to the Young's modulus (YTD) in the width direction, YMD / YTD being 0.5 to 1.0 is stable contact with the above-mentioned head and fluctuation in tension. It is preferable from the viewpoint that both can prevent deformation in the longitudinal direction. A more preferable range of YMD / YTD is 0.55 to 0.9, particularly preferably 0.6 to 0.8.
本発明の磁気記録媒体用支持体は、その幅方向の温度膨張係数が、４ｐｐｍ／℃以下〜−５ｐｐｍ／℃以上の範囲にあることが好ましい。より好ましい磁気記録媒体用支持体の幅方向の温度膨張係数は、上限が３ｐｍ／℃以下であり、下限が−４ｐｐｍ／℃以上、さらに−３ｐｐｍ／℃以上である。一般的に磁気記録装置に用いられている磁気ヘッドの温度膨張係数は７ｐｐｍ／℃前後である。支持体の幅方向の温度膨張係数が４ｐｍ／℃以上の場合には、磁気テープとしたときの幅方向の温度膨張が磁気ヘッドの温度膨張よりも大きくなりすぎるため、磁気データを記録・再生する環境が低温から高温に変化した際に、テープの幅方向に磁気ヘッドに対して相対的に膨張し、再生不良を起こしやすい。また、支持体幅方向の温度膨張係数が−５ｐｐｍ／℃より小さい場合には、フィルムの温度膨張が磁気ヘッドの温度膨張よりも小さすぎるため、低温から高温に変化した際に、テープの幅方向に磁気ヘッドに対して相対的に収縮し、再生不良を起こしやすくなる。 The support for a magnetic recording medium of the present invention preferably has a temperature expansion coefficient in the width direction of 4 ppm / ° C. or less to −5 ppm / ° C. or more. A more preferable temperature expansion coefficient in the width direction of the support for a magnetic recording medium has an upper limit of 3 pm / ° C. or lower, a lower limit of −4 ppm / ° C. or higher, and further −3 ppm / ° C. or higher. Generally, the temperature expansion coefficient of a magnetic head used in a magnetic recording apparatus is around 7 ppm / ° C. When the temperature expansion coefficient in the width direction of the support is 4 pm / ° C. or more, the temperature expansion in the width direction of the magnetic tape is too large than the temperature expansion of the magnetic head, so that magnetic data is recorded / reproduced. When the environment changes from a low temperature to a high temperature, the tape expands relative to the magnetic head in the width direction of the tape and easily causes a reproduction failure. When the temperature expansion coefficient in the width direction of the support is smaller than −5 ppm / ° C., the temperature expansion of the film is too small than the temperature expansion of the magnetic head. In other words, the magnetic head contracts relatively to the magnetic head, which tends to cause a reproduction failure.
このような幅方向の温度膨張係数は、Ｍ層の材質や厚み、さらにＭ層を設けるＦ層の幅方向の温度膨張係数とヤング率によって調整できる。具体的には、Ｆ層の幅方向の温度膨張係数は、その方向の分子鎖の配向を高めること、すなわち延伸倍率を高くすることなどによって小さく小さくすることができる。そして、Ｍ層はＦ層と比較して非常に大きな値のヤング率を有しており、また材質によっては大きな温度膨張係数を有することから、使用するＦ層の温度膨張係数がマイナスサイドにある場合は、温度膨張係数の大きなＭ層を使用したり、Ｍ層の厚みを厚くし、他方使用するＦ層の温度膨張係数がさほどマイナスサイドにない場合は、温度膨張係数の小さなＭ層を使用したり、Ｍ層の厚みを薄くするなど組合せによる最適化も可能である。 The temperature expansion coefficient in the width direction can be adjusted by the material and thickness of the M layer, and the temperature expansion coefficient in the width direction of the F layer in which the M layer is provided and the Young's modulus. Specifically, the temperature expansion coefficient in the width direction of the F layer can be made small and small by increasing the orientation of molecular chains in that direction, that is, by increasing the draw ratio. The M layer has a very large Young's modulus compared to the F layer, and has a large temperature expansion coefficient depending on the material, so that the temperature expansion coefficient of the F layer used is on the negative side. If the M layer with a large temperature expansion coefficient is used, or if the thickness of the M layer is increased and the temperature expansion coefficient of the F layer to be used is not so negative, use the M layer with a small temperature expansion coefficient. It is also possible to optimize by a combination such as reducing the thickness of the M layer.
本発明の磁気記録媒体用支持体の磁性層を形成する側の表面は、表面粗さＲａ（ｍ）が１〜５ｎｍが好ましく、より好ましくは２〜４．５ｎｍであることが好ましい。Ｒａ（ｍ）が５ｎｍより大きい場合には、高密度磁気記録媒体として十分な電磁変換特性を得られない場合がある。また、Ｒａ（ｍ）が１ｎｍより小さい場合には、搬送工程や、テープ走行中に、搬送不良のトラブルを引き起こしたり、走行面の突起が転写したり、走行中にゴミによる傷が付きやすくなったりする。このような磁気記録媒体用支持体の表面粗さは、Ｆ層の表面粗さやＭ層の厚さで制御することが可能である。Ｒａ（ｍ）を好ましい範囲に制御するためには、Ｆ層の一方の表面粗さは、１〜７ｎｍが好ましく、より好ましくは、２〜５ｎｍである。上記範囲を外れる場合には、搬送性不良、電磁変換特性の低下を招くことがある。Ｍ層の厚みは前記のとおりであり、厚みが厚いほど、表面が粗くなりやすい。 The surface on the side on which the magnetic layer of the support for magnetic recording media of the present invention is formed preferably has a surface roughness Ra (m) of 1 to 5 nm, more preferably 2 to 4.5 nm. When Ra (m) is larger than 5 nm, there may be a case where sufficient electromagnetic conversion characteristics as a high-density magnetic recording medium cannot be obtained. Further, when Ra (m) is smaller than 1 nm, troubles of conveyance failure are caused during the conveyance process or tape traveling, protrusions on the traveling surface are transferred, and dust is easily damaged during traveling. Or The surface roughness of such a magnetic recording medium support can be controlled by the surface roughness of the F layer and the thickness of the M layer. In order to control Ra (m) within a preferable range, one surface roughness of the F layer is preferably 1 to 7 nm, and more preferably 2 to 5 nm. When it is out of the above range, it may cause poor transportability and deterioration of electromagnetic conversion characteristics. The thickness of the M layer is as described above, and the thicker the thickness is, the easier the surface becomes.
本発明の磁気記録媒体用支持体の磁性層を形成しない側の表面は、表面粗さＲａ（ｂ）が３〜２０ｎｍが好ましく、より好ましくは４〜１５ｎｍ特に好ましくは５〜１２ｎｍである。Ｒａ（ｂ）が２０ｎｍより大きい場合には、保存中に磁性面側へ転写が起こり、磁性面側の表面粗さが粗くなることがある。また、Ｒａ（ｂ）が３ｎｍより小さい場合には、テープの走行性が低下し、ドライブ中で走行不良を引き起こすことがある。このような磁気記録媒体用支持体の磁性層を形成しない側の表面粗さは、Ｍ層を形成しない場合はＦ層の表面粗さであり、Ｍ層を形成する場合はＭ層を形成するＦ層の表面粗さやＭ層の厚さで制御することが可能である。Ｒａ（ｂ）を好ましい範囲に制御するためには、Ｆ層のもう一方の表面粗さは、５〜１５ｎｍが好ましく、より好ましくは、６〜１０ｎｍである。上記範囲を外れる場合には、搬送性不良、平面性の悪化を招くことがある。また、磁気記録媒体用支持体の磁性層を形成しない側の表面にＭ層を形成する場合の厚みは、前記の磁気記録媒体用支持体の磁性層を形成する側の表面でsつ瞑したのと同様なことが言え、厚みが厚いほど、表面が粗くなりやすい。 The surface of the support for a magnetic recording medium of the present invention on the side where the magnetic layer is not formed has a surface roughness Ra (b) of preferably 3 to 20 nm, more preferably 4 to 15 nm, and particularly preferably 5 to 12 nm. When Ra (b) is larger than 20 nm, transfer may occur to the magnetic surface side during storage, and the surface roughness on the magnetic surface side may become rough. On the other hand, when Ra (b) is smaller than 3 nm, the running performance of the tape is lowered, and running failure may occur in the drive. The surface roughness of the magnetic recording medium support on the side where the magnetic layer is not formed is the surface roughness of the F layer when the M layer is not formed, and the M layer is formed when the M layer is formed. It can be controlled by the surface roughness of the F layer and the thickness of the M layer. In order to control Ra (b) within a preferable range, the other surface roughness of the F layer is preferably 5 to 15 nm, and more preferably 6 to 10 nm. When it is out of the above range, poor transportability and poor flatness may be caused. Further, the thickness of the M layer formed on the surface of the magnetic recording medium support on which the magnetic layer is not formed is adjusted to the thickness on the surface of the magnetic recording medium support on which the magnetic layer is formed. The same can be said, and the thicker the thickness, the more likely the surface becomes rough.
本発明の磁気記録媒体用支持体の全厚みは、２．０〜８μｍが好ましい。より好ましくは２．５〜７μｍ、さらに好ましくは３〜６μｍ、特に好ましくは３．５〜５．５μｍである。厚みが２．０μｍより小さい場合は、テープに腰がなくなるため、電磁変換特性が低下する。厚みが７μｍを超える場合は、テープ１巻あたりのテープ長さが短くなるため、磁気テープの小型化、高容量化が困難になりやすい。そのような観点から、好ましいＦ層の厚みは、２〜８μｍが好ましく、より好ましくは２．５〜７μｍ、さらに好ましくは３〜６μｍ、特に好ましくは３．５〜５．５μｍである。 The total thickness of the magnetic recording medium support of the present invention is preferably 2.0 to 8 μm. More preferably, it is 2.5-7 micrometers, More preferably, it is 3-6 micrometers, Most preferably, it is 3.5-5.5 micrometers. When the thickness is smaller than 2.0 μm, the tape loses its elasticity, so that the electromagnetic conversion characteristics are deteriorated. When the thickness exceeds 7 μm, since the tape length per one tape is shortened, it is difficult to reduce the size and increase the capacity of the magnetic tape. From such a viewpoint, the thickness of the F layer is preferably 2 to 8 μm, more preferably 2.5 to 7 μm, still more preferably 3 to 6 μm, and particularly preferably 3.5 to 5.5 μm.
本発明の磁気記録媒体用支持体は、高い寸法安定性を必要とする塗布型のデジタル記録方式の磁気記録テープの支持体として好ましく用いられる。中でも、データストレージ用高密度磁気記録用テープやデジタルビデオテープなどの支持体に特に適したものである。 The support for a magnetic recording medium of the present invention is preferably used as a support for a coating type digital recording magnetic recording tape that requires high dimensional stability. Among them, it is particularly suitable for a support such as a high-density magnetic recording tape for data storage or a digital video tape.
本発明の磁気記録媒体用支持体を用いた磁気記録テープとしては、磁性層−非磁性層−支持体―バックコート層がこの順で積層されたものあることが好ましく、磁性層の表面をより高度に平坦にしやすいことから、非磁性層の厚みは０．９〜１．１μｍ、磁性層の厚みは０．０５〜０．２５μｍの範囲にあることが好ましい。また、磁気記録テープの走行性を高度に発現させやすいことから、バックコート層の厚みは０．３〜０．７μｍの範囲にあることが好ましい。特に本発明の効果の点からは、磁気記録テープ中に占めるコート層（磁性層、非磁性層、バックコート層など）の厚みの割合は、１５〜３５％、さらに２２〜３０％の範囲にあることが好ましい。コート層の厚みが下限未満では、非磁性層などの厚みが薄くなり、磁性層の平坦化向上効果が乏しくなりやすく、他方上限を超えると寸法安定性の向上効果が損なわれやすくなる。 The magnetic recording tape using the magnetic recording medium support of the present invention preferably has a magnetic layer-nonmagnetic layer-support-backcoat layer laminated in this order. It is preferable that the nonmagnetic layer has a thickness of 0.9 to 1.1 μm and the magnetic layer has a thickness of 0.05 to 0.25 μm because it is highly flat. Further, the back coat layer preferably has a thickness in the range of 0.3 to 0.7 [mu] m because the traveling property of the magnetic recording tape is easily expressed. In particular, from the viewpoint of the effect of the present invention, the ratio of the thickness of the coating layer (magnetic layer, nonmagnetic layer, backcoat layer, etc.) in the magnetic recording tape is in the range of 15 to 35%, and further 22 to 30%. Preferably there is. If the thickness of the coat layer is less than the lower limit, the thickness of the non-magnetic layer and the like is reduced, and the flattening improvement effect of the magnetic layer tends to be poor. On the other hand, if the upper limit is exceeded, the improvement effect of dimensional stability is easily lost.
以下、本発明の磁気記録媒体用支持体の製造方法について説明する。
まず、前述の方法で作成したＦ層にＭ層を設ける。なお、ここでは、真空蒸着法を用いたＭ層の製造方法の例を挙げる。
Hereinafter, a method for producing the magnetic recording medium support of the present invention will be described.
First, the M layer is provided on the F layer prepared by the method described above. Here, an example of the manufacturing method of the M layer using the vacuum deposition method will be given.
真空蒸着装置内に設置されたフィルム走行装置に、ポリエステルフィルムをセットし、真空蒸着を行う。１．００×１０−５〜１．００×１０−１Ｐａの高真空で蒸着することが好ましい。０〜５０℃の冷却金属ドラムを介して、走行させ、蒸着物を加熱蒸発させ、フィルムの両面に形成して巻取る。フィルム走行速度は、１０〜２００ｍ／分が好ましく、より好ましくは、５０〜１５０ｍ／分である。走行速度が上記範囲を外れる場合には、Ｍ層の厚みを好ましい範囲に設定することが困難となったり、生産性が劣る場合がある。Ｆ層の両側にＭ層を設ける場合には、同一の真空層内に２つの加熱蒸着装置と冷却ドラムを設けて、１パスで両面を蒸着することが好ましいが、一度片面に蒸着を行ない、巻き取った後に、再びもう一方の面にＭ層を設ける２パスで行っても良い。２パスの場合は勿論であるが、１パスの場合でも、Ｍ層を設ける順序としては、磁性層側、バックコート層側とした方が、カッピングを抑制できるため好ましい。 A polyester film is set on a film running device installed in a vacuum deposition apparatus, and vacuum deposition is performed. It is preferable to deposit in a high vacuum of 1.00 × 10 −5 to 1.00 × 10 −1 Pa. It is made to travel through a cooling metal drum of 0 to 50 ° C., the deposited material is heated and evaporated, and is formed and wound on both surfaces of the film. The film running speed is preferably 10 to 200 m / min, and more preferably 50 to 150 m / min. When the traveling speed is out of the above range, it may be difficult to set the thickness of the M layer within a preferable range, or productivity may be inferior. When providing the M layer on both sides of the F layer, it is preferable to provide two heating vapor deposition devices and a cooling drum in the same vacuum layer and deposit both sides in one pass, but once vapor deposition is performed on one side, After winding, it may be performed by two passes in which an M layer is provided on the other surface again. Of course, in the case of two passes, even in the case of one pass, the order of providing the M layer is preferably the magnetic layer side and the back coat layer side because cupping can be suppressed.
さらに、上記の方法で磁気記録媒体支持体を作製した後、エージング処理を行うことが、クリープ変形を抑制し、寸法安定性を向上するために好ましい。処理温度は１００〜１２０℃が好ましく、処理時間は１０〜４０時間が好ましく、より好ましくは、１５〜２０時間である。上記、エージング処理の好ましい条件のなかでも、処理温度が短い場合は処理時間を長くとる方が好ましいし、処理温度が比較的高めの場合には処理時間は短い方がよい。この温度と時間の両方に関係する処理条件は、示差走査熱量測定（ＤＳＣ）によって得られる磁気記録媒体のエンタルピー緩和のピーク面積を指標として表すことができ、ピーク面積ΔＨは、０．５Ｊ／ｇ〜１Ｊ／ｇが好ましい。 Furthermore, after producing a magnetic recording medium support by the above method, it is preferable to perform an aging treatment in order to suppress creep deformation and improve dimensional stability. The treatment temperature is preferably from 100 to 120 ° C., and the treatment time is preferably from 10 to 40 hours, more preferably from 15 to 20 hours. Among the preferable conditions for the aging process, it is preferable to increase the processing time when the processing temperature is short, and it is preferable that the processing time is short when the processing temperature is relatively high. The processing conditions related to both temperature and time can be expressed by using the peak area of enthalpy relaxation of the magnetic recording medium obtained by differential scanning calorimetry (DSC) as an index, and the peak area ΔH is 0.5 J / g. ~ 1 J / g is preferred.
エージング処理は、Ｆ層を作製した後、Ｍ層を設ける前に行うことも可能であるが、この場合、Ｆ層の長手方向の熱収縮率が低くなり、蒸着工程でキャンとの密着が低下して、表面が粗くなったり、オリゴマーがフィルム表面に析出して、蒸着工程トラブルを引き起こしやすい。このため、エージング処理は、Ｍ層を設けた後に行う方が好ましい。 The aging treatment can be performed after the F layer is formed and before the M layer is provided, but in this case, the thermal contraction rate in the longitudinal direction of the F layer is lowered, and the adhesion with the can is reduced in the vapor deposition process. Then, the surface becomes rough or oligomers are deposited on the film surface, which easily causes trouble in the vapor deposition process. For this reason, it is preferable to perform the aging treatment after providing the M layer.
以下に実施例及び比較例を挙げ、本発明をより具体的に説明する。なお、本発明におけるポリエステル、ポリエステルフィルムおよびデータストレージの特性は、下記の方法で測定および評価した。 Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. In addition, the characteristic of the polyester in this invention, the polyester film, and data storage was measured and evaluated by the following method.
（１）固有粘度
得られたポリエステルの固有粘度は、前述のとおり、ｏ-クロロフェノール、３５℃で測定し、ｏ−クロロフェノールでは均一に溶解するのが困難な場合は、Ｐ−クロロフェノール／１，１，２，２−テトラクロロエタン（４０／６０重量比）の混合溶媒を用いて３５℃で測定して求めた。
(1) Intrinsic viscosity As described above, the intrinsic viscosity of the obtained polyester is measured at o-chlorophenol at 35 ° C. When it is difficult to dissolve uniformly with o-chlorophenol, P-chlorophenol / It was determined by measurement at 35 ° C. using a mixed solvent of 1,1,2,2-tetrachloroethane (40/60 weight ratio).
（２）第１および第２フィルターのろ過精度
試験粉体のガラスビーズ（ＪＩＳ−Ｚ８９０１：２００６記載）を蒸留水中に分散させ、フィルターろ過前後の粒度分布の変化を測定し、９５％カット値を持ってろ過精度とする。
(2) Filtration accuracy of first and second filters Disperse test powder glass beads (described in JIS-Z8901: 2006) in distilled water, measure the change in particle size distribution before and after filter filtration, and determine the 95% cut value. Take it with filtration accuracy.
（３）粗大突起の数
フィルムサンプルをゴミなどが入らないように注意しつつ石英オプティカルフラットに重ね、オプティカルフラット側から２６０ｎｍ付近に最短波長ピークを有する水銀ランプを中心波長２６０ｎｍのバンドパスフィルターを通して照射した。そして、ＵＶ−ＣＤＤカメラで干渉縞から観測される粗大突起の数を確認した。測定は、面積２５ｃｍ２について行い、１００ｃｍ２当りの個数に換算した。
(3) Number of coarse protrusions A film sample is superimposed on a quartz optical flat while being careful not to enter dust, and a mercury lamp having the shortest wavelength peak near 260 nm from the optical flat side is irradiated through a bandpass filter having a central wavelength of 260 nm. did. Then, the number of coarse protrusions observed from the interference fringes was confirmed with a UV-CDD camera. The measurement was performed for an area of 25 cm 2 and converted to the number per 100 cm 2 .
（４）中心面平均粗さ（Ｒａ）
非接触式三次元表面粗さ計（ＺＹＧＯ社製：Ｎｅｗ Ｖｉｅｗ５０２２）を用いて測定倍率２５倍、測定面積２８３μｍ×２１３μｍ（＝０．０６０３ｍｍ２）の条件にて測定し、該粗さ計に内蔵された表面解析ソフトＭｅｔｒｏＰｒｏにより中心面平均粗さ（Ｒａ）を求めた。
(4) Center plane average roughness (Ra)
Measured using a non-contact type three-dimensional surface roughness meter (manufactured by ZYGO: New View 5022) at a measurement magnification of 25 times and a measurement area of 283 μm × 213 μm (= 0.0603 mm 2 ), and incorporated in the roughness meter The center plane average roughness (Ra) was determined by the surface analysis software MetroPro.
（５）不活性粒子の平均粒径
添加する不活性粒子の平均粒径は、ＪＩＳ Ｚ８８２３−１に準拠する遠心沈降法で得られる粒度分布から体積分率が５０％になる点を平均粒径として算出した。
(5) Average particle diameter of inert particles The average particle diameter of the inert particles to be added is the average particle diameter at which the volume fraction becomes 50% from the particle size distribution obtained by the centrifugal sedimentation method according to JIS Z8823-1. Calculated as
（６）ガラス転移点および融点
ガラス転移点、融点はＤＳＣ（ＴＡインスツルメンツ株式会社製、商品名：Ｔｈｅｒｍａｌ Ａｎａｌｙｓｔ２１００）により昇温速度２０℃／ｍｉｎで測定した。
(6) Glass transition point and melting point The glass transition point and melting point were measured by DSC (TA Instruments Co., Ltd., trade name: Thermal Analyst 2100) at a heating rate of 20 ° C / min.
（７）ヤング率
得られたＦ層および磁気記録媒体支持体を試料巾１０ｍｍ、長さ１５ｃｍで切り取り、チャック間１００ｍｍ、引張速度１０ｍｍ／分、チャート速度５００ｍｍ／分の条件で万能引張試験装置（東洋ボールドウィン製、商品名：テンシロン）にて引っ張る。得られた荷重―伸び曲線の立ち上がり部の接線よりヤング率を計算する。
(7) Young's modulus The obtained F layer and the magnetic recording medium support were cut out with a sample width of 10 mm and a length of 15 cm, and a universal tensile testing apparatus (100 mm between chucks, tensile speed of 10 mm / min, chart speed of 500 mm / min) Pull with Toyo Baldwin (trade name: Tensilon). The Young's modulus is calculated from the tangent of the rising portion of the obtained load-elongation curve.
（８）温度膨張係数（αｔ）
磁気記録媒体支持体を、幅方向が測定方向となるように幅４ｍｍのサンプルを切り出し、チャック間長さ２０ｍｍとなるように、セイコーインスツル製ＴＭＡ／ＳＳ６０００にセットし、窒素雰囲気下（０％ＲＨ）、８０℃で３０分前処理し、その後室温まで降温させた。その後３０℃から８０℃まで２℃／ｍｉｎで昇温して、各温度でのサンプル長を測定し、次式より温度膨張係数（αｔ）を算出した。なお、測定方向が切り出した試料の長手方向であり、５回測定し、その平均値を用いた。
αｔ＝｛（Ｌ６０−Ｌ４０）｝／（Ｌ４０×△Ｔ）｝＋０．５×１０−６
ここで、上記式中のＬ４０は４０℃のときのサンプル長（ｍｍ）、Ｌ６０は６０℃のときのサンプル長（ｍｍ）、△Ｔは２０（＝６０−４０）℃、０．５×１０−６／℃は石英ガラスの温度膨張係数（αｔ）である。
(8) Temperature expansion coefficient (αt)
A sample with a width of 4 mm is cut out from the magnetic recording medium support so that the width direction is the measurement direction, and is set on a TMA / SS6000 made by Seiko Instruments so that the length between chucks is 20 mm. RH), pre-treatment at 80 ° C. for 30 minutes, and then cooled to room temperature. Thereafter, the temperature was raised from 30 ° C. to 80 ° C. at 2 ° C./min, the sample length at each temperature was measured, and the temperature expansion coefficient (αt) was calculated from the following equation. In addition, the measurement direction is the longitudinal direction of the sample cut out, the measurement was performed 5 times, and the average value was used.
αt = {(L60−L40)} / (L40 × ΔT)} + 0.5 × 10 −6
Here, L40 in the above formula is a sample length (mm) at 40 ° C., L60 is a sample length (mm) at 60 ° C., ΔT is 20 (= 60-40) ° C., 0.5 × 10 −6 / ° C. is the temperature expansion coefficient (αt) of quartz glass.
（９）湿度膨張係数（αｈ）
磁気記録媒体支持体を、幅方向が測定方向となるように幅５ｍｍのサンプルを切り出し、チャック間長さ１５ｍｍとなるように、ブルカーＡＸＳ製ＴＭＡ４０００ＳＡにセットし、３０℃の窒素雰囲気下で、湿度２０％ＲＨと湿度８０％ＲＨにおけるそれぞれのサンプルの長さを測定し、次式にて湿度膨張係数（αｈ）を算出した。なお、測定方向が切り出した試料の長手方向であり、５回測定し、その平均値をαｈとした。
αｈ＝（Ｌ８０−Ｌ２０）／（Ｌ２０×△Ｈ）
ここで、上記式中のＬ２０は２０％ＲＨのときのサンプル長（ｍｍ）、Ｌ８０は８０％ＲＨのときのサンプル長（ｍｍ）、△Ｈ：６０（＝８０−２０）％ＲＨである。
(9) Humidity expansion coefficient (αh)
A magnetic recording medium support was cut out of a sample having a width of 5 mm so that the width direction was the measurement direction, set to TMA4000SA made by Bruker AXS so that the length between chucks was 15 mm, and the humidity was measured in a nitrogen atmosphere at 30 ° C. The length of each sample at 20% RH and humidity 80% RH was measured, and the humidity expansion coefficient (αh) was calculated by the following equation. In addition, the measurement direction is the longitudinal direction of the cut out sample, the measurement was performed 5 times, and the average value was αh.
αh = (L80−L20) / (L20 × ΔH)
Here, L20 in the above formula is the sample length (mm) at 20% RH, L80 is the sample length (mm) at 80% RH, and ΔH: 60 (= 80-20)% RH.
（１０）磁気テープの寸法安定性
１ｍ幅にスリットした支持体を、張力２０ｋｇ／ｍで搬送させ、フィルムの平滑面側の表面に下記組成の磁性塗料および非磁性塗料をエクストルージョンコーターにより重層塗布（上層は磁性塗料で、塗布厚０．１μｍ、非磁性下層の厚みは１．０μｍとした。）し、磁気配向させ、乾燥温度１００℃で乾燥させる。次いで反対面に下記組成のバックコートを固形分の厚みが０．５μｍとなるように塗布した後、小型テストカレンダー装置（スチール／ナイロンロール、５段）で、温度８５℃、線圧２００ｋｇ／ｃｍでカレンダー処理し、巻き取る。上記テープ原反を１／２インチ幅にスリットし、それをＬＴＯ用のケースに組み込み、長さが８５０ｍで磁気記録容量が０．８ＴＢのデータストレージカートリッジを作成した。
(10) Dimensional stability of magnetic tape
A support slit to a width of 1 m is conveyed with a tension of 20 kg / m, and a magnetic coating and a non-magnetic coating having the following composition are applied to the surface on the smooth surface side of the film with an extrusion coater (the upper layer is a magnetic coating and the coating thickness is 0.1 μm and the thickness of the non-magnetic lower layer was 1.0 μm), magnetically oriented, and dried at a drying temperature of 100 ° C. Next, a back coat having the following composition was applied to the opposite surface so that the solid content had a thickness of 0.5 μm, and then a small test calender (steel / nylon roll, 5 steps) at a temperature of 85 ° C. and a linear pressure of 200 kg / cm. Calendar and roll up. The original tape was slit into a 1/2 inch width and incorporated into an LTO case to produce a data storage cartridge having a length of 850 m and a magnetic recording capacity of 0.8 TB.
（非磁性塗料の組成）
・非磁性無機質粉末（α−酸化鉄：平均長軸長：０．１５μｍ，平均針状比：７，ＢＥＴ比表面積：５２ｍ２／ｇ）：１００重量部
・エスレックＡ（積水化学製塩化ビニル／酢酸ビニル共重合体：１０重量部
・ニッポラン２３０４（日本ポリウレタン製ポリウレタンエラストマ）：１０重量部
・コロネートＬ（日本ポリウレタン製ポリイソシアネート）：５重量部
・レシチン：１重量部
・メチルエチルケトン：７５重量部
・メチルイソブチルケトン：７５重量部
・トルエン：７５重量部
・カーボンブラック（平均粒子径：２０ｎｍ）：２重量部
・ラウリン酸：１．５重量部
(Composition of non-magnetic paint)
Nonmagnetic inorganic powder (α-iron oxide: average major axis length: 0.15 μm, average needle ratio: 7, BET specific surface area: 52 m 2 / g): 100 parts by weight Vinyl acetate copolymer: 10 parts by weight-Nipporan 2304 (polyurethane elastomer made by Nippon Polyurethane): 10 parts by weight-Coronate L (polyisocyanate made by Nippon Polyurethane): 5 parts by weight-Lecithin: 1 part by weight-Methyl ethyl ketone: 75 parts by weight- Methyl isobutyl ketone: 75 parts by weight Toluene: 75 parts by weight Carbon black (average particle size: 20 nm): 2 parts by weight Lauric acid: 1.5 parts by weight
（磁性塗料の組成）
・磁性粉（戸田工業株式会社製、商品名：ＮＦ３０ｘ）：１００重量部
・エスレックＡ（積水化学製塩化ビニル／酢酸ビニル共重合体）：１０重量部
・ニッポラン２３０４（日本ポリウレタン製ポリウレタンエラストマ）：１０重量部
・コロネートＬ（日本ポリウレタン製ポリイソシアネート）：５重量部
・レシチン： １重量部
・メチルエチルケトン：７５重量部
・メチルイソブチルケトン：７５重量部
・トルエン：７５重量部
・カーボンブラック（平均粒子径：２０ｎｍ）：２重量部
・ラウリン酸：１．５重量部
(Composition of magnetic paint)
Magnetic powder (manufactured by Toda Kogyo Co., Ltd., trade name: NF30x): 100 parts by weight Eslek A (vinyl chloride / vinyl acetate copolymer made by Sekisui Chemical): 10 parts by weight Nipponran 2304 (polyurethane elastomer made by Nippon Polyurethane): 10 parts by weight Coronate L (polyisocyanate made from Japanese polyurethane): 5 parts by weight Lecithin: 1 part by weight Methyl ethyl ketone: 75 parts by weight Methyl isobutyl ketone: 75 parts by weight Toluene: 75 parts by weight Carbon black (average particle size : 20 nm): 2 parts by weightLauric acid: 1.5 parts by weight
（バックコートの組成）
・カーボンブラック（平均粒径２０ｎｍ）：９５重量部
・カーボンブラック（平均粒径２８０ｎｍ）：１０重量部
・αアルミナ：０．１重量部
・変成ポリウレタン：２０重量部
・変成塩化ビニル共重合体：３０重量部
・シクロヘキサノン：２００重量部
・メチルエチルケトン：３００重量部
・トルエン：１００重量部
(Backcoat composition)
Carbon black (average particle size 20 nm): 95 parts by weight
Carbon black (average particle size 280 nm): 10 parts by weight
・ Α alumina: 0.1 parts by weight
・ Modified polyurethane: 20 parts by weight
・ Modified vinyl chloride copolymer: 30 parts by weight
・ Cyclohexanone: 200 parts by weight
・ Methyl ethyl ketone: 300 parts by weight
-Toluene: 100 parts by weight
上記、磁気テープを、恒温恒湿槽中に設置したフィルム走行装置にセットし、テープを走行させながら、下記の条件でテープの幅を測定した。
測定方法（イ） テープの幅方向熱膨張係数が７ｐｐｍ／℃以上の場合
（Ａ）張力を０．８５Ｎに変更し、温湿度条件を、１０℃１０％ＲＨに変更し（設定条件までは１時間で到達）、１０℃１０％ＲＨ条件で２３時間保持した。テープ幅は温度変更開始後３時間（放置後２時間）の時点で観測した。
（Ｂ）次に、張力を０．５５Ｎに変更し、湿度条件を、３０℃８０％ＲＨに変更し（設定条件までは１時間で到達）、同様に２３時間保持した。テープ幅は温度変更開始後３時間（放置後２時間）の時点で観測した。
（Ｃ）上記（Ａ）→（Ｂ）→（Ａ）→（Ｂ）→（Ａ）→（Ｂ）と工程を連続して繰り返し行ない、それぞれテープ幅を測定した。
上記の６点の中でのテープ幅の最大値と最小値の差を、１２．６５（ｍｍ）で割り、ｐｐｍ単位に変換（１，０００，０００倍する）し、さらに磁気ヘッドの温度変化分７ｐｐｍ／℃に測定温度差（３０−１０＝２０℃）を乗じた数値である１４０ｐｐｍを減じたものを、テープの相対的な幅変化とした。
The magnetic tape was set in a film running device installed in a constant temperature and humidity chamber, and the width of the tape was measured under the following conditions while running the tape.
Measurement method (a) When the thermal expansion coefficient in the width direction of the tape is 7 ppm / ℃ or more
(A) The tension was changed to 0.85 N, and the temperature and humidity conditions were changed to 10 ° C. and 10% RH (the setting conditions were reached in 1 hour), and the conditions were maintained at 10 ° C. and 10% RH for 23 hours. The tape width was observed at 3 hours after the start of temperature change (2 hours after standing).
(B) Next, the tension was changed to 0.55 N, and the humidity condition was changed to 30 ° C. and 80% RH (the setting condition was reached in 1 hour), and similarly held for 23 hours. The tape width was observed at 3 hours after the start of temperature change (2 hours after standing).
(C) The above steps (A) → (B) → (A) → (B) → (A) → (B) were repeated continuously, and the tape width was measured.
The difference between the maximum value and the minimum value of the tape width among the above six points is divided by 12.65 (mm), converted to ppm units (1,000,000 times), and the temperature change of the magnetic head The relative width change of the tape was obtained by subtracting 140 ppm, which is a value obtained by multiplying the measured temperature difference (30-10 = 20 ° C.) by 7 ppm / ° C. per minute.
測定方法（ロ） テープの幅方向温度膨張係数が７ｐｐｍ／℃未満の場合
上記測定方法（イ）の（Ａ）の温湿度条件を４５℃１０％ＲＨ、Ｂ）の温湿度条件を１０℃８０％ＲＨ とし、磁気ヘッドの温度変化分７ｐｐｍ／℃に測定温度差（４５−１０＝３５℃）を乗じた数値である２４５ｐｐｍを加算したものをテープの相対的な寸法変化量とした。
そして、上記（イ）もしくは（ロ）の評価で得られた相対的な寸法変化量を寸法安定性とした。なお、寸法安定性は、小さいほど良好であることを意味する。
Measurement method (b) When the temperature expansion coefficient in the width direction of the tape is less than 7 ppm / ° C. The temperature and humidity condition of (A) in the measurement method (A) is 45 ° C. and 10% RH, and the temperature and humidity condition of B) is 10 ° C. % RH, and a value obtained by adding 245 ppm, which is a value obtained by multiplying the measured temperature difference (45-10 = 35 ° C.) by 7 ppm / ° C. of the temperature change of the magnetic head, was used as the relative dimensional change amount of the tape.
Then, the relative dimensional change obtained by the evaluation of the above (A) or (B) was defined as dimensional stability. The smaller the dimensional stability, the better.
（１１）ドロップアウト（ＤＯ）
上記（１０）で作成されたデータストレージカートリッジを、ＩＢＭ社製ＬＴＯ４ドライブ（記録ヘッドはインダクティブヘッド、再生ヘッドはＭＲヘッドを搭載）に装填してデータ信号を１４ＧＢ記録し、それを再生した。平均信号振幅に対して５０％以下の振幅（Ｐ−Ｐ値）の信号をミッシングパルスとし、４個以上連続したミッシングパルスをドロップアウトとして検出した。なお、ドロップアウトは８５０ｍ長１巻を評価し、１ｍ当たりの個数に換算した。ドロップアウトは、少ないほど優れた特性であることを意味する。
(11) Dropout (DO)
The data storage cartridge created in (10) above was loaded into an IBM LTO4 drive (recording head equipped with an inductive head and playback head equipped with an MR head) to record a data signal of 14 GB and reproduce it. A signal having an amplitude (PP value) of 50% or less with respect to the average signal amplitude was detected as a missing pulse, and four or more consecutive missing pulses were detected as dropouts. In addition, dropout evaluated 1 volume of 850m length, and converted into the number per 1m. The smaller the dropout, the better the characteristics.
［参考例１］樹脂１の作成
蒸留による精製を繰り返した２，６−ナフタレンジカルボン酸ジメチルエステルとエチレングリコールとをそれぞれ１００部と７０部用意し、それらを攪拌機、精留塔、冷却器を供えた反応槽に仕込み、１５０℃まで昇温した。その後、トリメリット酸チタンをＴｉ元素量として、全ジカルボン酸成分のモル数に対して７ｍｍｏｌ％となるように添加し、反応槽全体を窒素により０．２５ＭＰａの圧力下で加熱して、反応槽内部温度を２４０℃に昇温した。反応の進行に従い、圧力一定のまま内温を２５０℃まで上げた。その後、反応槽内の圧力を常圧にゆっくりと戻し、トリメチルホスフェートをリン元素量で、全ジカルボン酸成分のモル数に対して１２ｍｍｏｌ％となるように添加し、余剰のエチレングリコールを追い出して、エステル交換反応を終了させた。
得られた反応生成物を重合反応槽へと移送した。このとき、移送途中で９５％ろ過精度５μｍの金属繊維製のフィルターを通してろ過した。重合反応槽では２５０℃からゆっくりと昇温しながら、また減圧させながら重縮合反応を行い、最終的に２９０℃、３０Ｐａで所定の重合度になるまで重縮合を行い、実質的に不活性粒子を含有しない、固有粘度０.６ｄｌ／ｇのポリエチレン−２，６−ナフタレートを得た。
[Reference Example 1] Preparation of Resin 1 100 parts and 70 parts of 2,6-naphthalenedicarboxylic acid dimethyl ester and ethylene glycol, each of which was repeatedly purified by distillation, were prepared and provided with a stirrer, a rectifying column, and a cooler. The reaction vessel was charged and heated to 150 ° C. Thereafter, titanium trimellitic acid as Ti element amount was added so as to be 7 mmol% with respect to the number of moles of all dicarboxylic acid components, and the whole reaction vessel was heated with nitrogen under a pressure of 0.25 MPa, The internal temperature was raised to 240 ° C. As the reaction progressed, the internal temperature was increased to 250 ° C. with the pressure kept constant. Thereafter, the pressure in the reaction vessel is slowly returned to normal pressure, trimethyl phosphate is added in an amount of phosphorus element so as to be 12 mmol% with respect to the number of moles of the total dicarboxylic acid component, and excess ethylene glycol is driven out. The transesterification reaction was terminated.
The obtained reaction product was transferred to a polymerization reaction tank. At this time, it was filtered through a metal fiber filter with 95% filtration accuracy of 5 μm during transfer. In the polymerization reaction tank, the polycondensation reaction is carried out while slowly raising the temperature from 250 ° C. while reducing the pressure, and finally the polycondensation is carried out at 290 ° C. and 30 Pa until a predetermined polymerization degree is obtained. Thus, polyethylene-2,6-naphthalate having an intrinsic viscosity of 0.6 dl / g was obtained.
［参考例２］樹脂２の作成
蒸留による精製を繰り返した２，６−ナフタレンジカルボン酸ジメチルエステルとエチレングリコールとをそれぞれ１００部と７０部用意し、それらを攪拌機、精留塔、冷却器を供えた反応槽に仕込み、１５０℃まで昇温した。その後、トリメリット酸チタンをＴｉ元素量として、全ジカルボン酸成分のモル数に対して３ｍｍｏｌ％となるように添加し、反応槽全体を窒素により０．２５ＭＰａの圧力下で加熱して、反応槽内部温度を２４０℃に昇温した。反応の進行に従い、圧力一定のまま内温を２５０℃まで上げた。その後、反応槽内の圧力を常圧にゆっくりと戻し、トリメチルホスフェートをリン元素量で、全ジカルボン酸成分のモル数に対して７ｍｍｏｌ％となるように添加し、余剰のエチレングリコールを追い出して、エステル交換反応を終了させた。
得られた反応生成物を重合反応槽へと移送した。このとき、移送途中で９５％ろ過精度５μｍの金属繊維製のフィルターを通してろ過した。重合反応槽では２５０℃からゆっくりと昇温しながら、また減圧させながら重縮合反応を行い、最終的に２９０℃、３０Ｐａで所定の重合度になるまで重縮合を行い、実質的に不活性粒子を含有しない、固有粘度０.６ｄｌ／ｇのポリエチレンテレフタレートを得た。
[Reference Example 2] Preparation of Resin 2 100 parts and 70 parts of 2,6-naphthalenedicarboxylic acid dimethyl ester and ethylene glycol, each of which was repeatedly purified by distillation, were prepared and provided with a stirrer, a rectifying column, and a cooler. The reaction vessel was charged and heated to 150 ° C. Thereafter, titanium trimellitic acid as Ti element amount was added so as to be 3 mmol% with respect to the number of moles of all dicarboxylic acid components, and the whole reaction vessel was heated with nitrogen at a pressure of 0.25 MPa, The internal temperature was raised to 240 ° C. As the reaction progressed, the internal temperature was increased to 250 ° C. with the pressure kept constant. Thereafter, the pressure in the reaction vessel is slowly returned to normal pressure, trimethyl phosphate is added in an amount of phosphorus element so as to be 7 mmol% with respect to the number of moles of all dicarboxylic acid components, and excess ethylene glycol is expelled, The transesterification reaction was terminated.
The obtained reaction product was transferred to a polymerization reaction tank. At this time, it was filtered through a metal fiber filter with 95% filtration accuracy of 5 μm during transfer. In the polymerization reaction tank, the polycondensation reaction is carried out while slowly raising the temperature from 250 ° C. while reducing the pressure, and finally the polycondensation is carried out at 290 ° C. and 30 Pa until a predetermined polymerization degree is obtained. Thus, polyethylene terephthalate having an intrinsic viscosity of 0.6 dl / g was obtained.
［参考例３］樹脂３の作成
平均粒径が０．１μｍで相対標準偏差が０．１３のアルコキシド法で作成した真球状シリカ粒子を、エチレングリコールに１０重量％となるように添加して、１００℃で２０分間過熱したのち、９５％ろ過精度５μｍの金属繊維製のフィルターを通過するように循環させて、真球状シリカ粒子の含有量が１０重量％のエチレングリコールスラリーを作成した。そして、このエチレングリコールスラリーを、エステル交換反応の段階で、真球状シリカ粒子の含有量が、得られるポリエステルの重量に対して、０．５重量％となるように添加したほかは、参考例１と同様な操作を繰り返して、樹脂３を作成した。
[Reference Example 3] Preparation of Resin 3 True spherical silica particles prepared by an alkoxide method having an average particle diameter of 0.1 μm and a relative standard deviation of 0.13 were added to ethylene glycol so as to be 10% by weight, After heating at 100 ° C. for 20 minutes, the mixture was circulated through a metal fiber filter having a 95% filtration accuracy of 5 μm to prepare an ethylene glycol slurry having a true spherical silica particle content of 10% by weight. Reference Example 1 was made except that this ethylene glycol slurry was added so that the content of the spherical silica particles was 0.5% by weight with respect to the weight of the polyester obtained at the stage of the transesterification reaction. The same operation was repeated to prepare Resin 3.
［参考例４］樹脂４の作成
平均粒径が０．１μｍで相対標準偏差が０．１３のアルコキシド法で作成した真球状シリカ粒子を、エチレングリコールに１０重量％となるように添加して、１００℃で２０分間過熱したのち、９５％ろ過精度５μｍの金属繊維製のフィルターを通過するように循環させて、真球状シリカ粒子の含有量が１０重量％のエチレングリコールスラリーを作成した。そして、このエチレングリコールスラリーを、エステル交換反応の段階で、真球状シリカ粒子の含有量が、得られるポリエステルの重量に対して、０．５重量％となるように添加したほかは、参考例２と同様な操作を繰り返して、樹脂４を作成した。
[Reference Example 4] Preparation of Resin 4 True spherical silica particles prepared by an alkoxide method having an average particle size of 0.1 μm and a relative standard deviation of 0.13 were added to ethylene glycol so as to be 10% by weight, After heating at 100 ° C. for 20 minutes, the mixture was circulated through a metal fiber filter having a 95% filtration accuracy of 5 μm to prepare an ethylene glycol slurry having a true spherical silica particle content of 10% by weight. Reference Example 2 was added except that this ethylene glycol slurry was added so that the content of the spherical silica particles was 0.5% by weight based on the weight of the polyester obtained at the stage of the transesterification reaction. The same operation was repeated to prepare Resin 4.
［参考例５］樹脂５の作成
真球状シリカ粒子を、平均粒径が０．３μｍで相対標準偏差が０．１２の真球状シリカ粒子に変更したほかは、参考例３と同様な操作を繰り返して、樹脂５を作成した。
[Reference Example 5] Preparation of Resin 5 The same operation as in Reference Example 3 was repeated except that the true spherical silica particles were changed to true spherical silica particles having an average particle size of 0.3 μm and a relative standard deviation of 0.12. Resin 5 was prepared.
［参考例６］樹脂６の作成
真球状シリカ粒子を、平均粒径が０．３μｍで相対標準偏差が０．１２の真球状シリカ粒子に変更したほかは、参考例４と同様な操作を繰り返して、樹脂６を作成した。
Reference Example 6 Preparation of Resin 6 The same operation as in Reference Example 4 was repeated except that the true spherical silica particles were changed to true spherical silica particles having an average particle size of 0.3 μm and a relative standard deviation of 0.12. Resin 6 was prepared.
［参考例７］樹脂７の作成
真球状シリカ粒子の変わりに、平均粒径が０．１μｍで相対標準偏差が０．１９のシリコーン粒子を用いたほかは、参考例３と同様な操作を繰り返して、樹脂７を作成した。
[Reference Example 7] Preparation of Resin 7 The same procedure as in Reference Example 3 was repeated except that silicone particles having an average particle size of 0.1 μm and a relative standard deviation of 0.19 were used instead of the spherical silica particles. Resin 7 was prepared.
［参考例８］樹脂８の作成
真球状シリカ粒子の変わりに、平均粒径が０．０８μｍで相対標準偏差が０．１８の架橋ポリスチレン粒子を用いたほかは、参考例４と同様な操作を繰り返して、樹脂８を作成した。
Reference Example 8 Preparation of Resin 8 The same procedure as in Reference Example 4 was performed, except that crosslinked polystyrene particles having an average particle size of 0.08 μm and a relative standard deviation of 0.18 were used instead of the spherical silica particles. Repeatedly, Resin 8 was prepared.
［参考例９］樹脂９の作成
参考例１において、金属繊維製のフィルターを９５％ろ過精度１０μｍのものに変更したほかは、同様な操作を繰り返して、樹脂９を作成した。
[Reference Example 9] Preparation of Resin 9 Resin 9 was prepared in the same manner as in Reference Example 1, except that the metal fiber filter was changed to one having a 95% filtration accuracy of 10 μm.
［参考例１０］樹脂１０の作成
参考例２において、金属繊維製のフィルターを９５％ろ過精度１０μｍのものに変更したほかは、同様な操作を繰り返して、樹脂１０を作成した。
[Reference Example 10] Preparation of Resin 10 Resin 10 was prepared by repeating the same operation as in Reference Example 2, except that the metal fiber filter was changed to one having a 95% filtration accuracy of 10 μm.
［実施例１］
Ａ層用ポリマーとして樹脂１と３とを表１の不活性粒子の割合になるように用意し、また、Ｂ層用のポリマーとして樹脂１と３と５とを表１の不活性粒子の割合になるように用意し、それぞれ、１７０℃で６時間乾燥させた。こうして、乾燥チップを表１に示した層厚み構成になるような比率にて、２台の押出機ホッパーに供給し、溶融温度３１０℃で溶融し、マルチマニホールド型共押出ダイを用いてＡ層の片側にＢ層を積層させて積層未延伸フィルムを得た。なお、Ａ層用のポリマーとＢ層用のポリマーは、溶融状態にした後、ダイに供給する前に、それぞれ９５％ろ過精度が１μｍの金属繊維製のフィルター（第２フィルター）でろ過した。
このようにして得られた積層未延伸フィルムを１２０℃に予熱し、さらに低速、高速のロール間でフィルムを１３０℃に加熱して４．８倍に延伸し後、急冷し、縦延伸フィルムを得た。
続いてステンターに供給し、１５０℃にて横方向に５．１倍に延伸した。得られた二軸延伸フィルムを２００℃の熱風で３秒間熱固定しつつ横方向に１０％延伸を行い、厚み４．５μｍの積層二軸配向ポリエステルフィルムを得た。このフィルムのヤング率は縦方向５．８ＧＰａ、横方向８．８ＧＰａであった。
上記の方法で作成した二軸延伸フィルムの両面に、以下の方法で、Ｍ層を設けた。まず、真空蒸着装置内に設置されたフィルム走行装置に、得られた二軸延伸フィルムをセットし、１．００×１０−３Ｐａの高真空にした後に、２０℃の冷却金属ドラムを介して走行させた。このとき、酸素ガスを導入しつつアルミを電子ビームで加熱蒸発させ、アルミナの強化膜層（Ｍ層：厚み１００ｎｍ）を形成し、さらに連続で、反対側の面に同様にして強化膜層を形成し、磁気記録媒体用支持体を作成した。
得られた磁気記録媒体用支持体の特性を表１に示す。
[Example 1]
Resins 1 and 3 are prepared as the polymer for the A layer so as to have the ratio of inactive particles in Table 1, and the resins 1, 3 and 5 are prepared as the polymer for the B layer in the ratio of inactive particles in Table 1. And dried at 170 ° C. for 6 hours. Thus, the dried chips are supplied to the two extruder hoppers at a ratio so as to have the layer thickness configuration shown in Table 1, and melted at a melting temperature of 310 ° C., and the A layer is formed using a multi-manifold coextrusion die. A layer B was laminated on one side of the film to obtain a laminated unstretched film. The polymer for the A layer and the polymer for the B layer were each filtered through a metal fiber filter (second filter) having a 95% filtration accuracy of 1 μm before being fed to the die.
The laminated unstretched film thus obtained is preheated to 120 ° C., further heated to 130 ° C. between low-speed and high-speed rolls, stretched 4.8 times, and then rapidly cooled to obtain a longitudinally stretched film. Obtained.
Then, it supplied to the stenter and extended | stretched 5.1 times in the horizontal direction at 150 degreeC. The obtained biaxially stretched film was stretched 10% in the transverse direction while being heat-fixed with hot air at 200 ° C. for 3 seconds to obtain a laminated biaxially oriented polyester film having a thickness of 4.5 μm. The Young's modulus of this film was 5.8 GPa in the vertical direction and 8.8 GPa in the horizontal direction.
M layers were provided on both sides of the biaxially stretched film prepared by the above method by the following method. First, the obtained biaxially stretched film was set in a film traveling device installed in a vacuum deposition apparatus, and after making a high vacuum of 1.00 × 10 −3 Pa, through a cooling metal drum at 20 ° C. I made it run. At this time, aluminum is heated and evaporated with an electron beam while introducing oxygen gas to form an alumina reinforced film layer (M layer: thickness 100 nm). Then, a magnetic recording medium support was formed.
Table 1 shows the characteristics of the obtained magnetic recording medium support.
［実施例２および３］
表１の不活性粒子の量となるように、それぞれ上記参考例で作成した樹脂の割合を変更したほかは、実施例１と同様な操作を繰り返した。得られた磁気記録媒体用支持体の特性を表１に示す。
[Examples 2 and 3]
The same operation as in Example 1 was repeated except that the ratio of the resin prepared in each of the above reference examples was changed so that the amount of inert particles in Table 1 was reached. Table 1 shows the characteristics of the obtained magnetic recording medium support.
［実施例４］
樹脂３の代わりに、表１に示す不活性粒子の割合となるように樹脂７を用いたほかは、実施例１と同様な操作を繰り返した。得られた磁気記録媒体用支持体の特性を表１に示す。
[Example 4]
The same operation as in Example 1 was repeated except that the resin 7 was used so that the ratio of the inert particles shown in Table 1 was used instead of the resin 3. Table 1 shows the characteristics of the obtained magnetic recording medium support.
［実施例５］
実施例１において、Ａ層用のポリマーとＢ層用のポリマーとをダイの手前でろ過するフィルターを、それぞれ９５％ろ過精度が０．７μｍの金属繊維製のフィルター（第２フィルター）に変更したほかは、実施例１と同様な操作を繰り返した。得られた磁気記録媒体用支持体の特性を表１に示す。
[Example 5]
In Example 1, the filter for filtering the polymer for the A layer and the polymer for the B layer in front of the die was changed to a metal fiber filter (second filter) with a 95% filtration accuracy of 0.7 μm. Otherwise, the same operation as in Example 1 was repeated. Table 1 shows the characteristics of the obtained magnetic recording medium support.
［実施例６］
実施例１において、Ａ層用のポリマーとＢ層用のポリマーとをダイの手前でろ過するフィルターを、それぞれ９５％ろ過精度が１．２μｍの金属繊維製のフィルター（第２フィルター）に変更したほかは、実施例１と同様な操作を繰り返した。得られた磁気記録媒体用支持体の特性を表１に示す。
[Example 6]
In Example 1, the filter for filtering the polymer for the A layer and the polymer for the B layer in front of the die was changed to a metal fiber filter (second filter) having a 95% filtration accuracy of 1.2 μm. Otherwise, the same operation as in Example 1 was repeated. Table 1 shows the characteristics of the obtained magnetic recording medium support.
［実施例７］
実施例１において、Ａ層用のポリマーを樹脂１のみに変更したほかは、実施例１と同様な操作を繰り返した。得られた磁気記録媒体用支持体の特性を表１に示す。
[Example 7]
In Example 1, the same operation as in Example 1 was repeated except that the polymer for layer A was changed to resin 1 only. Table 1 shows the characteristics of the obtained magnetic recording medium support.
［実施例８、９、比較例３，４］
実施例１において、表1に示すとおり、アルミナの強化膜層の厚みを変更したほかは、実施例１と同様な操作を繰り返した。得られた磁気記録媒体用支持体の特性を表１に示す。
[Examples 8 and 9, Comparative Examples 3 and 4]
In Example 1, as shown in Table 1, the same operation as Example 1 was repeated except that the thickness of the alumina reinforcing film layer was changed. Table 1 shows the characteristics of the obtained magnetic recording medium support.
［実施例１０］
実施例１において、蒸着源を酸化ケイ素に変更したほかは、実施例１と同様な操作を繰り返した。得られた磁気記録媒体用支持体の特性を表１に示す。
[Example 10]
In Example 1, the same operation as in Example 1 was repeated except that the vapor deposition source was changed to silicon oxide. Table 1 shows the characteristics of the obtained magnetic recording medium support.
［実施例１１］
実施例１において、真空蒸着装置内に酸素ガスを導入しなかったほかは、実施例１と同様な操作を繰り返した。得られた磁気記録媒体用支持体の特性を表１に示す。
[Example 11]
In Example 1, the same operation as in Example 1 was repeated except that oxygen gas was not introduced into the vacuum deposition apparatus. Table 1 shows the characteristics of the obtained magnetic recording medium support.
［比較例１］
実施例１において、Ａ層用のポリマーとＢ層用のポリマーとをダイの手前でろ過するフィルターを、それぞれ９５％ろ過精度が１．５μｍの金属繊維製のフィルター（第２フィルター）に変更したほかは、実施例１と同様な操作を繰り返した。得られた磁気記録媒体用支持体の特性を表１に示す。
[Comparative Example 1]
In Example 1, the filter for filtering the polymer for the A layer and the polymer for the B layer in front of the die was changed to a metal fiber filter (second filter) having a 95% filtration accuracy of 1.5 μm. Otherwise, the same operation as in Example 1 was repeated. Table 1 shows the characteristics of the obtained magnetic recording medium support.
［比較例２］
実施例１において、Ａ層およびＢ層用のポリマーとして用いた樹脂１の代わりに、樹脂９を用い、またＡ層用のポリマーとＢ層用のポリマーとをダイの手前でろ過するフィルターを、それぞれ９５％ろ過精度が１．５μｍの金属繊維製のフィルター（第２フィルター）に変更したほかは、実施例１と同様な操作を繰り返した。得られた磁気記録媒体用支持体の特性を表１に示す。
[Comparative Example 2]
In Example 1, instead of the resin 1 used as the polymer for the A layer and the B layer, a resin 9 is used, and a filter that filters the polymer for the A layer and the polymer for the B layer in front of the die, The same operation as in Example 1 was repeated except that each filter was changed to a metal fiber filter (second filter) with a 95% filtration accuracy of 1.5 μm. Table 1 shows the characteristics of the obtained magnetic recording medium support.
［比較例５］
実施例１において、強化膜層を形成しなかった以外は、同様な操作を繰り返した。得られた磁気記録媒体用支持体の特性を表１に示す。
[Comparative Example 5]
In Example 1, the same operation was repeated except that the reinforcing film layer was not formed. Table 1 shows the characteristics of the obtained magnetic recording medium support.
表１中の、樹脂種は、１〜１０がそれぞれ参考例１〜１０の樹脂１〜１０、粗大突起数は上記（３）の測定で得た高さ１３０ｎｍ以上の突起の数、超粗大突起数は、波長２６０ｎｍの上記（３）の測定で得た高さ２６０ｎｍ以上の突起の数を意味する。 In Table 1, resin types 1 to 10 are resins 1 to 10 of Reference Examples 1 to 10, respectively, and the number of coarse protrusions is the number of protrusions having a height of 130 nm or more obtained by the measurement of (3) above, and super coarse protrusions. The number means the number of protrusions having a height of 260 nm or more obtained by the measurement of (3) above at a wavelength of 260 nm.
［実施例１２］
Ａ層用ポリマーとして樹脂２と４を表２の不活性粒子の割合になるように用意し、また、Ｂ層用のポリマーとして樹脂２と４と６とを表２の不活性粒子の割合になるように用意し、それぞれ、１５０℃で３時間乾燥させた。こうして、乾燥チップを表１に示した層厚み構成になるような比率にて、２台の押出機ホッパーに供給し、溶融温度２５０℃で溶融し、マルチマニホールド型共押出ダイを用いてＡ層の片側にＢ層を積層させて積層未延伸フィルムを得た。なお、Ａ層用のポリマーとＢ層用のポリマーは、溶融状態にした後、ダイに供給する前に、それぞれ９５％ろ過精度が１μｍのフィルター金属繊維製の（第２フィルター）でろ過した。
このようにして得られた積層未延伸フィルムを１００℃に予熱し、さらに低速、高速のロール間でフィルムを１１０℃に加熱して３．５倍に延伸し後、急冷し、縦延伸フィルムを得た。
続いてステンターに供給し、１０５℃にて横方向に４．６倍に延伸した。得られた二軸延伸フィルムを２１０℃の熱風で３秒間熱固定しつつ横方向に５％延伸を行い、厚み４．５μｍの積層二軸配向ポリエステルフィルムを得た。このフィルムのヤング率は縦方向４．４ＧＰａ、横方向６．１ＧＰａであった。得られた磁気記録媒体用支持体の特性を表２に示す。
[Example 12]
Resins 2 and 4 as the polymer for the A layer are prepared so as to have the ratio of the inert particles in Table 2, and the resins 2, 4 and 6 as the polymer for the B layer are set to the ratio of the inert particles in Table 2. Each was prepared and dried at 150 ° C. for 3 hours. Thus, the dried chips are supplied to the two extruder hoppers at a ratio such that the layer thickness configuration shown in Table 1 is obtained, melted at a melting temperature of 250 ° C., and layer A is formed using a multi-manifold coextrusion die. A layer B was laminated on one side of the film to obtain a laminated unstretched film. The polymer for the A layer and the polymer for the B layer were filtered with a (second filter) made of filter metal fibers each having a 95% filtration accuracy of 1 μm before being fed to the die.
The laminated unstretched film thus obtained is preheated to 100 ° C., heated to 110 ° C. between low-speed and high-speed rolls and stretched 3.5 times, and then rapidly cooled to obtain a longitudinally stretched film. Obtained.
Then, it supplied to the stenter and extended | stretched 4.6 times in the horizontal direction at 105 degreeC. The obtained biaxially stretched film was stretched 5% in the transverse direction while being heat-fixed with hot air at 210 ° C. for 3 seconds to obtain a laminated biaxially oriented polyester film having a thickness of 4.5 μm. The Young's modulus of this film was 4.4 GPa in the vertical direction and 6.1 GPa in the horizontal direction. Table 2 shows the characteristics of the obtained magnetic recording medium support.
［実施例１３および１４］
表２の不活性粒子の量となるように、それぞれ上記参考例で作成した樹脂の割合を変更したほかは、実施例１２と同様な操作を繰り返した。得られた磁気記録媒体用支持体の特性を表２に示す。
[Examples 13 and 14]
The same operation as in Example 12 was repeated except that the ratio of the resin prepared in each of the above reference examples was changed so that the amount of the inert particles in Table 2 was obtained. Table 2 shows the characteristics of the obtained magnetic recording medium support.
［実施例１５］
樹脂４の代わりに、表１に示す不活性粒子の割合となるように樹脂８を用いたほかは、実施例８と同様な操作を繰り返した。得られた磁気記録媒体用支持体の特性を表２に示す。
[Example 15]
The same operation as in Example 8 was repeated except that the resin 8 was used so that the ratio of the inert particles shown in Table 1 was used instead of the resin 4. Table 2 shows the characteristics of the obtained magnetic recording medium support.
［実施例１６］
実施例１２において、Ａ層用のポリマーとＢ層用のポリマーとをダイの手前でろ過するフィルターを、それぞれ９５％ろ過精度が０．７μｍの金属繊維製のフィルター（第２フィルター）に変更したほかは、実施例１２と同様な操作を繰り返した。得られた磁気記録媒体用支持体の特性を表２に示す。
[Example 16]
In Example 12, the filter for filtering the polymer for the A layer and the polymer for the B layer in front of the die was changed to a metal fiber filter (second filter) with a 95% filtration accuracy of 0.7 μm. Otherwise, the same operation as in Example 12 was repeated. Table 2 shows the characteristics of the obtained magnetic recording medium support.
［実施例１７］
実施例１２において、Ａ層用のポリマーとＢ層用のポリマーとをダイの手前でろ過するフィルターを、それぞれ９５％ろ過精度が１．２μｍの金属繊維製のフィルター（第２フィルター）に変更したほかは、実施例１２と同様な操作を繰り返した。得られた磁気記録媒体用支持体の特性を表２に示す。
[Example 17]
In Example 12, the filter for filtering the polymer for the A layer and the polymer for the B layer in front of the die was changed to a metal fiber filter (second filter) with a 95% filtration accuracy of 1.2 μm. Otherwise, the same operation as in Example 12 was repeated. Table 2 shows the characteristics of the obtained magnetic recording medium support.
［実施例１８］
実施例１２において、Ａ層用のポリマーを樹脂２のみに変更したほかは、実施例１２と同様な操作を繰り返した。得られた磁気記録媒体用支持体の特性を表２に示す。
[Example 18]
In Example 12, the same operation as in Example 12 was repeated except that the polymer for layer A was changed to resin 2 only. Table 2 shows the characteristics of the obtained magnetic recording medium support.
表２中の、樹脂種は、１〜１０がそれぞれ参考例１〜１０の樹脂１〜１０、粗大突起数は上記（３）の測定で得た高さ１３０ｎｍ以上の突起の数、超粗大突起数は、波長２６０ｎｍの上記（３）の測定で得た高さ２６０ｎｍ以上の突起の数を意味する。 In Table 2, resin types 1 to 10 are resins 1 to 10 of Reference Examples 1 to 10, respectively, and the number of coarse protrusions is the number of protrusions having a height of 130 nm or more obtained by the measurement of (3) above, and super coarse protrusions. The number means the number of protrusions having a height of 260 nm or more obtained by the measurement of (3) above at a wavelength of 260 nm.
本発明の磁気記録媒体用支持体は、記憶容量が０．８ＴＢ以上の、特にリニア記録方式のデータストレージのベースフィルムとして好適に使用することができる。 The support for a magnetic recording medium of the present invention can be suitably used as a base film for data storage of a linear recording system having a storage capacity of 0.8 TB or more.
Claims (6)
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| Application Number | Priority Date | Filing Date | Title |
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| JP2009101080A JP2010250910A (en) | 2009-04-17 | 2009-04-17 | Support for magnetic recording medium and data storage using the same |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012119040A (en) * | 2010-12-02 | 2012-06-21 | Teijin Dupont Films Japan Ltd | Two-axial alignment laminate film and data storage using the same |
| JP2015039801A (en) * | 2013-08-21 | 2015-03-02 | 帝人デュポンフィルム株式会社 | Laminate polyester film and coat-type magnetic recording tape using the same |
| JP2020189407A (en) * | 2019-05-20 | 2020-11-26 | 東洋紡フイルムソリューション株式会社 | Laminated polyester film and coat-type magnetic recording tape using the same |
| US11869545B2 (en) * | 2022-03-14 | 2024-01-09 | Fujifilm Corporation | Magnetic tape management device, magnetic tape cartridge, magnetic tape, magnetic tape system, magnetic tape management method, and program |
-
2009
- 2009-04-17 JP JP2009101080A patent/JP2010250910A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012119040A (en) * | 2010-12-02 | 2012-06-21 | Teijin Dupont Films Japan Ltd | Two-axial alignment laminate film and data storage using the same |
| JP2015039801A (en) * | 2013-08-21 | 2015-03-02 | 帝人デュポンフィルム株式会社 | Laminate polyester film and coat-type magnetic recording tape using the same |
| JP2020189407A (en) * | 2019-05-20 | 2020-11-26 | 東洋紡フイルムソリューション株式会社 | Laminated polyester film and coat-type magnetic recording tape using the same |
| JP7303999B2 (en) | 2019-05-20 | 2023-07-06 | 東洋紡株式会社 | LAMINATED POLYESTER FILM AND MAGNETIC RECORDING TAPE USING THE SAME |
| US11869545B2 (en) * | 2022-03-14 | 2024-01-09 | Fujifilm Corporation | Magnetic tape management device, magnetic tape cartridge, magnetic tape, magnetic tape system, magnetic tape management method, and program |
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