JP4074126B2 - Polishing composition - Google Patents
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- JP4074126B2 JP4074126B2 JP2002132738A JP2002132738A JP4074126B2 JP 4074126 B2 JP4074126 B2 JP 4074126B2 JP 2002132738 A JP2002132738 A JP 2002132738A JP 2002132738 A JP2002132738 A JP 2002132738A JP 4074126 B2 JP4074126 B2 JP 4074126B2
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【０００１】
【発明の属する技術分野】
本発明は、コンピュータ等の記憶装置に使用される磁気ディスク基板等の研磨に好適な研磨用組成物に関し、さらに詳しくは、磁気ヘッドが低浮上量で飛行するのに適した研磨精度の高い磁気ディスク表面を提供し得る磁気ディスク基板等の研磨用組成物に関する。
【０００２】
【従来の技術】
コンピューターやワードプロセッサーの外部記憶装置の中で高速でアクセスできる手段として磁気ディスク（メモリーハードディスク）が広く使われている。この磁気ディスクの代表的な一例は、Ａｌ合金基板の表面にＮｉＰを無電解メッキしたものを基板とし、この基板を表面研磨した後、Ｃｒ合金下地膜、Ｃｏ合金磁性膜、カーボン保護膜を順次スパッターで形成したものである。
しかしながら、磁気ディスク表面に磁気ヘッド浮上量以上の高さを有する突起が残っていると、所定高さにて浮上しながら高速で飛行する磁気ヘッドがその突起に衝突して損傷する原因になる。また、磁気ディスク基板に突起や研磨傷などがあるとＣｒ合金下地膜やＣｏ合金磁性膜などを形成したとき、それらの膜の表面に突起が現れ、また研磨傷に基づく欠陥が生じ、磁気ディスク表面が精度の高い平滑面にならないので、ディスク表面の精度を上げるには基板を精密に研磨する必要がある。
【０００３】
このため、磁気ディスク基板の研磨において、突起物をなくし、またはその高さをできるだけ低くし、かつ研磨傷が生じ難い研磨用組成物として多くのものが提案されてきた。
【０００４】
中でも、特開平９−２０４６５７号公報にはコロイダルシリカに硝酸アルミニウム、ゲル化防止剤を添加してなる組成物の使用が開示され、また特開平９−２０４６５８号公報にはヒュームドシリカに硝酸アルミニウムを添加してなる組成物の使用が開示されている。これらの公報に開示の組成物は、砥粒に硬度の小さい酸化ケイ素微粒子を使用しているため、面精度は得られやすいが、現状の実生産に使用できる研磨速度の達成が困難である。
さらには、特開平１０−２０４４１６号公報には研磨速度を高める手段として、多くの酸化剤の使用とＦｅ塩の使用がそれぞれ提案されている。しかしながら、これらについても現状の実生産に使用できる研磨速度に比べ不十分であった。
【０００５】
【発明が解決しようとする課題】
高密度磁気記録を可能とするアルミニウム磁気ディスク基板研磨用組成物に要求される品質は、ヘッドの低浮上を可能とする高精度ディスク面の達成である。従って、本発明の目的は、磁気ディスク基板の表面粗さが小さく、かつ突起や研磨傷を発生させず、高密度記録が達成可能であり、しかも経済的な速度で研磨できる磁気ディスク基板の研磨用組成物を提供することにある。
【０００６】
【課題を解決するための手段】
本発明者らは、低浮上量型アルミニウム磁気ディスク基板に要求される高精度の研磨面を達成するための研磨剤について鋭意研究した結果、特にＮｉ−Ｐメッキを施したアルミニウム磁気ディスク基板の研磨に優れた性能を示す研磨用組成物を見出し本発明に至った。
即ち、本発明は基本的には以下の各発明からなる。
（１）水性媒体に砥粒、リンを含む無機酸またはその塩及び他の無機酸またはその塩、酸化剤を配合したことを特徴とする研磨用組成物。
（２）砥粒が、アルミナ、チタニア、シリカ、ジルコニアからなる群より選ばれた少なくとも１種である上記（１）に記載の研磨用組成物。
（３）砥粒の平均粒子径が、０．００１〜０．５μｍである上記（１）または（２）に記載の研磨用組成物。
（４）砥粒が、コロイド粒子である上記（１）乃至（３）のいずれか１項に記載の研磨用組成物。
（５）リンを含む無機酸がリン酸またはホスホン酸である上記（１）乃至（４）のいずれか１項に記載の研磨用組成物。
（６）他の無機酸が、硝酸、硫酸、アミド硫酸、ホウ酸からなる群より選ばれた少なくとも１種である上記（１）乃至（５）のいずれか１項に記載の研磨用組成物。
（７）酸化剤が過酸化物、過ホウ酸塩、過硫酸塩、硝酸塩から選ばれた少なくとも１種である上記（１）乃至（６）のいずれか１項に記載の研磨用組成物。
（８）過酸化物が、過酸化水素である上記（７）に記載の研磨用組成物。
（９）過ホウ酸塩が、過ホウ酸ソーダである上記（７）に記載の研磨用組成物。
（１０）ｐＨが１〜５である上記（１）乃至（９）のいずれか１項に記載の研磨用組成物。
（１１）砥粒の含有量が３〜３０質量％の範囲内であり、無機酸またはその塩の含有量が０．１〜８質量％の範囲内であり、酸化剤の含有量が０．２〜５質量％の範囲内であることを特徴とする上記（１）乃至（１０）のいずれか１項に記載の研磨用組成物。
（１２）研磨用組成物が、磁気ディスク基板研磨用組成物である上記（１）乃至（１１）のいずれか１項に記載の研磨用組成物。
（１３） 上記（１２）の研磨用組成物で研磨された磁気ディスク基板。
研磨用組成物。
【０００７】
【発明の実施の形態】
本発明の研磨用組成物は水性媒体に砥粒、リンを含む無機酸またはその塩及び他の無機酸またはその塩、酸化剤を配合したことを特徴とする研磨用組成物である。
本発明の研磨用組成物に研磨材として含まれる砥粒は、特に限定されるものではなく、例えばアルミナ、チタニア、シリカ、ジルコニア等を使用することができる。また、それらの結晶型には限定されるものではない。例えば、アルミナ（酸化アルミニウム）には結晶型としてα型、γ型、δ型、η型、θ型、κ型、χ型等があり、チタニア（酸化チタン）には結晶型としてルチル型、アナターゼ型、ブルーカイト型等があり、シリカ（酸化ケイ素）にはコロイダルシリカ、フュームドシリカ、ホワイトカーボン等があり、ジルコニア（酸化ジルコニウム）には単斜晶系、正方晶系、非晶質等があり、いずれも好ましく使用できる。これらの砥粒はコロイド状粒子だとマイクロスクラッチの発生抑止効果が大きく好ましい。
【０００８】
上記砥粒の平均粒子径は、通常０．００１〜０．５μｍの範囲、好ましくは０．０１〜０．２μｍの範囲、より好ましくは０．０２〜０．２μｍの範囲、最も好ましくは０．０３〜０．２μｍの範囲であり、更に、コロイド状粒子であれば前記したようにより好ましい。ここで、平均粒子径はレーザードップラー周波数解析式粒度分布測定器、マイクロトラックＵＰＡ１５０（Ｈｏｎｅｙｗｅｌｌ社製）により測定した値が適用される。
砥粒の粒子径が大きくなると細目粒子によるゲル化、凝集は抑制しやすくなるが、粗い粒子の存在確率も高くなるため、研磨傷発生の原因となる。また、粒子径が小さくなると、前述のゲル化、凝集が起きやすくなり、この場合も研磨傷発生の原因となる。
【０００９】
本発明の研磨用組成物中の砥粒濃度が３質量％（以下断りない場合の％は質量％とする）未満の場合は研磨速度が著しく低下する。また、濃度が高くなるにつれて研磨速度は高くなるが、３０％を越えると研磨速度の上昇が見られないだけでなく、特にコロイド状粒子ではゲル化しやすくなる。経済性を加味すると実用的には３０％が上限となる。従って、砥粒の組成物中濃度としては３〜３０％の範囲であることが好ましく、更には５〜１５％が好ましい。
本発明の研磨用組成物ではリンを含む無機酸またはその塩及び他の無機酸またはその塩が併用されている。リンを含む無機酸は化合物の構成元素としてリンを含むものでリン酸またはホスホン酸が好ましい。リンを含む無機酸にはその誘導体も含む。リンを含む無機酸は２種以上を併用してもよい。
リンを含む無機酸に混合して用いられる他の無機酸としては塩酸、硫酸、クロム酸、炭酸、アミド硫酸、ホウ酸等を用いることができるが、硝酸、硫酸、アミド硫酸、ホウ酸が好ましい。これらの酸はその誘導体である場合も含む。リンを含む無機酸またはその塩及び他の無機酸の塩としてはＬｉ、Ｂｅ、Ｎａ、Ｍｇ、Ｋ、Ｃａ、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ａｌ、Ｚｒ、Ｎｂ、Ｍｏ、Ｐｄ、Ａｇ、Ｈｆ、Ｔａ、Ｗ等の金属の塩を用いることができる。これらの塩は例えば上記金属の酸化物または炭酸塩をリンを含む無機酸及び他の無機酸に溶解して得ることができる。
【００１０】
本発明の研磨用組成物中における、リンを含む無機酸またはその塩及び他の無機酸またはその塩の合計の配合量は０．１〜８％、好ましくは０．２〜６％、さらに好ましくは０．４〜４％の範囲がよい。無機酸またはその塩の配合量が０．１％未満ではマイクロスクラッチの抑制及び研磨速度の増大効果が見られない。また８％を越えるとｐＨ低下が著しく、研磨機材に与えるダメージが大きく、取り扱い上問題となる。リンを含む無機酸またはその塩と他の無機酸またはその塩の混合割合は前者１モルに対し、後者が０．１〜５モルの範囲が好ましい。
後者が０．１モル未満ではスラリーの分散性が悪化しマイクロスクラッチが増加する。また５モルを越えるとｐＨが低下し、研磨機材に与えるダメージが大きくなる。
【００１１】
本発明の研磨組成物は特定の無機酸またはその塩が２種以上含まれるが、リンを含む無機酸またはその塩を必須成分とすることにより、研磨速度の増大、マイクロスクラッチの発生抑止効果が高まる。
本発明において、特定の無機酸またはその塩を２種以上用いることの作用効果の機構については定かでないが一つは研磨組成物としての分散状態が良好になるためと推測される。
本発明の研磨用組成物に含まれる酸化剤は、好ましくは過酸化物、過ホウ酸塩、過硫酸塩、硝酸塩から少なくとも１種が選ばれるが、その代表例としては過酸化物として、過酸化水素、過ホウ酸塩として過ホウ酸ソーダ、過硫酸塩として過硫酸アンモニウム、硝酸塩として硝酸アンモニウムが好ましい。なお、前記の他の無機酸またはその塩が酸化作用を有する場合は酸化剤として兼用し、無機酸またはその塩のみとしてもよい。例えば硝酸塩は他の酸の塩として及び酸化剤として用いられる。勿論他の無機酸またはその塩が酸化作用を有する場合でも、これとは異なる酸化剤を加えてもよい。
酸化剤の効果として研磨速度の増大、面粗度の低下が挙げられる。その機構については明らかではないが、Ｎｉ−Ｐ表面のエッチング剤としての効果が考えられている。
酸化剤（例えば過酸化水素）の配合量は０．２〜５％、好ましくは０．５〜２％である。酸化剤の配合量が０．２％未満では研磨速度の増大、面粗度の低下の効果が少なく、また５％を越えるとその効果は飽和状態となる。
他の無機酸またはその塩が酸化剤を兼用する場合の配合量は両者の合量、即ち、他の無機酸またはその塩としての量と酸化剤としての量の合量となる。したがってリンを含む無機酸またはその塩と他の無機酸またはその塩の合計量は好ましくは０．３〜１３％、より好ましくは０．７〜８％である。
さらに上記の組成に兼用でない無機酸またはその塩、酸化剤を含む場合は兼用の無機酸またはその塩をいずれか一方に最大限含めて兼用でない残りの酸化剤等の配合量の上限を決めることができる。例えばリン酸、硝酸塩（他の無機酸の塩であり、かつ酸化剤）、過酸化水素の場合、硝酸塩をすべて他の無機酸の塩として配合量を定め、過酸化水素は酸化剤として、その上限を５％とすることができる。また例えば硝酸塩に酸化剤でない無機酸またはその塩を含める場合は硝酸塩を酸化剤として５％を限度として含め、残りの酸化剤でない無機酸またはその塩の量を定めることができる。いずれの場合もリンを含む無機酸またはその塩、他の無機酸またはその塩、酸化剤の合計の配合量は好ましくは０．３〜１３％、より好ましくは０．７〜８％である。
本発明の研磨用組成物において、ｐＨの範囲は１〜５であることが好ましく、更には２〜４、また更には２〜３であることがより好ましい。液性を酸性とすることでＮｉの酸化を促進し研磨速度を向上させることができるが、ｐＨが低すぎると装置の腐食等の問題もあるため、ｐＨは２〜３であることがより好ましい。ｐＨ調整には過ホウ酸ソーダを使用することができる。
【００１２】
なお、上記の各成分濃度は磁気ディスク基板を研磨する際の濃度である。研磨用組成物を製造し、運搬等する場合は上記濃度より濃厚な組成物とし、使用に際して上記の濃度に薄めて使用するのが効率的である。
本発明の磁気ディスク基板の研磨用組成物は、上記の各成分の他に界面活性剤及び防腐剤等を添加してもよい。しかし、その種類及び添加量はゲル化を引き起こさないよう細心の注意が必要である。
ゲル化の抑制のため、本研磨用組成物にゲル化防止剤を添加してもよい。用いられるゲル化防止剤として好ましくはホスホン酸系化合物、フェナントロリン及びアセチルアセトンアルミニウム塩から選ばれた少なくとも１種が好ましい。具体的には、ホスホン酸系化合物としては、１−ヒドロキシエタン−１，１−ジホスホン酸（Ｃ2 Ｈ6 Ｏ7 Ｐ2 ）若しくはアミノトリメチレンホスホン酸（Ｃ2 Ｈ12Ｏ9 Ｐ3 Ｎ）を例示することが出来る。フェナントロリンとしては、１，１０−フェナントロリン一水和物（Ｃ１2Ｈ8 Ｎ2 ・Ｈ2 Ｏ）を、アセチルアセトンアルミニウム塩としては、アセチルアセトンのアルミニウム錯塩（Ａｌ2 〔ＣＨ（ＣＯＣＨ3 ）3 〕）をそれぞれ例示することができる。これらは２％以内で添加することが好ましい。
【００１３】
本発明の研磨用組成物は、従来の研磨用組成物と同様に、水に砥粒を懸濁し、例えば、これにリン酸及び硝酸等の無機酸、過酸化水素を添加して調製することができる。使用の際には、全ての成分を混合したものを薄めて使用しても良いが、添加成分を２組、例えば水、砥粒、硝酸と水、リン酸、過酸化水素に分けて準備しておき、その２組を混合する方法をとっても良い。
【００１４】
本発明の研磨用組成物は、例えば磁気抵抗（ＭＲ）効果を利用した磁気ヘッド用磁気ディスクに代表される高記録密度用の基板（通常、３Ｇｂｉｔ／ｉｎｃｈ2 以上の記録密度を有する）に有利に適用できるが、それ以下の記録密度を有する磁気ディスクに対しても信頼性向上という見地から効果的に応用できる。
【００１５】
本発明の研磨用組成物を適用する磁気ハードディスク基板は格別限定されるものではないが、アルミニウム基板（合金を含む）、とくに、ＮｉＰを例えば無電解メッキしたアルミニウム基板に本発明の組成物を適用すると、高品質の研磨面が工業上有利に得られる。
研磨方法は一般にスラリー状研磨材に用いられる研磨パッドを磁気ディスク基板上に摺り合わせ、パッドと基板の間にスラリーを供給しながらパッドまたは基板を回転させる方法である。
本発明の研磨用組成物により研磨した基板からつくられた磁気ディスクは、マイクロピット、マイクロスクラッチ等微細な欠陥について発生頻度が非常に低く、また表面粗さ（Ｒａ）も２〜３μｍ位であり、非常に平滑性に優れている。
【００１６】
以下、本発明の実施例について具体的に説明するが、本発明はこれらの実施例に限定されるものではない。
【００１７】
【実施例】
実施例、比較例において用いた砥粒及びその特徴を表１に示す。
（実施例１〜１５）
デュポン(株)製のコロイダルシリカ（サイトンＨＴ−５０Ｆ）に水、無機酸１、無機酸２、酸化剤を表２に示す割合で添加し、種々の水性研磨用組成物を調製し、以下に示す研磨装置及び研磨条件で研磨を行った。その結果を表２に示す。平均粒子経はレーザードップラー周波数解析式粒度分布測定器、マイクロトラック ＵＰＡ１５０（Ｈｏｎｅｙｗｅｌｌ社製）により測定した。その粒度測定値を表１に示す。組成物のｐＨは(株)堀場製作所製Ｄ−１３ガラス電極式水素イオン濃度計により測定した。
（実施例１６、１７）
日本シリカ工業（株）製のホワイトカーボン（Ｅ−１５０Ｊ）及び日本アエロジル（株）製のヒュームドシリカ（ＡＥＲＯＳＩＬ−５０）を媒体攪拌ミルにより粉砕、整粒により粗粒子を除去し、平均粒子径が０．１μｍの酸化ケイ素をまず得た。次に、水、無機酸１、無機酸２、酸化剤を表２に示す割合で添加し、種々の水性研磨用組成物を調製し、以下に示す研磨装置および研磨条件で研磨を行った。その結果を表２に示す。
（実施例１８〜２０）
昭和タイタニウム（株）製の酸化チタニウム（スーパータイタニアＦ−４）、アルミナ、ジルコニアを媒体攪拌ミルにより粉砕、整粒により粗粒子を除去し、平均粒子径が０．２μｍの酸化チタニウム、アルミナ、ジルコニアをまず得た。次に、水、無機酸１、無機酸２、酸化剤を表２に示す割合で添加し、種々の水性研磨用組成物を調製し、以下に示す研磨装置および研磨条件で研磨を行った。その結果を表２に示す。
（実施例２１）
日産化学工業（株）製のコロイダルシリカ（スノーテックス３０）に、水、無機酸１、無機酸２、酸化剤を表２に示す割合で添加し、水性研磨用組成物を調製し、以下に示す研磨装置及び研磨条件で研磨を行った。その結果を表２に示す。（研磨条件）
基板として、ＮｉＰを無電解メッキした３．５インチサイズのアルミディスクを使用した。
（研磨装置および研磨条件）
研磨試験機‥‥‥‥‥４ウェイ式両面ポリシングマシン
研磨パッド‥‥‥‥‥スエードタイプ（ポリテックスＤＧ、ロデール製）
下定盤回転速度‥‥‥６０ｒｐｍ
スラリー供給速度‥‥５０ｍｌ／分
研磨時間‥‥‥‥‥‥５分
加工圧力‥‥‥‥‥‥５０ｇ／ｃｍ2
（研磨特性の評価）
研磨レート‥‥アルミディスクの研磨前後の重量減より換算
表面粗さ‥‥‥タリステップ、タリデータ２０００（ランクテーラーホブソン社製）を使用
研磨傷の深さは触針式表面解析装置Ｐ−１２（ＴＥＮＣＯＲ社製）の３次元モードにより形状解析し深さをもとめた。
研磨特性の評価結果を表２に示す。表２中の研磨傷Ａは研磨傷深さが２ｎｍ以下である。研磨傷Ｂは研磨傷深さが２〜１０ｎｍである。研磨傷深さが１０ｎｍより大なものは、実施例、比較例共に発生しなかった。
（比較例１〜７）
デュポン（株）製のコロイダルシリカ（サイトンＨＴ−５０Ｆ）に水、硝酸アルミニウム等、過酸化水素を表２に示す割合で添加し、水性研磨用組成物を調製し、実施例と同様に研磨した。その結果を表２に示す。
（比較例８）
昭和タイタニウム（株）製の酸化チタニウム（スーパータイタニアＦ−２）を媒体攪拌ミルにより粉砕、整粒により粗粒子を除去し、平均粒子径が０．３μｍの酸化チタニウムをまず得た。次に、水、硝酸アルミニウムを表２に示す割合で添加し、水性研磨用組成物を調製し、実施例と同様に研磨した。その結果を表２に示す。
（比較例９）
昭和タイタニウム（株）製の酸化チタニウム（スーパータイタニアＦ−４）を媒体攪拌ミルにより粉砕、整粒により粗粒子を除去し、平均粒子径が０．２μｍの酸化チタニウムをまず得た。次に、水、硝酸アルミニウムを表２に示す割合で添加し、水性研磨用組成物を調製し、実施例と同様に研磨した。その結果を表２に示す。
【００１８】
【表１】
【表２】
【発明の効果】
本発明の研磨用組成物を用いてディスクの研磨を行うと、表面粗さが非常に小さく、しかも高い速度で研磨することができる。研磨したディスクを用いた磁気ディスクは低浮上型ハードディスクとして有用であり、高密度記録が可能である。
特に、研磨したディスクを用いた磁気ディスク磁気抵抗効果を利用したＭＲヘッド用メディアに代表される高記録密度媒体（３Ｇｂｉｔ／ｉｎｃｈ2 以上の記録密度を有する）として有用度が高いが、それ以下のメディアにおいても高信頼性媒体あると言う観点で有用である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a polishing composition suitable for polishing a magnetic disk substrate or the like used in a storage device such as a computer. More specifically, the present invention relates to a magnetic material having high polishing accuracy suitable for a magnetic head to fly with a low flying height. The present invention relates to a polishing composition such as a magnetic disk substrate that can provide a disk surface.
[0002]
[Prior art]
Magnetic disks (memory hard disks) are widely used as a means for high-speed access in external storage devices of computers and word processors. A typical example of this magnetic disk is a substrate obtained by electrolessly plating NiP on the surface of an Al alloy substrate. After polishing the surface of the substrate, a Cr alloy underlayer, a Co alloy magnetic layer, and a carbon protective layer are sequentially formed. It is formed with a sputter.
However, if a protrusion having a height higher than the flying height of the magnetic head remains on the surface of the magnetic disk, the magnetic head flying at a high speed while flying at a predetermined height may collide with the protrusion and be damaged. Also, if there are protrusions or polishing scratches on the magnetic disk substrate, when a Cr alloy underlayer film or Co alloy magnetic film is formed, protrusions appear on the surface of those films, and defects based on the polishing scratches occur, resulting in magnetic disk Since the surface does not become a highly accurate smooth surface, it is necessary to polish the substrate precisely in order to increase the accuracy of the disk surface.
[0003]
For this reason, many polishing compositions have been proposed in which the protrusions are eliminated or the height thereof is made as low as possible and polishing scratches hardly occur in polishing of the magnetic disk substrate.
[0004]
Among them, JP-A-9-204657 discloses the use of a composition obtained by adding aluminum nitrate and an antigelling agent to colloidal silica, and JP-A-9-204658 discloses aluminum nitrate on fumed silica. Is disclosed. Since the compositions disclosed in these publications use silicon oxide fine particles having low hardness for the abrasive grains, it is easy to obtain surface accuracy, but it is difficult to achieve a polishing rate that can be used in actual production.
Furthermore, Japanese Patent Application Laid-Open No. 10-204416 proposes the use of many oxidizing agents and the use of Fe salts as means for increasing the polishing rate. However, these are also insufficient compared to the polishing rate that can be used in actual production.
[0005]
[Problems to be solved by the invention]
The quality required for an aluminum magnetic disk substrate polishing composition that enables high-density magnetic recording is to achieve a high-precision disk surface that enables low head flying. Accordingly, an object of the present invention is to polish a magnetic disk substrate that has a small surface roughness of the magnetic disk substrate, can generate high-density recording without generating protrusions or polishing scratches, and can be polished at an economical speed. It is to provide a composition for use.
[0006]
[Means for Solving the Problems]
As a result of diligent research on an abrasive for achieving a highly accurate polished surface required for a low flying height type aluminum magnetic disk substrate, the present inventors have polished an aluminum magnetic disk substrate subjected to Ni-P plating in particular. The present inventors have found a polishing composition exhibiting excellent performance and have arrived at the present invention.
That is, the present invention basically comprises the following inventions.
(1) A polishing composition comprising an aqueous medium containing abrasive grains, phosphorus-containing inorganic acid or a salt thereof, another inorganic acid or a salt thereof, and an oxidizing agent.
(2) The polishing composition according to (1), wherein the abrasive grains are at least one selected from the group consisting of alumina, titania, silica, and zirconia.
(3) Polishing composition as described in said (1) or (2) whose average particle diameter of an abrasive grain is 0.001-0.5 micrometer.
(4) The polishing composition according to any one of (1) to (3), wherein the abrasive grains are colloidal particles.
(5) The polishing composition according to any one of (1) to (4), wherein the inorganic acid containing phosphorus is phosphoric acid or phosphonic acid.
(6) The polishing composition according to any one of (1) to (5), wherein the other inorganic acid is at least one selected from the group consisting of nitric acid, sulfuric acid, amidosulfuric acid, and boric acid. .
(7) The polishing composition according to any one of (1) to (6), wherein the oxidizing agent is at least one selected from peroxides, perborates, persulfates, and nitrates.
(8) The polishing composition according to (7), wherein the peroxide is hydrogen peroxide.
(9) The polishing composition according to (7), wherein the perborate is sodium perborate.
(10) The polishing composition according to any one of (1) to (9), wherein the pH is 1 to 5.
(11) The content of the abrasive grains is in the range of 3 to 30% by mass, the content of the inorganic acid or its salt is in the range of 0.1 to 8% by mass, and the content of the oxidizing agent is 0.00. The polishing composition according to any one of (1) to (10) above, which is in the range of 2 to 5% by mass.
(12) The polishing composition according to any one of (1) to (11), wherein the polishing composition is a magnetic disk substrate polishing composition.
(13) A magnetic disk substrate polished with the polishing composition according to (12) above.
Polishing composition.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The polishing composition of the present invention is a polishing composition comprising an aqueous medium containing abrasive grains, phosphorus-containing inorganic acid or a salt thereof, other inorganic acid or a salt thereof, and an oxidizing agent.
The abrasive grains contained in the polishing composition of the present invention as an abrasive are not particularly limited, and for example, alumina, titania, silica, zirconia and the like can be used. Moreover, it is not limited to those crystal forms. For example, alumina (aluminum oxide) includes α-type, γ-type, δ-type, η-type, θ-type, κ-type, χ-type, etc., and titania (titanium oxide) includes rutile-type and anatase-type crystal types. Type, blue kite type, etc., silica (silicon oxide) includes colloidal silica, fumed silica, white carbon, etc., zirconia (zirconium oxide) includes monoclinic, tetragonal, amorphous, etc. Yes, both can be used preferably. These abrasive grains are preferably colloidal particles because they have a great effect of suppressing the generation of micro scratches.
[0008]
The average particle size of the abrasive grains is usually in the range of 0.001 to 0.5 μm, preferably in the range of 0.01 to 0.2 μm, more preferably in the range of 0.02 to 0.2 μm, most preferably 0.00. In the range of 03 to 0.2 μm, colloidal particles are more preferable as described above. Here, the average particle diameter is a value measured by a laser Doppler frequency analysis type particle size distribution analyzer, Microtrac UPA150 (manufactured by Honeywell).
When the particle diameter of the abrasive grains is increased, gelation and agglomeration due to fine particles are easily suppressed, but the existence probability of coarse particles is also increased, which causes polishing scratches. Further, when the particle diameter is reduced, the above-mentioned gelation and aggregation are liable to occur, and in this case as well, it causes the generation of polishing scratches.
[0009]
When the abrasive grain concentration in the polishing composition of the present invention is less than 3% by mass (hereinafter, “%” unless otherwise specified is mass%), the polishing rate is remarkably reduced. Further, the polishing rate increases as the concentration increases. However, when the concentration exceeds 30%, not only the polishing rate does not increase, but particularly colloidal particles are easily gelled. In consideration of economy, the upper limit is practically 30%. Therefore, the concentration of the abrasive grains in the composition is preferably in the range of 3 to 30%, more preferably 5 to 15%.
In the polishing composition of the present invention, an inorganic acid containing phosphorus or a salt thereof and another inorganic acid or a salt thereof are used in combination. The inorganic acid containing phosphorus is one containing phosphorus as a constituent element of the compound and is preferably phosphoric acid or phosphonic acid. The inorganic acid containing phosphorus includes its derivatives. Two or more inorganic acids containing phosphorus may be used in combination.
As other inorganic acids used by mixing with an inorganic acid containing phosphorus, hydrochloric acid, sulfuric acid, chromic acid, carbonic acid, amidosulfuric acid, boric acid and the like can be used, but nitric acid, sulfuric acid, amidosulfuric acid and boric acid are preferable. . These acids include cases where they are derivatives thereof. Examples of inorganic acids containing phosphorus or salts thereof and other inorganic acids include Li, Be, Na, Mg, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Al, and Zr. Metal salts such as Nb, Mo, Pd, Ag, Hf, Ta, and W can be used. These salts can be obtained, for example, by dissolving the metal oxide or carbonate in an inorganic acid containing phosphorus and other inorganic acids.
[0010]
In the polishing composition of the present invention, the total amount of phosphorus-containing inorganic acid or salt thereof and other inorganic acid or salt thereof is 0.1 to 8%, preferably 0.2 to 6%, more preferably. Is preferably in the range of 0.4 to 4%. If the blending amount of the inorganic acid or its salt is less than 0.1%, the effect of suppressing the micro scratch and increasing the polishing rate is not observed. On the other hand, if it exceeds 8%, the pH is remarkably lowered and the damage to the polishing equipment is large, which causes a problem in handling. The mixing ratio of the inorganic acid or its salt containing phosphorus and the other inorganic acid or its salt is preferably in the range of 0.1 to 5 mol with respect to 1 mol of the former.
When the latter is less than 0.1 mol, the dispersibility of the slurry is deteriorated and the micro scratch is increased. On the other hand, when the amount exceeds 5 moles, the pH is lowered and the damage to the polishing equipment is increased.
[0011]
The polishing composition of the present invention contains two or more specific inorganic acids or salts thereof. By using an inorganic acid or salt thereof containing phosphorus as an essential component, the polishing rate can be increased and the occurrence of micro scratches can be suppressed. Rise.
In the present invention, the mechanism of the effect of using two or more specific inorganic acids or salts thereof is not clear, but one is presumed to be because the dispersion state as a polishing composition becomes good.
The oxidizing agent contained in the polishing composition of the present invention is preferably at least one selected from peroxides, perborates, persulfates, and nitrates. Hydrogen peroxide, sodium perborate as perborate, ammonium persulfate as persulfate, and ammonium nitrate as nitrate are preferable. In addition, when said other inorganic acid or its salt has an oxidizing action, it may serve as an oxidizing agent, and it is good also as only an inorganic acid or its salt. For example, nitrates are used as salts of other acids and as oxidizing agents. Of course, even when another inorganic acid or a salt thereof has an oxidizing action, an oxidizing agent different from this may be added.
Examples of the effect of the oxidizing agent include an increase in polishing rate and a decrease in surface roughness. Although the mechanism is not clear, an effect as an etchant on the Ni-P surface is considered.
The blending amount of the oxidizing agent (for example, hydrogen peroxide) is 0.2 to 5%, preferably 0.5 to 2%. If the blending amount of the oxidizing agent is less than 0.2%, the effect of increasing the polishing rate and decreasing the surface roughness is small, and if it exceeds 5%, the effect becomes saturated.
When the other inorganic acid or its salt also serves as the oxidizing agent, the blending amount is the total amount of both, that is, the total amount as the other inorganic acid or its salt and the amount as the oxidizing agent. Therefore, the total amount of the inorganic acid or salt thereof containing phosphorus and the other inorganic acid or salt thereof is preferably 0.3 to 13%, more preferably 0.7 to 8%.
In addition, if the above composition contains an inorganic acid or salt or oxidant that is not used in combination, the maximum amount of the remaining oxidant that is not used in combination should be determined by including the combined inorganic acid or salt in the maximum. Can do. For example, in the case of phosphoric acid, nitrate (which is a salt of other inorganic acids and an oxidizing agent), and hydrogen peroxide, the amount of nitrate is determined as a salt of other inorganic acids, and hydrogen peroxide is used as an oxidizing agent. The upper limit can be 5%. For example, when an inorganic acid that is not an oxidizing agent or a salt thereof is included in the nitrate, the amount of the remaining inorganic acid that is not an oxidizing agent or a salt thereof can be determined by including nitrate up to 5%. In any case, the total amount of the inorganic acid or salt thereof containing phosphorus, the other inorganic acid or salt thereof, and the oxidizing agent is preferably 0.3 to 13%, more preferably 0.7 to 8%.
In the polishing composition of the present invention, the pH range is preferably 1 to 5, more preferably 2 to 4, and even more preferably 2 to 3. By making the liquid property acidic, it is possible to promote the oxidation of Ni and improve the polishing rate. However, if the pH is too low, there is a problem such as corrosion of the apparatus, so the pH is more preferably 2 to 3. . Sodium perborate can be used for pH adjustment.
[0012]
The above-mentioned component concentrations are concentrations when the magnetic disk substrate is polished. When a polishing composition is produced and transported, it is efficient to use a composition thicker than the above concentration and dilute to the above concentration when used.
The polishing composition for a magnetic disk substrate of the present invention may contain a surfactant, a preservative and the like in addition to the above components. However, it is necessary to pay close attention to the type and amount of addition so as not to cause gelation.
In order to suppress gelation, an antigelling agent may be added to the polishing composition. The antigelling agent used is preferably at least one selected from phosphonic acid compounds, phenanthroline and acetylacetone aluminum salt. Specifically, as the phosphonic acid compound, 1-hydroxyethane-1,1-diphosphonic acid (C 2 H 6 O 7 P 2 ) or aminotrimethylene phosphonic acid (C 2 H 12 O 9 P 3 N) is used. Can be illustrated. As phenanthroline, 1,10-phenanthroline monohydrate (C1 2 H 8 N 2 .H 2 O) is used, and as acetylacetone aluminum salt, aluminum complex salt of acetylacetone (Al 2 [CH (COCH 3 ) 3 ]) is used. Each can be illustrated. These are preferably added within 2%.
[0013]
The polishing composition of the present invention is prepared by suspending abrasive grains in water and adding, for example, an inorganic acid such as phosphoric acid and nitric acid, and hydrogen peroxide to the polishing composition as in the conventional polishing composition. Can do. In use, the mixture of all components may be diluted and used, but the additive components are prepared in two sets, for example, water, abrasive grains, nitric acid and water, phosphoric acid, and hydrogen peroxide. In addition, a method of mixing the two sets may be used.
[0014]
The polishing composition of the present invention is advantageous for high recording density substrates (typically having a recording density of 3 Gbit / inch 2 or more) typified by a magnetic disk for a magnetic head using the magnetoresistive (MR) effect, for example. However, it can be effectively applied to a magnetic disk having a recording density lower than that from the viewpoint of improving reliability.
[0015]
The magnetic hard disk substrate to which the polishing composition of the present invention is applied is not particularly limited, but the composition of the present invention is applied to an aluminum substrate (including an alloy), particularly an aluminum substrate plated with NiP, for example, electrolessly. Then, a high-quality polished surface can be advantageously obtained industrially.
The polishing method is a method in which a polishing pad generally used for a slurry-like abrasive is slid onto a magnetic disk substrate, and the pad or the substrate is rotated while supplying the slurry between the pad and the substrate.
The magnetic disk made from the substrate polished with the polishing composition of the present invention has a very low frequency of occurrence of fine defects such as micropits and microscratches, and the surface roughness (Ra) is about 2 to 3 μm. Excellent in smoothness.
[0016]
Examples of the present invention will be specifically described below, but the present invention is not limited to these examples.
[0017]
【Example】
Table 1 shows the abrasive grains used in Examples and Comparative Examples and their characteristics.
(Examples 1 to 15)
Water, an inorganic acid 1, an inorganic acid 2, and an oxidizing agent are added to DuPont's colloidal silica (Cyton HT-50F) in the proportions shown in Table 2 to prepare various aqueous polishing compositions. Polishing was performed with the polishing apparatus and polishing conditions shown. The results are shown in Table 2. The average particle diameter was measured by a laser Doppler frequency analysis type particle size distribution analyzer, Microtrac UPA150 (manufactured by Honeywell). The measured particle size is shown in Table 1. The pH of the composition was measured with a D-13 glass electrode type hydrogen ion concentration meter manufactured by Horiba, Ltd.
(Examples 16 and 17)
White silica (E-150J) manufactured by Nippon Silica Kogyo Co., Ltd. and fumed silica (AEROSIL-50) manufactured by Nippon Aerosil Co., Ltd. were pulverized with a medium agitating mill, coarse particles were removed by sizing, and the average particle size First, 0.1 μm of silicon oxide was obtained. Next, water, inorganic acid 1, inorganic acid 2, and oxidizing agent were added in the proportions shown in Table 2 to prepare various aqueous polishing compositions, and polishing was performed with the following polishing apparatus and polishing conditions. The results are shown in Table 2.
(Examples 18 to 20)
Titanium oxide manufactured by Showa Titanium Co., Ltd. (super titania F-4), alumina and zirconia were pulverized by a medium stirring mill, coarse particles were removed by sizing, and titanium oxide, alumina and zirconia having an average particle size of 0.2 μm I got first. Next, water, inorganic acid 1, inorganic acid 2, and oxidizing agent were added in the proportions shown in Table 2 to prepare various aqueous polishing compositions, and polishing was performed with the following polishing apparatus and polishing conditions. The results are shown in Table 2.
(Example 21)
Water, an inorganic acid 1, an inorganic acid 2, and an oxidizing agent are added to the colloidal silica (Snowtex 30) manufactured by Nissan Chemical Industries, Ltd. in the proportions shown in Table 2, to prepare an aqueous polishing composition. Polishing was performed with the polishing apparatus and polishing conditions shown. The results are shown in Table 2. (Polishing conditions)
As the substrate, a 3.5-inch size aluminum disk on which NiP was electrolessly plated was used.
(Polishing equipment and polishing conditions)
Polishing test machine ... 4-way double-sided polishing machine polishing pad ... Suede type (Polytex DG, manufactured by Rodel)
Lower platen rotation speed 60rpm
Slurry supply speed 50ml / min Polishing time 5 minutes Processing pressure 50g / cm 2
(Evaluation of polishing characteristics)
Polishing rate ··· Surface roughness converted from weight loss before and after polishing of aluminum disk ··········································· The shape was analyzed by the three-dimensional mode (manufactured by TENCOR) to determine the depth.
Table 2 shows the evaluation results of the polishing characteristics. The polishing flaw A in Table 2 has a polishing flaw depth of 2 nm or less. The polishing flaw B has a polishing flaw depth of 2 to 10 nm. No polishing flaw depth greater than 10 nm occurred in both the examples and the comparative examples.
(Comparative Examples 1-7)
A water-based polishing composition was prepared by adding hydrogen peroxide such as water and aluminum nitrate to a colloidal silica (Cyton HT-50F) manufactured by DuPont Co., Ltd. and polished in the same manner as in the examples. . The results are shown in Table 2.
(Comparative Example 8)
Titanium oxide (Super Titania F-2) manufactured by Showa Titanium Co., Ltd. was pulverized with a medium stirring mill and coarse particles were removed by sizing to obtain titanium oxide having an average particle size of 0.3 μm. Next, water and aluminum nitrate were added in the proportions shown in Table 2 to prepare an aqueous polishing composition, which was polished in the same manner as in the examples. The results are shown in Table 2.
(Comparative Example 9)
Titanium oxide (Super Titania F-4) manufactured by Showa Titanium Co., Ltd. was pulverized with a medium stirring mill and coarse particles were removed by sizing to obtain titanium oxide having an average particle size of 0.2 μm. Next, water and aluminum nitrate were added in the proportions shown in Table 2 to prepare an aqueous polishing composition, which was polished in the same manner as in the examples. The results are shown in Table 2.
[0018]
[Table 1]
[Table 2]
【The invention's effect】
When the disk is polished using the polishing composition of the present invention, the surface roughness is very small and the polishing can be performed at a high speed. A magnetic disk using a polished disk is useful as a low flying type hard disk, and high density recording is possible.
In particular, it is highly useful as a high recording density medium (having a recording density of 3 Gbit / inch 2 or more) typified by an MR head medium using a magnetoresistive effect of a magnetic disk using a polished disk. The media is also useful from the viewpoint that there is a highly reliable medium.
Claims (13)
リンを含む無機酸またはその塩と他の無機酸又はその塩の合計の含有量が０．１〜８質量％の範囲内であり、リンを含む無機酸またはその塩と他の無機酸またはその塩の混合割合は前者１モルに対し、後者が０．１〜５モルの範囲内であり、酸化剤の含有量が０．２〜５質量％の範囲内であり、砥粒が３〜３０質量％の範囲内であることを特徴とする研磨用組成物。 A polishing composition comprising an aqueous medium containing abrasive grains, phosphorus-containing inorganic acid or a salt thereof, and other inorganic acid or a salt thereof, an oxidizing agent ,
The total content of the inorganic acid or its salt containing phosphorus and the other inorganic acid or its salt is in the range of 0.1 to 8% by mass, and the inorganic acid or its salt containing phosphorus and the other inorganic acid or its The mixing ratio of the salt is 1 to 5 mol of the former, the latter is in the range of 0.1 to 5 mol, the content of the oxidizing agent is in the range of 0.2 to 5 mass%, and the abrasive grains are 3 to 30. Polishing composition characterized by being in the range of mass%.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002132738A JP4074126B2 (en) | 2001-09-03 | 2002-05-08 | Polishing composition |
| AU2002334406A AU2002334406A1 (en) | 2001-09-03 | 2002-09-03 | Polishing composition |
| US10/488,296 US20050028449A1 (en) | 2001-09-03 | 2002-09-03 | Polishing composition |
| CN 02819416 CN1561376A (en) | 2001-09-03 | 2002-09-03 | Polishing composition |
| EP02797709A EP1425357A1 (en) | 2001-09-03 | 2002-09-03 | Polishing composition |
| PCT/JP2002/008925 WO2003020839A1 (en) | 2001-09-03 | 2002-09-03 | Polishing composition |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001266315 | 2001-09-03 | ||
| JP2001-266315 | 2001-09-03 | ||
| JP2002132738A JP4074126B2 (en) | 2001-09-03 | 2002-05-08 | Polishing composition |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JP2003147337A JP2003147337A (en) | 2003-05-21 |
| JP2003147337A5 JP2003147337A5 (en) | 2005-09-22 |
| JP4074126B2 true JP4074126B2 (en) | 2008-04-09 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002132738A Expired - Lifetime JP4074126B2 (en) | 2001-09-03 | 2002-05-08 | Polishing composition |
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| Country | Link |
|---|---|
| JP (1) | JP4074126B2 (en) |
| CN (1) | CN1561376A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4986099B2 (en) * | 2003-06-09 | 2012-07-25 | 花王株式会社 | Substrate manufacturing method |
| JP2005001018A (en) * | 2003-06-09 | 2005-01-06 | Kao Corp | Method of manufacturing substrate |
| JP4202201B2 (en) * | 2003-07-03 | 2008-12-24 | 株式会社フジミインコーポレーテッド | Polishing composition |
| DE102006007888A1 (en) * | 2006-02-21 | 2007-08-23 | Degussa Gmbh | Aqueous alumina dispersion for use in melamine resin formulation for making cured product e.g. laminate for furniture or flooring contains highly disperse alumina surface modified with amino- and/or hydroxy-substituted organophosphonic acid |
| JP2008080486A (en) * | 2007-10-04 | 2008-04-10 | Kao Corp | Polishing kit for magnetic disk |
| JP7061859B2 (en) * | 2017-09-29 | 2022-05-02 | 株式会社フジミインコーポレーテッド | Method for manufacturing polishing composition and magnetic disk substrate |
-
2002
- 2002-05-08 JP JP2002132738A patent/JP4074126B2/en not_active Expired - Lifetime
- 2002-09-03 CN CN 02819416 patent/CN1561376A/en active Pending
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| Publication number | Publication date |
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| JP2003147337A (en) | 2003-05-21 |
| CN1561376A (en) | 2005-01-05 |
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