JP5034027B2 - Perfluoropolyether compound, lubricant using the same, and magnetic disk - Google Patents

Perfluoropolyether compound, lubricant using the same, and magnetic disk Download PDF

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JP5034027B2
JP5034027B2 JP2007539908A JP2007539908A JP5034027B2 JP 5034027 B2 JP5034027 B2 JP 5034027B2 JP 2007539908 A JP2007539908 A JP 2007539908A JP 2007539908 A JP2007539908 A JP 2007539908A JP 5034027 B2 JP5034027 B2 JP 5034027B2
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永芳 小林
和徳 白井
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Moresco Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
    • C07F9/65812—Cyclic phosphazenes [P=N-]n, n>=3
    • C07F9/65815—Cyclic phosphazenes [P=N-]n, n>=3 n = 3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
    • C08G65/005—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens
    • C08G65/007—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/74—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/48—Lubricating compositions characterised by the base-material being a macromolecular compound containing phosphorus
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B5/00—Recording by magnetisation or demagnetisation of a record carrier; Reproducing by magnetic means; Record carriers therefor
    • G11B5/62—Record carriers characterised by the selection of the material
    • G11B5/72—Protective coatings, e.g. anti-static or antifriction
    • G11B5/725—Protective coatings, e.g. anti-static or antifriction containing a lubricant, e.g. organic compounds
    • G11B5/7253—Fluorocarbon lubricant
    • G11B5/7257—Perfluoropolyether lubricant
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/08—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-nitrogen bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/08—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-nitrogen bonds
    • C10M2223/083—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-nitrogen bonds used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/14—Electric or magnetic purposes
    • C10N2040/18—Electric or magnetic purposes in connection with recordings on magnetic tape or disc

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  • General Health & Medical Sciences (AREA)
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Description

本発明は、パーフルオロポリエーテル誘導体およびそれを含有する潤滑剤、およびこれを用いた磁気ディスクに関する。さらに詳しくは、大容量記録媒体である磁気ディスクなどの記録媒体用の潤滑剤に使用される化合物およびそれを含有する潤滑剤に関する。   The present invention relates to a perfluoropolyether derivative, a lubricant containing the perfluoropolyether derivative, and a magnetic disk using the same. More specifically, the present invention relates to a compound used as a lubricant for a recording medium such as a magnetic disk which is a large capacity recording medium, and a lubricant containing the compound.

磁気ディスクの記録密度の増大に伴い、記録媒体である磁気ディスクと情報の記録・再生を行うヘッドとの距離は殆ど接触するまで狭くなっている。磁気ディスク表面にはヘッドとの接触・摺動の際の摩耗を抑える目的で潤滑層が設けられている。この潤滑層は通常潤滑剤を磁気ディスク表面に塗布して形成している。
該潤滑剤としては一般にパーフルオロポリエーテルが用いられ、なかでもヘッドとの粘着力が低く、低摩擦力を有するＳｏｌｖａｙ Ｓｏｌｅｘｉｓ製のＦｏｍｂｌｉｎ系化合物が主流である。Ｆｏｍｂｌｉｎ系化合物の基本骨格は繰返し単位が（ＣＦ２ＣＦ２Ｏ）ｍ−（ＣＦ２Ｏ）ｎ−のパーフルオロポリエーテルである。
しかし、Ｆｏｍｂｌｉｎ系のパーフルオロポリエーテル鎖中の酸素原子は、ルイス酸として作用するヘッドの部材中のＡｌ２Ｏ３と反応し、その鎖は切断される（例えば非特許文献１参照）。この切断が進行するとＦｏｍｂｌｉｎ系のパーフルオロポリエーテルは低分子化し、最終的には磁気ディスク上から揮発する。
一方、両末端に水酸基を有するパーフルオロポリエーテルの少なくともひとつの末端が、アリーロキシ基で置換されたシクロホスファゼン基である化合物が開示され、この化合物を成分とする潤滑剤が、良好なコンタクト・スタート・ストップ（ＣＳＳ）耐久性を有することが開示されている（例えば特許文献１参照。）。該化合物は、分子内にパーフルオロポリエーテル鎖を有しているにもかかわらずルイス酸に対する化学的安定性が高い（例えば非特許文献２参照。）ため、ルイス酸であるＡｌ２Ｏ３から構成されるヘッドと磁気ディスクとの接触によっても分解せず、磁気ディスク表面に安定に存在すると考えられる。また、ディスクの回転数は近い将来１５，０００ｒｐｍ以上となる可能性が高い。潤滑剤は、高速回転時でも飛散することなく磁気ディスク表面にとどまる必要がある。すなわち、磁気ディスクの信頼性を確保する上で、潤滑剤の化学的安定性と吸着性の両立が必要とされている。
Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ、１９９２年、２５巻、ｐ．６７９１−６７９９ Ｄｉｇｅｓｔｓ ｏｆ Ｔｈｅ Ｍａｇｎｅｔｉｃ Ｒｅｃｏｒｄｉｎｇ Ｃｏｎｆｅｒｅｎｃｅ、Ｃｏｌｏｒａｄｏ、２００４年８月 ｐ．Ｄ６ 国際出願公開ＷＯ０１／２１６３０Ａ１パンフレット As the recording density of the magnetic disk increases, the distance between the magnetic disk, which is a recording medium, and the head for recording / reproducing information is reduced until it almost comes into contact. A lubricating layer is provided on the surface of the magnetic disk for the purpose of suppressing wear during contact and sliding with the head. This lubricating layer is usually formed by applying a lubricant to the surface of the magnetic disk.
As the lubricant, perfluoropolyether is generally used, and among these, Fomblin compounds made by Solvay Solexis, which have a low adhesive force with the head and have a low frictional force, are the mainstream. The basic skeleton of the Fomblin compound is a perfluoropolyether having a repeating unit of (CF 2 CF 2 O) m- (CF 2 O) n-.
However, the oxygen atom in the Fomblin perfluoropolyether chain reacts with Al 2 O 3 in the head member acting as a Lewis acid, and the chain is cleaved (see, for example, Non-Patent Document 1). As this cutting progresses, Fomblin-based perfluoropolyether has a low molecular weight and eventually volatilizes from the magnetic disk.
On the other hand, a compound in which at least one end of a perfluoropolyether having a hydroxyl group at both ends is a cyclophosphazene group substituted with an aryloxy group is disclosed, and a lubricant containing this compound as a component has good contact start. -It is disclosed that it has stop (CSS) durability (for example, refer patent document 1). The compound has a high chemical stability to spite Lewis acid has a perfluoropolyether chain in the molecule (e.g., Non-Patent Document 2 referred to.), From Al 2 O 3 is a Lewis acid It is considered that it does not decompose even by contact between the constructed head and the magnetic disk, and exists stably on the surface of the magnetic disk. In addition, the number of revolutions of the disk is likely to be 15,000 rpm or more in the near future. The lubricant needs to stay on the surface of the magnetic disk without scattering even at high speed rotation. That is, in order to ensure the reliability of the magnetic disk, it is necessary to satisfy both the chemical stability and the adsorptivity of the lubricant.
Macromolecules, 1992, 25, p. 6791-6799 Digests of The Magnetic Recording Conference, Colorado, August 2004 p. D6 International Application Publication WO01 / 21630A1 Brochure

情報の記録容量の増大、記録・再生の高速化を図るため、ヘッドとディスクの距離（浮上量）はほとんど接触する領域まで低くなり、ディスクの回転数は近い将来１５，０００ｒｐｍ以上となる可能性が高い。
ディスク表面に位置する潤滑剤は、長期間安定に存在しつづける必要がある。しかし、浮上量が小さく、かつ高速で磁気ディスクを回転させると、潤滑剤はディスクの外周方向へ移動しやすくなり、ディスクの全面において十分な潤滑作用を示さないことが考えられる。この場合、潤滑不良によりヘッドの破壊やディスクの損傷を起こし、最終的にディスクの記録層の破壊に至る可能性がある。ヘッドとの接触により潤滑剤が分解する場合にも、同様に記録層の破壊に至る可能性がある。記録装置の信頼性を確保する上で、ディスク表面に対する充分な吸着性を示し、かつ分解しにくい潤滑剤が必要である。
本発明の課題は、ディスク表面で充分な吸着性を示し、かつ分解しにくい化合物、およびこれを用いた吸着性と潤滑剤分解抑制という２つの課題を同時に達成する潤滑剤ならびに磁気ディスクを提供することにある。In order to increase the recording capacity of information and increase the speed of recording / reproducing, the distance between the head and the disk (flying height) will be lowered to almost the contact area, and the rotation speed of the disk may be over 15,000 rpm in the near future. Is expensive.
The lubricant located on the disk surface needs to exist stably for a long time. However, if the flying height is small and the magnetic disk is rotated at a high speed, the lubricant is likely to move in the outer circumferential direction of the disk, and it is considered that the entire surface of the disk does not exhibit a sufficient lubricating action. In this case, there is a possibility that the head may be destroyed or the disk may be damaged due to poor lubrication, and eventually the recording layer of the disk may be destroyed. When the lubricant is decomposed by contact with the head, the recording layer may be similarly destroyed. In order to ensure the reliability of the recording apparatus, a lubricant that exhibits sufficient adsorptivity to the disk surface and is difficult to decompose is required.
An object of the present invention is to provide a compound that exhibits sufficient adsorptivity on the disk surface and is difficult to decompose, and a lubricant and magnetic disk that simultaneously achieve the two problems of adsorptivity and suppression of lubricant decomposition using the compound. There is.

本発明は、以下の発明に係る。
（１）式（Ｉ）で表される化合物。
Ａ−ＣＨ２ＣＦ２Ｏ（ＣＦ２ＣＦ２Ｏ）ｍ−（ＣＦ２Ｏ）ｎ−ＣＦ２ＣＨ２−Ｂ （Ｉ）
（式中Ａは、下記式（ａ）で表される基である。式中Ｂは、下記式（ｂ）で表される基である。ここで、Ｒは、Ｃ２〜５のフルオロアルキル基であり、ｍは０または１〜４０の実数、ｎは０または１〜４０の実数である。ｐは、１〜３の実数である。）

Figure 0005034027
（２）ｍおよびｎが４〜２１の実数であり、ｐが１または２である上記（１）に記載の化合物。
（３）式（Ｉ）の化合物を含有する潤滑剤。
（４）ｍおよびｎが４〜２１の実数であり、ｐが１または２である上記に記載の潤滑剤。
（５）支持体上に少なくとも記録層、保護層を形成し、その表面にパーフルオロポリエーテル構造を有する化合物からなる潤滑層を有する磁気ディスクにおいて、該潤滑層が式（Ｉ）で表される化合物を含有することを特徴とする磁気ディスク。
（６）ｍおよびｎが４〜２１の実数であり、ｐが１または２である上記に記載の磁気ディスク。
本発明においては、パーフルオロポリエーテルにおいて、一方の末端にフルオロアルコキシ基で置換されたシクロホスファゼン基、もう一方の末端に２つ以上の水酸基を含むオキシアルキレン基を有する、パーフルオロポリエーテル化合物が上記課題を克服することを見出した。
本発明の化合物の分解が抑制されるのは、分子内に存在するホスファゼン環がルイス塩基として働き、パーフルオロポリエーテルに先立ちＡｌ２Ｏ３と相互作用することで、パーフルオロポリエーテルの分解を抑制すると考えられる。また、本発明の化合物が優れた吸着性を示すのは、潤滑剤が有する２つ以上の水酸基が、磁気ディスク表面と水素結合を形成するためと考えられる。
［１］本発明の式（Ｉ）で表されるパーフルオロポリエーテルは、一方の末端にフルオロアルコキシ（ＲＯ）基で置換されたシクロホスファゼン基、もう一方の末端に２つ以上の水酸基を含むオキシアルキレン基を有する、パーフルオロポリエーテル化合物である。
ここで、Ｒは、Ｃ２〜５のフルオロアルキル基であり、例えば、２，２，２−トリフルオロエチル基、２，２，３，３−テトラフルオロプロピル基、２，２，３，３，３−ペンタフルオロプロピル基、１，１，１，３，３，３−ヘキサフルオロ−２−プロピル基、２，２，３，４，４，４−ヘキサフルオロブチル基、２，２，３，３，４，４，４−ヘプタフルオロブチル基、２，２，３，３，４，４，５，５−オクタフルオロペンチル基等を例示できる。
［１−１］合成方法
本発明の化合物（Ｉ）は例えば下記のように二段階の合成方法により製造される。一段階目は、パーフルオロポリエーテルにおいて、一方の末端にフルオロアルコキシ基で置換されたシクロホスファゼン基、もう一方の末端に１つの水酸基を有するパーフルオロポリエーテル化合物の合成である。例えばＲ−ＯＨで示されるフルオロアルコールを予めアルカリ金属等と反応させてフルオロアルコラートとしておき、次いでシクロトリホスホニトリルハライドと反応させ、さらに両末端が水酸基のパーフルオロポリエーテルとアルカリ金属等を投入し合成する。さらに詳しくは、フルオロアルコールを炭化水素系エーテルに溶解し、これに金属ナトリウムを加える。金属ナトリウムの添加量はフルオロアルコールに対して５０〜１００％当量、好ましくは８０〜９０％当量である。次いで該混合液を−２０〜１０℃、好ましくは−５〜５℃で５〜５０時間、好ましくは２０〜３０時間攪拌後、シクロトリホスホニトリルハライドを添加し、さらに室温で０．５〜５時間、好ましくは１〜３時間攪拌する。これを水洗、蒸留した後、パーフルオロポリエーテルと金属ナトリウムを加えて、９０〜１００℃で２０〜６０時間、好ましくは４０〜５０時間攪拌する。ここで使用するパーフルオロポリエーテルと金属ナトリウムは、最初に使用したフルオロアルコールに対してそれぞれ２〜３％当量と３〜４％当量が好ましい。その後、水洗およびカラムクロマトグラフィーによる精製を行い、一段階目の目的化合物であるパーフルオロポリエーテルの両末端において、一方の末端にフルオロアルコキシ基で置換されたシクロホスファゼン基、もう一方の末端に１つの水酸基を有するパーフルオロポリエーテル化合物が得られる。
二段階目の合成で、本発明の化合物（Ｉ）を得る。例えば一段階目で得られる化合物とグリシドールを反応させることによって本発明の化合物（Ｉ）が製造される。さらに詳しくは、一段階目で得られた化合物とグリシドールを６０〜８０℃で約０．５〜５時間、好ましくは１〜３時間反応させる。グリシドールの添加量は、一段階目で得られた化合物の水酸基に対し、１〜２倍当量が好ましい。次いで、水洗および分子蒸留を行い、目的物が得られる。
両末端に水酸基を有するパーフルオロポリエーテルとしてはＳｏｌｖａｙ Ｓｏｌｅｘｉｓ製Ｆｏｍｂｌｉｎ Ｚｄｏｌ、Ｚｄｏｌ−ＴＸ、Ｚｔｅｔｒａｏｌなどがある。例えば、Ｆｏｍｂｌｉｎ Ｚｄｏｌの化学構造は、
ＨＯ−ＣＨ２ＣＦ２Ｏ（ＣＦ２ＣＦ２Ｏ）ｍ−（ＣＦ２Ｏ）ｎ−ＣＦ２ＣＨ２ＯＨであり、ｍ＝０〜４０、ｎ＝０〜４０、分子量分布があり、平均分子量は約１０００〜７０００である。
［１−２］用途
本発明の化合物の用途は磁気ディスク装置内の磁気ディスクの摺動特性を向上させるための潤滑剤としての用途が挙げられる。この場合、本発明の化合物を単独使用する以外にも、例えばＳｏｌｖａｙ Ｓｏｌｅｘｉｓ製のＦｏｍｂｌｉｎ ＺｄｏｌやＺｔｅｔｒａｏｌ、Ｚｄｏｌ ＴＸ、ＡＭ、ダイキン工業製のＤｅｍｎｕｍ、Ｄｕｐｏｎｔ製のＫｒｙｔｏｘなどと任意の比率で混合して使用することもできる。また、磁気ディスク以外にも、おなじく磁気ディスク装置内の磁気ヘッドや、光磁気記録装置、光記録装置、磁気テープ等の記録装置、さらには記録装置に限らず摺動を伴う部分を有する機器の潤滑剤や、撥水性、撥油性が必要とされる表面のコート剤としての用途も考えられる。これらの用途でも、本発明の化合物を単独使用する以外に、炭化水素系やフッ素系、シリコン系の潤滑剤と混合して使用することもできる。
［１−３］使用方法
本発明の化合物を用いて潤滑層を形成するにはバルクの状態で表面に塗布する方法もあるが、必要以上に厚く付着してしまうことがある。この場合は溶剤に希釈して塗布する。溶剤は含フッ素のものが本発明の化合物との相溶性が良好である。例えば３Ｍ製ＰＦ−５０６０、ＰＦ−５０８０、ＨＦＥ−７１００，ＨＦＥ−７２００、ＤｕＰｏｎｔ製Ｖｅｒｔｒｅｌ−ＸＦ等が挙げられる。希釈後の本発明の化合物の濃度は１％以下、好ましくは０．００１〜０．１％である。なお磁気ディスクの潤滑剤として用いる際は一般に塗布法による。
［２］磁気ディスクについて
［２−１］磁気ディスクの構成
図１に本発明の磁気ディスクの断面の模式図を示す。
本発明の磁気ディスクは、まず支持体１上に少なくとも１層以上の記録層２、その上に保護層３、更にその上に本発明の化合物を含有する潤滑層４を最外層として有するという構成である。
支持体としてはアルミニウム合金、ガラス等セラミックス、ポリカーボネート等が挙げられる。
磁気ディスクの記録層である磁性層の構成材料としては鉄、コバルト、ニッケル等の強磁性体を形成可能な元素を中心として、これにクロム、白金、タンタル等を加えた合金、又はそれらの酸化物が挙げられる。これらはメッキ法、或いはスパッタ法等で形成される。
保護層はカーボン、ＳｉＣ，ＳｉＯ２等の材質が挙げられる。これらはスパッタ法、或いはＣＶＤ法で形成される。
［２−２］潤滑層の形成方法
現在潤滑層の厚さは３ｎｍ以下であるため、粘性が２０℃で１００ｍＰａ・ｓ程度以上の潤滑剤をそのまま塗布したのでは膜厚が大きくなりすぎる恐れがある。そこで塗布の際は溶剤に溶解したものを用いる。本発明の化合物を潤滑剤として単独で使用する場合も、例えばＳｏｌｖａｙ Ｓｏｌｅｘｉｓ製のＦｏｍｂｌｉｎ ＺｄｏｌやＺｔｅｔｒａｏｌ、Ｚｄｏｌ ＴＸ、ＡＭ、ダイキン工業製のＤｅｍｎｕｍ、Ｄｕｐｏｎｔ製のＫｒｙｔｏｘなどと混合して使用する場合も、溶剤に溶解した方が必要な膜厚に制御しやすい。但し、濃度は塗布方法・条件、混合割合等により異なる。
塗布方法はディップ法、スピンコート法等が挙げられる。
用いる溶剤は本発明の化合物を溶解するものを選択する。具体的には３Ｍ製ＰＦ−５０６０，ＰＦ−５０８０，ＨＦＥ−７１００，ＨＦＥ−７２００、ＤｕＰｏｎｔ社製のＶｅｒｔｒｅｌ−ＸＦ等の含フッ素溶媒が挙げられる。希釈後の本発明の化合物の濃度は１％以下、好ましくは０．００１〜０．１％である。
［２−３］応用
本発明の磁気ディスクは、ディスクを格納し、情報の記録・再生・消去を行うためのヘッドやディスクを回転するためのモーター等が装備されている磁気ディスクドライブとそのドライブを制御するための制御系からなる磁気ディスク装置に応用できる。
本発明の磁気ディスク、およびそれを応用した磁気ディスク装置の用途としてはコンピューターのほかにも、デジタルビデオレコーダー、デジタルビデオカメラ、デジタルカメラ、テレビなどのデジタル家電製品、さらにはカーナビゲーションシステム、ゲーム機、携帯電話、ＰＨＳ、ワードプロセッサーなどのデジタル情報の記録再生を行う電子機器への適用が可能である。The present invention relates to the following inventions.
(1) A compound represented by the formula (I).
A-CH 2 CF 2 O ( CF 2 CF 2 O) m- (CF 2 O) n-CF 2 CH 2 -B (I)
(In the formula, A is a group represented by the following formula (a). In the formula, B is a group represented by the following formula (b). Here, R is a C 2-5 fluoroalkyl. And m is 0 or a real number of 1 to 40, n is 0 or a real number of 1 to 40. p is a real number of 1 to 3.)
Figure 0005034027
(2) The compound according to (1) above, wherein m and n are real numbers of 4 to 21, and p is 1 or 2.
(3) A lubricant containing a compound of the formula (I).
(4) The lubricant as described above, wherein m and n are real numbers of 4 to 21, and p is 1 or 2.
(5) In a magnetic disk having at least a recording layer and a protective layer formed on a support and having a lubricating layer made of a compound having a perfluoropolyether structure on the surface, the lubricating layer is represented by the formula (I) A magnetic disk comprising a compound.
(6) The magnetic disk as described above, wherein m and n are real numbers of 4 to 21, and p is 1 or 2.
In the present invention, a perfluoropolyether compound having a cyclophosphazene group substituted with a fluoroalkoxy group at one end and an oxyalkylene group containing two or more hydroxyl groups at the other end is provided in the perfluoropolyether. It has been found that the above problems can be overcome.
The decomposition of the compound of the present invention is suppressed because the phosphazene ring present in the molecule acts as a Lewis base and interacts with Al 2 O 3 prior to the perfluoropolyether, thereby decomposing the perfluoropolyether. It is thought to suppress. The reason why the compound of the present invention exhibits excellent adsorptivity is considered to be that two or more hydroxyl groups of the lubricant form hydrogen bonds with the magnetic disk surface.
[1] The perfluoropolyether represented by the formula (I) of the present invention contains a cyclophosphazene group substituted with a fluoroalkoxy (RO) group at one end and two or more hydroxyl groups at the other end. A perfluoropolyether compound having an oxyalkylene group.
Here, R is a fluoroalkyl group of C 2 to 5, for example, 2,2,2-trifluoroethyl group, 2,2,3,3-tetrafluoropropyl group, 2,2,3,3 , 3-pentafluoropropyl group, 1,1,1,3,3,3-hexafluoro-2-propyl group, 2,2,3,4,4,4-hexafluorobutyl group, 2,2,3 , 3,4,4,4-heptafluorobutyl group, 2,2,3,3,4,4,5,5-octafluoropentyl group and the like.
[1-1] Synthesis Method Compound (I) of the present invention is produced, for example, by a two-step synthesis method as described below. The first step is the synthesis of a perfluoropolyether compound having a cyclophosphazene group substituted with a fluoroalkoxy group at one end and one hydroxyl group at the other end in perfluoropolyether. For example, a fluoroalcohol represented by R—OH is reacted in advance with an alkali metal or the like to form a fluoro alcoholate, then reacted with cyclotriphosphonitrile halide, and a perfluoropolyether having hydroxyl groups at both ends and an alkali metal are added. Synthesize. More specifically, fluoroalcohol is dissolved in a hydrocarbon-based ether, and sodium metal is added thereto. The amount of sodium metal added is 50 to 100% equivalent, preferably 80 to 90% equivalent to the fluoroalcohol. The mixture is then stirred at −20 to 10 ° C., preferably −5 to 5 ° C. for 5 to 50 hours, preferably 20 to 30 hours. Stir for hours, preferably 1-3 hours. After this is washed with water and distilled, perfluoropolyether and sodium metal are added and stirred at 90-100 ° C. for 20-60 hours, preferably 40-50 hours. The perfluoropolyether and metallic sodium used here are preferably 2 to 3% equivalent and 3 to 4% equivalent respectively to the fluoroalcohol used first. Thereafter, washing with water and purification by column chromatography are performed. At both ends of the perfluoropolyether which is the target compound in the first step, a cyclophosphazene group substituted with a fluoroalkoxy group at one end and 1 at the other end. A perfluoropolyether compound having two hydroxyl groups is obtained.
The compound (I) of the present invention is obtained by the synthesis of the second step. For example, the compound (I) of the present invention is produced by reacting the compound obtained in the first step with glycidol. More specifically, the compound obtained in the first step and glycidol are reacted at 60 to 80 ° C. for about 0.5 to 5 hours, preferably 1 to 3 hours. The addition amount of glycidol is preferably 1 to 2 times equivalent to the hydroxyl group of the compound obtained in the first stage. Next, washing with water and molecular distillation are performed to obtain the target product.
Examples of perfluoropolyethers having hydroxyl groups at both ends include Fomblin Zdol, Zdol-TX, and Ztetraol manufactured by Solvay Solexis. For example, the chemical structure of Fomblin Zdol is
A HO-CH 2 CF 2 O ( CF 2 CF 2 O) m- (CF 2 O) n-CF 2 CH 2 OH, m = 0~40, n = 0~40, there is a molecular weight distribution, average molecular weight Is about 1000-7000.
[1-2] Application The compound of the present invention can be used as a lubricant for improving the sliding characteristics of the magnetic disk in the magnetic disk apparatus. In this case, in addition to using the compound of the present invention alone, for example, it is used by mixing in any ratio with Fomblin Zdol or Ztetraol, Ztetra TX, AM, Daikin manufactured by Daikin Industries, Krytox manufactured by Dupont, etc. manufactured by Solvay Solexis. You can also In addition to magnetic disks, the same applies to magnetic heads in magnetic disk devices, recording devices such as magneto-optical recording devices, optical recording devices, magnetic tapes, etc. Use as a lubricant and a coating agent for surfaces requiring water repellency and oil repellency are also conceivable. In these applications, in addition to using the compound of the present invention alone, it can also be used by mixing with a hydrocarbon-based, fluorine-based, or silicon-based lubricant.
[1-3] Usage method There is a method of applying a bulk state to the surface in order to form a lubricating layer using the compound of the present invention, but it sometimes adheres more than necessary. In this case, it is applied after diluted in a solvent. Solvents containing fluorine have good compatibility with the compound of the present invention. Examples include 3M PF-5060, PF-5080, HFE-7100, HFE-7200, DuPont Vertrel-XF, and the like. The concentration of the compound of the present invention after dilution is 1% or less, preferably 0.001 to 0.1%. When used as a lubricant for a magnetic disk, it is generally applied by a coating method.
[2] Magnetic Disk [2-1] Configuration of Magnetic Disk FIG. 1 is a schematic diagram of a cross section of the magnetic disk of the present invention.
The magnetic disk of the present invention has at least one recording layer 2 on a support 1, a protective layer 3 thereon, and a lubricating layer 4 containing the compound of the present invention as an outermost layer. It is.
Examples of the support include aluminum alloys, ceramics such as glass, and polycarbonate.
The constituent material of the magnetic layer that is the recording layer of the magnetic disk is mainly an element capable of forming a ferromagnetic material such as iron, cobalt, nickel, etc., and an alloy obtained by adding chromium, platinum, tantalum, etc. to this, or oxidation thereof. Things. These are formed by plating or sputtering.
Examples of the protective layer include materials such as carbon, SiC, and SiO 2 . These are formed by sputtering or CVD.
[2-2] Lubricating layer formation method Since the lubricating layer is currently 3 nm or less in thickness, if a lubricant having a viscosity of about 100 mPa · s or more at 20 ° C. is applied as it is, the film thickness may become too large. is there. Therefore, a solution dissolved in a solvent is used for coating. When the compound of the present invention is used alone as a lubricant, for example, when it is used by mixing with Fomblin Zdol or Ztetraol, Ztetra TX, AM, Dainum manufactured by Daikin Industries, Krytox manufactured by Dupont, etc. manufactured by Solvay Solexis, It is easier to control the required film thickness by dissolving in a solvent. However, the concentration varies depending on the application method, conditions, mixing ratio, and the like.
Examples of the coating method include a dip method and a spin coating method.
The solvent to be used is selected to dissolve the compound of the present invention. Specific examples include fluorine-containing solvents such as 3M PF-5060, PF-5080, HFE-7100, HFE-7200, and Vertrel-XF manufactured by DuPont. The concentration of the compound of the present invention after dilution is 1% or less, preferably 0.001 to 0.1%.
[2-3] Application The magnetic disk of the present invention is a magnetic disk drive equipped with a head for storing the disk and recording / reproducing / erasing information, a motor for rotating the disk, and the like. The present invention can be applied to a magnetic disk device comprising a control system for controlling the disk.
In addition to computers, the magnetic disk of the present invention and the magnetic disk device to which it is applied are used in digital home appliances such as digital video recorders, digital video cameras, digital cameras, and televisions, as well as car navigation systems and game machines. It can be applied to electronic devices that record and reproduce digital information, such as mobile phones, PHS, and word processors.

第１図は本発明の磁気ディスクの構成を示す断面模式図である。１は支持体、２は記録層、３は保護層、４は潤滑層である。   FIG. 1 is a schematic sectional view showing the structure of a magnetic disk of the present invention. Reference numeral 1 denotes a support, 2 denotes a recording layer, 3 denotes a protective layer, and 4 denotes a lubricating layer.

以下、実施例および試験例により本発明を更に具体的に説明するが、本発明の範囲はこれらの実施例等に限定されるものではない。   EXAMPLES Hereinafter, although an Example and a test example demonstrate this invention further more concretely, the scope of the present invention is not limited to these Examples.

（ＣＦ３ＣＨ２Ｏ）５−Ｐ３Ｎ３−ＯＣＨ２ＣＦ２Ｏ（ＣＦ２ＣＦ２Ｏ）ｍ−（ＣＦ２Ｏ）ｎ−ＣＦ２ＣＨ２Ｏ−ＣＨ２ＣＨ（ＯＨ）ＣＨ２ＯＨ（ただし、−Ｐ３Ｎ３−は環状）（化合物１）の合成
アルゴン雰囲気下、テトラヒドロフラン（２５００ｇ）、トリフルオロエタノール（８７０ｇ）および金属ナトリウム（１８０ｇ）を０℃で２４時間攪拌した後、０℃でシクロトリホスホニトリルクロライド（４２０ｇ）を徐々に添加した。反応混合物を室温で２時間攪拌した後、水洗、蒸留し、トリフルオロエトキシ基が置換したシクロトリホスホニトリル、８３０ｇを得た。これに、パーフルオロポリエーテルとして両末端が水酸基のＳｏｌｖａｙ Ｓｏｌｅｘｉｓ製Ｆｏｍｂｌｉｎ Ｚｄｏｌ−２０００（平均分子量２０００）５２０ｇと金属ナトリウム（７ｇ）を加えて、９０℃で４８時間攪拌した。これをメタノールで洗浄した後、カラムクロマトグラフィーにより精製することにより、パーフルオロポリエーテルの片末端が式（ａ）、もう片末端が水酸基１つの化合物１２０ｇを得た。この化合物にアルゴン雰囲気下、カリウムｔ−ブトキシドを触媒としてｔ−ブタノール中、グリシドール３．５ｇを７０℃で２時間かけて徐々に滴下し、滴下後さらに２時間攪拌した。反応後、溶液を水で洗浄し、分子蒸留で精製し目的とする化合物（Ｉ）７０ｇを得た。
化合物１は、無色透明液体であり、２０℃での密度は、１．７０ｇ／ｃｍ３であった。ＮＭＲを用いて行った化合物１の同定結果を示す。１９Ｆ−ＮＭＲについては、化合物１をそのまま分析に用いた。１Ｈ−ＮＭＲでは、化合物１に無水トリフルオロ酢酸を加えて、水酸基をエステルに変成した試料について分析を行った。
１９Ｆ−ＮＭＲ（溶媒；なし、基準物質：生成物中に微量含まれるＯＣＦ２ＣＦ２ＣＦ２ＣＦ２Ｏを−１２５．８ｐｐｍとする）
δ＝−７６．１ｐｐｍ
〔１５Ｆ，Ｒｆ−ＣＦ２ＣＨ２−Ｏ−Ｐ３Ｎ３−（ＯＣＨ２ＣＦ ３）５〕
δ＝−７７．９ｐｐｍ、−７９．９ｐｐｍ
〔２Ｆ，Ｒｆ−ＣＦ ２ＣＨ２−Ｏ−ＣＨ２ＣＨ（ＯＨ）ＣＨ２ＯＨ〕
δ＝−７８．８ｐｐｍ、−８０．８ｐｐｍ
〔２Ｆ，Ｒｆ−ＣＦ ２ＣＨ２−Ｏ−Ｐ３Ｎ３−（ＯＣＨ２ＣＦ３）５〕
δ＝−８０．６ｐｐｍ、−８２．６ｐｐｍ
〔０Ｆ，Ｒｆ−ＣＦ ２ＣＨ２−ＯＨ〕
ｍ＝１０．６， ｎ＝１０．１
１Ｈ−ＮＭＲ（溶媒：パーフルオロヘキサン、基準物質：重水）：
δ＝５．２６ｐｐｍ
〔１Ｈ，Ｒｆ−ＣＦ２ＣＨ２−Ｏ−ＣＨ２ＣＨ（ＯＣＯＣＦ３）ＣＨ２ＯＣＯＣＦ３〕，
δ＝５．１２ｐｐｍ
〔０Ｈ，Ｒｆ−ＣＦ２ＣＨ２−Ｏ−ＣＨ２ ＣＨ（ＯＣＯＣＦ３）ＣＨ２ＯＣＨ２ＣＨ（ＯＣＯＣＦ３）ＣＨ２ＯＣＯＣＦ３〕 (CF 3 CH 2 O) 5 -P 3 N 3 -OCH 2 CF 2 O (CF 2 CF 2 O) m- (CF 2 O) n-CF 2 CH 2 O-CH 2 CH (OH) CH 2 OH (However, -P 3 N 3 -is cyclic) (Compound 1) Synthesis Under a nitrogen atmosphere, tetrahydrofuran (2500 g), trifluoroethanol (870 g) and metallic sodium (180 g) were stirred at 0 ° C. for 24 hours, and then 0 Cyclotriphosphonitrile chloride (420 g) was added slowly at 0 ° C. The reaction mixture was stirred at room temperature for 2 hours, then washed with water and distilled to obtain 830 g of cyclotriphosphonitrile substituted with a trifluoroethoxy group. To this, 520 g of Fomblin Zdol-2000 (average molecular weight 2000) manufactured by Solvay Solexis having hydroxyl groups at both ends as perfluoropolyether and sodium metal (7 g) were added and stirred at 90 ° C. for 48 hours. This was washed with methanol and purified by column chromatography to obtain 120 g of a compound having one end of the perfluoropolyether of formula (a) and the other end having one hydroxyl group. Under an argon atmosphere, 3.5 g of glycidol in t-butanol was gradually added dropwise to this compound over 2 hours at 70 ° C. using potassium t-butoxide as a catalyst, followed by further stirring for 2 hours. After the reaction, the solution was washed with water and purified by molecular distillation to obtain 70 g of the intended compound (I).
Compound 1 was a colorless transparent liquid, and the density at 20 ° C. was 1.70 g / cm 3 . The identification result of the compound 1 performed using NMR is shown. For 19 F-NMR, compound 1 was used for analysis as it was. In 1 H-NMR, analysis was performed on a sample in which trifluoroacetic anhydride was added to Compound 1 to convert a hydroxyl group into an ester.
19 F-NMR (solvent; none, reference material: OCF 2 CF 2 CF 2 CF 2 O contained in a trace amount in the product is set to −125.8 ppm)
δ = -76.1 ppm
[15F, Rf-CF 2 CH 2 -O-P 3 N 3 - (OCH 2 C F 3) 5 ]
δ = −77.9 ppm, −79.9 ppm
[2F, Rf—C F 2 CH 2 —O—CH 2 CH (OH) CH 2 OH]
δ = −78.8 ppm, −80.8 ppm
[2F, Rf—C F 2 CH 2 —O—P 3 N 3 — (OCH 2 CF 3 ) 5 ]
δ = −80.6 ppm, −82.6 ppm
[0F, Rf—C F 2 CH 2 —OH]
m = 10.6, n = 10.1
1 H-NMR (solvent: perfluorohexane, reference material: heavy water):
δ = 5.26 ppm
[1H, Rf-CF 2 CH 2 -O-CH 2 C H (OCOCF 3) CH 2 OCOCF 3 ],
δ = 5.12 ppm
[0H, Rf-CF 2 CH 2 -O-CH 2 CH (OCOCF 3) CH 2 OCH 2 CH (OCOCF 3) CH 2 OCOCF 3 ]

（ＣＦ３ＣＨ２Ｏ）５−Ｐ３Ｎ３−ＯＣＨ２ＣＦ２Ｏ（ＣＦ２ＣＦ２Ｏ）ｍ−（ＣＦ２Ｏ）ｎ−ＣＦ２ＣＨ２Ｏ−ＣＨ２ＣＨ（ＯＨ）ＣＨ２ＯＨ（ただし、−Ｐ３Ｎ３−は環状）（化合物２）の合成
実施例１に記載のパーフルオロポリエーテルとして、Ｓｏｌｖａｙ Ｓｏｌｅｘｉｓ製Ｆｏｍｂｌｉｎ Ｚｄｏｌ−４０００（平均分子量４，０００）を用いた他は、実施例１記載の方法に従って合成し、目的とする（化合物２）３０ｇを得た。化合物２は、無色透明液体であり、２０℃での密度は、１．７５ｇ／ｃｍ３であった。ＮＭＲを用いて行った化合物２の同定結果を示す。１９Ｆ−ＮＭＲについては、化合物２をそのまま分析に用いた。
１Ｈ−ＮＭＲでは、実施例１に記載の方法に従い作成したエステル変成体について分析を行った。
１９Ｆ−ＮＭＲ（溶媒；なし、基準物質：生成物中に微量含まれるＯＣＦ２ＣＦ２ＣＦ２ＣＦ２Ｏを−１２５．８ｐｐｍとする）
δ＝−７６．３ｐｐｍ
〔１５Ｆ，Ｒｆ−ＣＦ２ＣＨ２−Ｏ−Ｐ３Ｎ３−（ＯＣＨ２ＣＦ ３）５〕
δ＝−７７．８ｐｐｍ、−７９．８ｐｐｍ
〔２Ｆ，Ｒｆ−ＣＦ ２ＣＨ２−Ｏ−ＣＨ２ＣＨ（ＯＨ）ＣＨ２ＯＨ〕
δ＝−７８．８ｐｐｍ、−８０．８ｐｐｍ
〔２Ｆ，Ｒｆ−ＣＦ ２ＣＨ２−Ｏ−Ｐ３Ｎ３−（ＯＣＨ２ＣＦ３）５〕
δ＝−８０．６ｐｐｍ、−８２．６ｐｐｍ
〔０Ｆ，Ｒｆ−ＣＦ ２ＣＨ２−ＯＨ〕
ｍ＝２３．５， ｎ＝２３．３
１Ｈ−ＮＭＲ（溶媒：パーフルオロヘキサン、基準物質：重水）：
δ＝５．２６ｐｐｍ
〔１Ｈ，Ｒｆ−ＣＦ２ＣＨ２−Ｏ−ＣＨ２ＣＨ（ＯＣＯＣＦ３）ＣＨ２ＯＣＯＣＦ３〕，
δ＝５．１２ｐｐｍ
〔０Ｈ，Ｒｆ−ＣＦ２ＣＨ２−Ｏ−ＣＨ２ ＣＨ（ＯＣＯＣＦ３）ＣＨ２ＯＣＨ２ＣＨ（ＯＣＯＣＦ３）ＣＨ２ＯＣＯＣＦ３〕 (CF 3 CH 2 O) 5 -P 3 N 3 -OCH 2 CF 2 O (CF 2 CF 2 O) m- (CF 2 O) n-CF 2 CH 2 O-CH 2 CH (OH) CH 2 OH (However, -P 3 N 3 - cyclic) perfluoropolyether described in synthesis example 1 (compound 2), except for using the Solvay Solexis made Fomblin Zdol-4000 (average molecular weight 4,000) is Synthesis was performed according to the method described in Example 1 to obtain 30 g of the intended compound (Compound 2). Compound 2 was a colorless transparent liquid, and the density at 20 ° C. was 1.75 g / cm 3 . The identification result of the compound 2 performed using NMR is shown. For 19 F-NMR, compound 2 was used as is for analysis.
In 1 H-NMR, the ester modified product prepared according to the method described in Example 1 was analyzed.
19 F-NMR (solvent; none, reference material: OCF 2 CF 2 CF 2 CF 2 O contained in a trace amount in the product is set to −125.8 ppm)
δ = −76.3 ppm
[15F, Rf-CF 2 CH 2 -O-P 3 N 3 - (OCH 2 C F 3) 5 ]
δ = −77.8 ppm, −79.8 ppm
[2F, Rf—C F 2 CH 2 —O—CH 2 CH (OH) CH 2 OH]
δ = −78.8 ppm, −80.8 ppm
[2F, Rf—C F 2 CH 2 —O—P 3 N 3 — (OCH 2 CF 3 ) 5 ]
δ = −80.6 ppm, −82.6 ppm
[0F, Rf—C F 2 CH 2 —OH]
m = 23.5, n = 23.3
1 H-NMR (solvent: perfluorohexane, reference material: heavy water):
δ = 5.26 ppm
[1H, Rf-CF 2 CH 2 -O-CH 2 C H (OCOCF 3) CH 2 OCOCF 3 ],
δ = 5.12 ppm
[0H, Rf-CF 2 CH 2 -O-CH 2 CH (OCOCF 3) CH 2 OCH 2 CH (OCOCF 3) CH 2 OCOCF 3 ]

（ＣＦ３ＣＨ２Ｏ）５−Ｐ３Ｎ３−ＯＣＨ２ＣＦ２Ｏ（ＣＦ２ＣＦ２Ｏ）ｍ−（ＣＦ２Ｏ）ｎ−ＣＦ２ＣＨ２Ｏ−ＣＨ２ＣＨ（ＯＨ）ＣＨ２ＯＣＨ２ＣＨ（ＯＨ）ＣＨ２ＯＨ（ただし、−Ｐ３Ｎ３−は環状）（化合物３）の合成
実施例１に記載のグリシドールを７．０ｇ用いた他は、実施例１記載の方法に従って合成し、目的とする（化合物３）４５ｇを得た。化合物３は、無色透明液体であり、２０℃での密度は、１．６１ｇ／ｃｍ３であった。ＮＭＲを用いて行った化合物３の同定結果を示す。１９Ｆ−ＮＭＲについては、化合物３をそのまま分析に用いた。１Ｈ−ＮＭＲでは、実施例１に記載の方法に従い作成したエステル変成体について分析を行った。
１９Ｆ−ＮＭＲ（溶媒；なし、基準物質：生成物中に微量含まれるＯＣＦ２ＣＦ２ＣＦ２ＣＦ２Ｏを−１２５．８ｐｐｍとする）
δ＝−７６．１ｐｐｍ
〔１５Ｆ，Ｒｆ−ＣＦ２ＣＨ２−Ｏ−Ｐ３Ｎ３−（ＯＣＨ２ＣＦ ３）５〕
δ＝−７７．９ｐｐｍ、−７９．９ｐｐｍ
〔２Ｆ，Ｒｆ−ＣＦ ２ＣＨ２−Ｏ−ＣＨ２ＣＨ（ＯＨ）ＣＨ２Ｏ−ＣＨ２ＣＨ（ＯＨ）ＣＨ２−ＯＨ〕
δ＝−７８．８ｐｐｍ、−８０．８ｐｐｍ
〔２Ｆ，Ｒｆ−ＣＦ ２ＣＨ２−Ｏ−Ｐ３Ｎ３−（ＯＣＨ２ＣＦ３）５〕
δ＝−８０．６ｐｐｍ、−８２．６ｐｐｍ
〔０Ｆ，Ｒｆ−ＣＦ ２ＣＨ２−ＯＨ〕
ｍ＝１０．６， ｎ＝１０．１
１Ｈ−ＮＭＲ（溶媒：パーフルオロヘキサン、基準物質：重水）：
δ＝５．２６ｐｐｍ
〔１Ｈ，Ｒｆ−ＣＦ２ＣＨ２−Ｏ−ＣＨ２ＣＨ（ＯＣＯＣＦ３）ＣＨ２ＯＣＨ２ ＣＨ（ＯＣＯＣＦ３）ＣＨ２ＯＣＯＣＦ３〕，
δ＝５．１２ｐｐｍ
〔１Ｈ，Ｒｆ−ＣＦ２ＣＨ２−Ｏ−ＣＨ２ ＣＨ（ＯＣＯＣＦ３）ＣＨ２ＯＣＨ２ＣＨ（ＯＣＯＣＦ３）ＣＨ２ＯＣＯＣＦ３〕 (CF 3 CH 2 O) 5 -P 3 N 3 -OCH 2 CF 2 O (CF 2 CF 2 O) m- (CF 2 O) n-CF 2 CH 2 OCH 2 CH (OH) CH 2 OCH Synthesis of 2 CH (OH) CH 2 OH (where —P 3 N 3 — is cyclic) (Compound 3) Synthesis according to the method described in Example 1 except that 7.0 g of glycidol described in Example 1 was used. 45 g of the intended compound (Compound 3) were obtained. Compound 3 was a colorless and transparent liquid, and the density at 20 ° C. was 1.61 g / cm 3 . The identification result of the compound 3 performed using NMR is shown. For 19 F-NMR, compound 3 was used for analysis as it was. In 1 H-NMR, the ester modified product prepared according to the method described in Example 1 was analyzed.
19 F-NMR (solvent; none, reference material: OCF 2 CF 2 CF 2 CF 2 O contained in a trace amount in the product is set to −125.8 ppm)
δ = -76.1 ppm
[15F, Rf-CF 2 CH 2 -O-P 3 N 3 - (OCH 2 C F 3) 5 ]
δ = −77.9 ppm, −79.9 ppm
[2F, Rf-C F 2 CH 2 -O-CH 2 CH (OH) CH 2 O-CH 2 CH (OH) CH 2 -OH ]
δ = −78.8 ppm, −80.8 ppm
[2F, Rf—C F 2 CH 2 —O—P 3 N 3 — (OCH 2 CF 3 ) 5 ]
δ = −80.6 ppm, −82.6 ppm
[0F, Rf—C F 2 CH 2 —OH]
m = 10.6, n = 10.1
1 H-NMR (solvent: perfluorohexane, reference material: heavy water):
δ = 5.26 ppm
[1H, Rf-CF 2 CH 2 -O-CH 2 CH (OCOCF 3) CH 2 OCH 2 CH (OCOCF 3) CH 2 OCOCF 3 ],
δ = 5.12 ppm
[1H, Rf—CF 2 CH 2 —O—CH 2 CH (OCOCF 3 ) CH 2 OCH 2 CH (OCOCF 3 ) CH 2 OCOCF 3 ]

（ＨＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＨ２Ｏ）５−Ｐ３Ｎ３−ＯＣＨ２ＣＦ２Ｏ（ＣＦ２ＣＦ２Ｏ）ｍ−（ＣＦ２Ｏ）ｎ−ＣＦ２ＣＨ２Ｏ−ＣＨ２ＣＨ（ＯＨ）ＣＨ２ＯＨ（ただし、−Ｐ３Ｎ３−は環状）（化合物４）の合成
実施例１に記載の、トリフルオロエタノールの代りに２，２，３，３，４，４，５，５−オクタフルオロペンタノールを用いた他は、実施例１記載の方法に従って合成し、目的とする（化合物４）６５ｇを得た。化合物４は、無色透明液体であり、２０℃での密度は、１．７４ｇ／ｃｍ３であった。ＮＭＲを用いて行った化合物４の同定結果を示す。１９Ｆ−ＮＭＲについては、化合物４をそのまま分析に用いた。１Ｈ−ＮＭＲでは、実施例１に記載の方法に従い作成したエステル変成体について分析を行った。
１９Ｆ−ＮＭＲ（溶媒；なし、基準物質：生成物中に微量含まれるＯＣＦ２ＣＦ２ＣＦ２ＣＦ２Ｏを−１２５．８ｐｐｍとする）
δ＝−１３７．９ｐｐｍ
〔１０Ｆ，Ｒｆ−［ＣＦ２ＣＨ２−Ｏ−Ｐ３Ｎ３−（ＯＣＨ２ＣＦ２ＣＦ２ＣＦ２ＣＦ ２Ｈ）５］〕
δ＝−１２９．５ｐｐｍ
〔１０Ｆ，Ｒｆ−［ＣＦ２ＣＨ２−Ｏ−Ｐ３Ｎ３−（ＯＣＨ２ＣＦ２ＣＦ２ＣＦ ２ＣＦ２Ｈ）５］〕
δ＝−１２４．８ｐｐｍ
〔１０Ｆ，Ｒｆ−［ＣＦ２ＣＨ２−Ｏ−Ｐ３Ｎ３−（ＯＣＨ２ＣＦ２ＣＦ ２ＣＦ２ＣＦ２Ｈ）５］〕
δ＝−１２０．４ｐｐｍ
〔１０Ｆ，Ｒｆ−［ＣＦ２ＣＨ２−Ｏ−Ｐ３Ｎ３−（ＯＣＨ２ＣＦ ２ＣＦ２ＣＦ２ＣＦ２Ｈ）５］〕
δ＝−７８．４ｐｐｍ、−８０．４ｐｐｍ
〔２Ｆ，Ｒｆ−［ＣＦ ２ＣＨ２−Ｏ−Ｐ３Ｎ３−（ＯＣＨ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２Ｈ）５］〕
δ＝−７７．９ｐｐｍ、−７９．９ｐｐｍ
〔２Ｆ，Ｒｆ−ＣＦ ２ＣＨ２−Ｏ−ＣＨ２ＣＨ（ＯＨ）ＣＨ２ＯＨ〕
δ＝−８０．６ｐｐｍ、−８２．６ｐｐｍ
〔０Ｆ，Ｒｆ−ＣＦ ２ＣＨ２−ＯＨ〕
ｍ＝１０．６， ｎ＝１０．１
１Ｈ−ＮＭＲ（溶媒：パーフルオロヘキサン、基準物質：重水）：
δ＝５．２６ｐｐｍ
〔１Ｈ，Ｒｆ−ＣＦ２ＣＨ２−Ｏ−ＣＨ２ＣＨ（ＯＣＯＣＦ３）ＣＨ２ＯＣＯＣＦ３〕，
δ＝５．１２ｐｐｍ
〔０Ｈ，Ｒｆ−ＣＦ２ＣＨ２−Ｏ−ＣＨ２ ＣＨ（ＯＣＯＣＦ３）ＣＨ２ＯＣＨ２ＣＨ（ＯＣＯＣＦ３）ＣＨ２ＯＣＯＣＦ３〕
試験例１ ボンド率の測定
実施例１〜３で合成した化合物（化合物１〜３）をそれぞれＤｕＰｏｎｔ製Ｖｅｒｔｒｅｌ−ＸＦに溶解する。この溶液の化合物１〜３の濃度はいずれも０．１重量％である。直径３．５インチの磁気ディスクをこの溶液に１分間浸漬し、速度４ｍｍ／ｓで引き上げた。その後１５０℃の恒温槽に１０分間この磁気ディスクを入れ、ディスク表面に対する潤滑剤の吸着を促進させる。この後、Ｆｏｕｒｉｅｒ Ｔｒａｎｓｆｏｒｍ Ｉｎｆｒａｒｅｄ Ｓｐｅｃｔｒｏｍｅｔｅｒ（ＦＴ−ＩＲ）でディスク上の化合物の平均膜厚を測定する。この膜厚をｆÅとする。次に、このディスクをＶｅｒｔｒｅｌ−ＸＦ中に１０分間浸漬し、速度１０ｍｍ／ｓで引き上げた後、室温下で静置して溶媒を揮発させる。この後、ディスク上に残った化合物の平均膜厚をＦＴ−ＩＲで測定する。この膜厚をｂÅとする。ディスクとの吸着性の強弱を示す指標として、一般に用いられているボンド率を採用した。ボンド率は、下記式で表される。
ボンド率（％）＝１００×ｂ／ｆ
また比較のため、両末端に水酸基を有するパーフルオロポリエーテルの少なくともひとつの末端が、アリーロキシ基で置換されたシクロホスファゼン基である化合物〔（株）松村石油研究所製モレスコホスファロールＡ２０Ｈ−２０００〕、および両末端にそれぞれ２つの水酸基を有するパーフルオロポリエーテル（Ｓｏｌｖａｙ Ｓｏｌｅｘｉｓ製Ｆｏｍｂｌｉｎ Ｚｔｅｔｒａｏｌ−２０００Ｓ）を使用した。なおモレスコホスファロールＡ２０Ｈ−２０００を今後化合物５と記述し、Ｓｏｌｖａｙ Ｓｏｌｅｘｉｓ製Ｆｏｍｂｌｉｎ Ｚｔｅｔｒａｏｌを今後化合物６と記述する。
Ｒ１−ＯＣＨ２ＣＦ２Ｏ（ＣＦ２ＣＦ２Ｏ）ｍ−（ＣＦ２Ｏ）ｎ−ＣＦ２ＣＨ２−ＯＨ（化合物５）
ここでＲ１は、（ｍ−ＣＦ３Ｃ６Ｈ４Ｏ）５−Ｐ３Ｎ３−（ただし、−Ｐ３Ｎ３−は環状）であり、ｍは１０．５、ｎは１０．１である。
ＨＯＣＨ２ＣＨ（ＯＨ）ＣＨ２−ＯＣＨ２ＣＦ２Ｏ（ＣＦ２ＣＦ２Ｏ）ｍ−（ＣＦ２Ｏ）ｎ−ＣＦ２ＣＨ２Ｏ−ＣＨ２ＣＨ（ＯＨ）ＣＨ２ＯＨ（化合物６）
ここでｍは１０．１、ｎは１０．９である。
これらの化合物のボンド率を測定した。結果を表１に示す。これらの結果から、本発明のパーフルオロポリエーテルにおいて、一方の末端にフルオロアルコキシ基で置換されたシクロホスファゼン基、もう一方の末端に２つ以上の水酸基を含むオキシアルキレン基を有するパーフルオロポリエーテル化合物は、磁気ディスクと強い吸着力で結合した潤滑層を形成できるという効果が確認された。

Figure 0005034027
試験例２ 酸化アルミニウムに対する耐分解性の測定
実施例１〜３で合成した化合物（化合物１〜３）のそれぞれに２０重量％のＡｌ２Ｏ３（ＭＰバイオメディカルズ製、ＩＣＮ Ａｌｕｍｉｎａ Ｂ，Ａｋｔ．Ｉ、平均粒子径；１００μｍ）を入れ、強く振とうしたのち超音波でさらに良く混合した試料を用いて、Ａｌ２Ｏ３の存在下における熱挙動の比較を熱分析装置（ＴＧ／ＴＤＡ）を使用して実施した。試験は、試料２０ｍｇをアルミ製容器に入れ、窒素雰囲気下、２５０℃の一定温度で加熱し、一定時間後の化合物の重量減少率を測定した。また比較のため、Ａｌ２Ｏ３を添加せずに、化合物１〜３のそれぞれを２０ｍｇ使用し、同様の熱分析を行った。さらに化合物１〜３に加えて、化合物５（松村石油研究所製モレスコホスファロールＡ２０Ｈ−２０００）および化合物６（Ｓｏｌｖａｙ Ｓｏｌｅｘｉｓ製Ｆｏｍｂｌｉｎ Ｚｔｅｔｒａｏｌ−２０００Ｓ）も用いた。
結果を表２に示す。表２から明らかなように、本発明のパーフルオロポリエーテルにおいて、一方の末端にフルオロアルコキシ基で置換されたシクロホスファゼン基、もう一方の末端に２つ以上の水酸基を含むオキシアルキレン基を有するパーフルオロポリエーテル化合物は、化合物５と同様に、Ａｌ２Ｏ３による重量減少の促進は見られず、耐分解性に優れることが確認された。なお、表１より、化合物５の吸着性が低いことは明らかであり、耐分解性と吸着性を両立するにおいて、本発明の化合物が有効であることが確認できる。
Figure 0005034027
 (HCF 2 CF 2 CF 2 CF 2 CH 2 O) 5 -P 3 N 3 -OCH 2 CF 2 O (CF 2 CF 2 O) m- (CF 2 O) n-CF 2 CH 2 O-CH 2 CH Synthesis of (OH) CH 2 OH (where —P 3 N 3 — is cyclic) (Compound 4) 2,2,3,3,4,4,5 instead of trifluoroethanol as described in Example 1 Except for using 1,5-octafluoropentanol, the compound was synthesized according to the method described in Example 1 to obtain 65 g of the intended compound (Compound 4). Compound 4 was a colorless and transparent liquid, and the density at 20 ° C. was 1.74 g / cm 3 . The identification result of the compound 4 performed using NMR is shown. For 19 F-NMR, compound 4 was used as is for analysis. In 1 H-NMR, the ester modified product prepared according to the method described in Example 1 was analyzed.
19 F-NMR (solvent; none, reference material: OCF 2 CF 2 CF 2 CF 2 O contained in a trace amount in the product is set to −125.8 ppm)
δ = -137.9 ppm
[10F, Rf- [CF 2 CH 2 -O-P 3 N 3 - (OCH 2 CF 2 CF 2 CF 2 C F 2 H) 5] ]
δ = -129.5 ppm
[10F, Rf- [CF 2 CH 2 -O-P 3 N 3 - (OCH 2 CF 2 CF 2 C F 2 CF 2 H) 5] ]
δ = -124.8 ppm
[10F, Rf- [CF 2 CH 2 -O-P 3 N 3 - (OCH 2 CF 2 C F 2 CF 2 CF 2 H) 5] ]
δ = −120.4 ppm
[10F, Rf- [CF 2 CH 2 -O-P 3 N 3 - (OCH 2 C F 2 CF 2 CF 2 CF 2 H) 5] ]
δ = −78.4 ppm, −80.4 ppm
[2F, Rf- [C 2 F 2 CH 2 —O—P 3 N 3 — (OCH 2 CF 2 CF 2 CF 2 CF 2 H) 5 ]]
δ = −77.9 ppm, −79.9 ppm
[2F, Rf—C F 2 CH 2 —O—CH 2 CH (OH) CH 2 OH]
δ = −80.6 ppm, −82.6 ppm
[0F, Rf—C F 2 CH 2 —OH]
m = 10.6, n = 10.1
1 H-NMR (solvent: perfluorohexane, reference material: heavy water):
δ = 5.26 ppm
[1H, Rf-CF 2 CH 2 -O-CH 2 C H (OCOCF 3) CH 2 OCOCF 3 ],
δ = 5.12 ppm
[0H, Rf-CF 2 CH 2 -O-CH 2 CH (OCOCF 3) CH 2 OCH 2 CH (OCOCF 3) CH 2 OCOCF 3 ]
Test Example 1 Measurement of Bond Rate The compounds synthesized in Examples 1 to 3 (Compounds 1 to 3) are each dissolved in Verponl-XF manufactured by DuPont. The concentrations of compounds 1 to 3 in this solution are all 0.1% by weight. A 3.5-inch diameter magnetic disk was immersed in this solution for 1 minute and pulled up at a speed of 4 mm / s. Thereafter, the magnetic disk is placed in a thermostat at 150 ° C. for 10 minutes to promote the adsorption of the lubricant to the disk surface. Thereafter, the average film thickness of the compound on the disk is measured by a Fourier Transform Infrared Spectrometer (FT-IR). This film thickness is defined as fÅ. Next, this disk is immersed in Vertrel-XF for 10 minutes, pulled up at a speed of 10 mm / s, and then allowed to stand at room temperature to evaporate the solvent. Thereafter, the average film thickness of the compound remaining on the disk is measured by FT-IR. This film thickness is defined as bÅ. As an index indicating the strength of the adsorptivity with the disc, a generally used bond rate was adopted. The bond rate is expressed by the following formula.
Bond rate (%) = 100 × b / f
For comparison, a compound in which at least one end of a perfluoropolyether having a hydroxyl group at both ends is a cyclophosphazene group substituted with an aryloxy group [Moleco Phosphorol A20H- manufactured by Matsumura Oil Research Co., Ltd.] 2000], and perfluoropolyether having two hydroxyl groups at both ends (Fomlin Ztetraol-2000S manufactured by Solvay Solexis). Morescophosphalol A20H-2000 is hereinafter referred to as Compound 5 and Fomblin Ztetraol from Solvay Solexis is hereinafter referred to as Compound 6.
R 1 -OCH 2 CF 2 O ( CF 2 CF 2 O) m- (CF 2 O) n-CF 2 CH 2 -OH ( Compound 5)
Here, R 1 is (m-CF 3 C 6 H 4 O) 5 -P 3 N 3- (where -P 3 N 3 -is cyclic), m is 10.5, and n is 10.1. It is.
HOCH 2 CH (OH) CH 2 -OCH 2 CF 2 O (CF 2 CF 2 O) m- (CF 2 O) n-CF 2 CH 2 O-CH 2 CH (OH) CH 2 OH ( Compound 6)
Here, m is 10.1 and n is 10.9.
The bond rate of these compounds was measured. The results are shown in Table 1. From these results, in the perfluoropolyether of the present invention, the perfluoropolyether having a cyclophosphazene group substituted with a fluoroalkoxy group at one end and an oxyalkylene group containing two or more hydroxyl groups at the other end It was confirmed that the compound can form a lubricating layer bonded to the magnetic disk with a strong adsorption force.
Figure 0005034027
 Test Example 2 Measurement of decomposition resistance against aluminum oxide 20% by weight of Al 2 O 3 (manufactured by MP Biomedicals, ICN Alumina B, Akt. I, average particle size; 100 μm), and using a sample that was vigorously shaken and then mixed further with ultrasonic waves, a thermal analyzer (TG / TDA) was used to compare the thermal behavior in the presence of Al 2 O 3. Carried out using. In the test, 20 mg of a sample was placed in an aluminum container, heated at a constant temperature of 250 ° C. in a nitrogen atmosphere, and the weight reduction rate of the compound after a certain time was measured. For comparison, the same thermal analysis was performed using 20 mg of each of Compounds 1 to 3 without adding Al 2 O 3 . Further, in addition to compounds 1 to 3, compound 5 (Moleco Phosphorol A20H-2000 manufactured by Matsumura Oil Research Institute) and compound 6 (Fomlin Ztetraol-2000S manufactured by Solvay Solexis) were also used.
The results are shown in Table 2. As is apparent from Table 2, in the perfluoropolyether of the present invention, the perfluoropolyether having one end with a cyclophosphazene group substituted with a fluoroalkoxy group and the other end with an oxyalkylene group containing two or more hydroxyl groups. As in the case of Compound 5, the fluoropolyether compound was confirmed to be superior in decomposition resistance without promoting weight reduction by Al 2 O 3 . In addition, it is clear from Table 1 that the adsorptivity of the compound 5 is low, and it can be confirmed that the compound of the present invention is effective in achieving both decomposition resistance and adsorptivity.
Figure 0005034027

磁気ディスクの作製
実施例１および２で得られた化合物１および２と、比較のため化合物６をそれぞれＤｕＰｏｎｔ製Ｖｅｒｔｒｅｌ−ＸＦに溶解する。この溶液の化合物の濃度はいずれも０．１重量％である。直径３．５インチの磁気ディスクをこの溶液に１分間浸漬し、速度４ｍｍ／ｓで引き上げた。その後１５０℃で１０分間乾燥し、塗布された化合物の膜厚をＦＴ−ＩＲで測定した。結果を表３に示す。

Figure 0005034027
試験例３ 潤滑剤を塗布した磁気ディスクの潤滑性の測定
潤滑剤の性能試験は、ヘッドにかかる摩擦力を測定できるように改造したスピンドルスタンドにて、ディスクとヘッドを接触摺動させ、摩擦力の変化を測定することにより実施した。ディスクの回転数は９０ｒｐｍとし、１回転ごとの最大、最小と平均の摩擦力を出力した。試験の良否は、最大摩擦係数が５０ｍＮを超えるまでの時間（耐久時間）で判定した。なお、接触摺動は、浮上系の磁気ディスクの摺動耐久性を評価する上での加速試験と位置付けられる。
試験には、表３に示す磁気ディスクを用いた。
結果を表４に示す。表４から明らかなように、本発のホスファゼン環を有するパーフルオロポリエーテル化合物は、摺動耐久性に優れることが確認された。
Figure 0005034027
 以上の結果より、本発明のパーフルオロポリエーテルにおいて、一方の末端にフルオロアルコキシ基で置換されたシクロホスファゼン基、もう一方の末端に２つ以上の水酸基を含むオキシアルキレン基を有するパーフルオロポリエーテル化合物は、高い吸着性と分解抑制効果を両立する効果が認められ、さらに、これらの化合物を有する磁気ディスクは摺動耐久性に優れることが確認された。Production of Magnetic Disk Compounds 1 and 2 obtained in Examples 1 and 2 and Compound 6 for comparison are dissolved in Vertrel-XF manufactured by DuPont, respectively. The concentration of the compound in this solution is 0.1% by weight. A 3.5-inch diameter magnetic disk was immersed in this solution for 1 minute and pulled up at a speed of 4 mm / s. Then, it dried at 150 degreeC for 10 minute (s), and measured the film thickness of the apply | coated compound by FT-IR. The results are shown in Table 3.
Figure 0005034027
 Test Example 3 Measurement of Lubricity of Magnetic Disk Coated with Lubricant The performance test of the lubricant was performed by sliding the disk and head in contact with a spindle stand modified to measure the frictional force applied to the head. It was carried out by measuring the change of. The rotation speed of the disk was 90 rpm, and the maximum, minimum and average frictional forces were output for each rotation. The quality of the test was judged by the time until the maximum friction coefficient exceeded 50 mN (endurance time). The contact sliding is regarded as an acceleration test for evaluating the sliding durability of the floating magnetic disk.
The magnetic disk shown in Table 3 was used for the test.
The results are shown in Table 4. As is clear from Table 4, it was confirmed that the perfluoropolyether compound having the present phosphazene ring was excellent in sliding durability.
Figure 0005034027
 From the above results, in the perfluoropolyether of the present invention, the perfluoropolyether having a cyclophosphazene group substituted with a fluoroalkoxy group at one end and an oxyalkylene group containing two or more hydroxyl groups at the other end It was confirmed that the compound was effective in achieving both high adsorptivity and decomposition inhibiting effect, and that the magnetic disk having these compounds was excellent in sliding durability.

本発明の、パーフルオロポリエーテルにおいて、一方の末端にフルオロアルコキシ基で置換されたシクロホスファゼン基、もう一方の末端に２つ以上の水酸基を含むオキシアルキレン基を有する、パーフルオロポリエーテル化合物は、従来困難であった優れた吸着性と潤滑剤分解抑制という２つの課題を同時に達成する潤滑剤を提供する。また、本発明の化合物を潤滑剤として用いた磁気ディスクは高回転での連続回転にも耐える効果を有する。   In the perfluoropolyether of the present invention, a perfluoropolyether compound having a cyclophosphazene group substituted with a fluoroalkoxy group at one end and an oxyalkylene group containing two or more hydroxyl groups at the other end is Provided is a lubricant that simultaneously achieves two problems of excellent adsorptivity and suppression of lubricant decomposition, which have been difficult in the past. Further, the magnetic disk using the compound of the present invention as a lubricant has an effect to withstand continuous rotation at high rotation.

Claims (6)

式（Ｉ）で表される化合物。
Ａ−ＣＨ２ＣＦ２Ｏ（ＣＦ２ＣＦ２Ｏ）ｍ−（ＣＦ２Ｏ）ｎ−ＣＦ２ＣＨ２−Ｂ （Ｉ）
（式中Ａは、下記式（ａ）で表される基である。式中Ｂは、下記式（ｂ）で表される基である。ここで、Ｒは、Ｃ２〜５のフルオロアルキル基であり、ｍは０または１〜４０の実数、ｎは０または１〜４０の実数である。ｐは、１〜３の実数である。）
Figure 0005034027
A compound represented by formula (I).
A-CH 2 CF 2 O ( CF 2 CF 2 O) m- (CF 2 O) n-CF 2 CH 2 -B (I)
(In the formula, A is a group represented by the following formula (a). In the formula, B is a group represented by the following formula (b). Here, R is a C 2-5 fluoroalkyl. And m is 0 or a real number of 1 to 40, n is 0 or a real number of 1 to 40. p is a real number of 1 to 3.)
Figure 0005034027
 ｍおよびｎが４〜２１の実数であり、ｐが１または２である請求の範囲第１項に記載の化合物。The compound according to claim 1, wherein m and n are real numbers of 4 to 21, and p is 1 or 2. 式（Ｉ）の化合物を含有する潤滑剤。
Ａ−ＣＨ２ＣＦ２Ｏ−（ＣＦ２ＣＦ２Ｏ）ｍ−（ＣＦ２Ｏ）ｎ−ＣＦ２ＣＨ２−Ｂ （Ｉ）
（式中Ａは、式（ａ）で表される基である。式中Ｂは、式（ｂ）で表される基である。ここで、Ｒは、Ｃ２〜５のフルオロアルキル基であり、ｍは０または１〜４０の実数、ｎは０または１〜４０の実数である。ｐは、１〜３の実数である。）
Figure 0005034027
A lubricant containing a compound of formula (I).
A-CH 2 CF 2 O- ( CF 2 CF 2 O) m- (CF 2 O) n-CF 2 CH 2 -B (I)
(In the formula, A is a group represented by the formula (a). In the formula, B is a group represented by the formula (b). Here, R is a C 2-5 fluoroalkyl group. M is 0 or a real number of 1 to 40, n is a real number of 0 or 1 to 40. p is a real number of 1 to 3)
Figure 0005034027
 ｍおよびｎが４〜２１の実数であり、ｐが１または２である請求の範囲際３項に記載の潤滑剤。The lubricant according to claim 3, wherein m and n are real numbers of 4 to 21, and p is 1 or 2. 支持体上に少なくとも記録層、保護層を形成し、その表面にパーフルオロポリエーテル構造を有する化合物からなる潤滑層を有する磁気ディスクにおいて、該潤滑層が下記式（Ｉ）で表される化合物を含有することを特徴とする磁気ディスク。
Ａ−ＣＨ２ＣＦ２Ｏ−（ＣＦ２ＣＦ２Ｏ）ｍ−（ＣＦ２Ｏ）ｎ−ＣＦ２ＣＨ２−Ｂ （Ｉ）
（式中Ａは、式（ａ）で表される基である。式中Ｂは、式（ｂ）で表される基である。ここで、Ｒは、Ｃ２〜５のフルオロアルキル基であり、ｍは０または１〜４０の実数、ｎは０または１〜４０の実数である。ｐは、１〜３の実数である。）
Figure 0005034027
Figure 0005034027
In a magnetic disk having at least a recording layer and a protective layer formed on a support and having a lubricating layer made of a compound having a perfluoropolyether structure on the surface, the lubricating layer comprises a compound represented by the following formula (I): A magnetic disk characterized by containing.
A-CH 2 CF 2 O- ( CF 2 CF 2 O) m- (CF 2 O) n-CF 2 CH 2 -B (I)
(In the formula, A is a group represented by the formula (a). In the formula, B is a group represented by the formula (b). Here, R is a C 2-5 fluoroalkyl group. M is 0 or a real number of 1 to 40, n is a real number of 0 or 1 to 40. p is a real number of 1 to 3)
Figure 0005034027
Figure 0005034027
 ｍおよびｎが４〜２１の実数であり、ｐが１または２である請求の範囲第５項に記載の磁気ディスク。6. The magnetic disk according to claim 5, wherein m and n are real numbers of 4 to 21, and p is 1 or 2.
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