JP6415967B2 - Polishing liquid composition - Google Patents
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本開示は、Ｎｉ−Ｐメッキされたアルミニウム合金基板用研磨液組成物、該研磨液組成物の保存方法、更にこの組成物を用いた研磨方法及び磁気ディスク基板の製造方法に関する。 The present disclosure relates to a Ni-P plated polishing composition for an aluminum alloy substrate, a method for storing the polishing composition, a polishing method using the composition, and a method for manufacturing a magnetic disk substrate.
近年、磁気ディスクドライブは小型化・大容量化が進み、高記録密度化が求められている。高記録密度化するために、単位記録面積を縮小し、弱くなった磁気信号の検出感度を向上するため、磁気ヘッドの浮上高さをより低くするための技術開発が進められている。磁気ディスク基板には、磁気ヘッドの低浮上化と記録面積の確保に対応するため、平滑性及び平坦性の向上（表面粗さ、うねり、端面ダレの低減）と欠陥低減（スクラッチ、突起、ピット等の低減）に対する要求が厳しくなっている。このような要求に対し、スクラッチの低減が可能な研磨液組成物として、ベンゾトリアゾール（ＢＴＡ）のようなアゾール類を含有する研磨液組成物が提案されている（例えば、特許文献１参照）。 In recent years, magnetic disk drives have been reduced in size and capacity, and high recording density has been demanded. In order to increase the recording density, the unit recording area is reduced, and in order to improve the detection sensitivity of the weakened magnetic signal, technological development for lowering the flying height of the magnetic head has been advanced. Magnetic disk substrates have improved smoothness and flatness (reduced surface roughness, waviness and edge sag) and reduced defects (scratches, protrusions, pits) to reduce the flying height of the magnetic head and secure a recording area. Etc.) is becoming stricter. In response to such demands, a polishing liquid composition containing an azole such as benzotriazole (BTA) has been proposed as a polishing liquid composition capable of reducing scratches (see, for example, Patent Document 1).
さらに、研磨後の基板表面のスクラッチに加えて、研磨後の基板表面のナノ突起欠陥をよりいっそう低減する研磨液組成物として、ＢＴＡのようなアゾール類に加えて所定のアミン化合物が添加された研磨液組成物も提案されている（特許文献２）。 Furthermore, in addition to scratches on the substrate surface after polishing, a predetermined amine compound was added in addition to azoles such as BTA as a polishing liquid composition for further reducing nanoprojection defects on the substrate surface after polishing. A polishing composition has also been proposed (Patent Document 2).
ベンゾトリアゾール（ＢＴＡ）やその誘導体を含有する研磨液組成物において、調製後の保存期間にＢＴＡ及びその誘導体が変質していることが見出された。品質安定性の点から、該研磨液組成物の貯蔵安定性の向上が望まれた。 In the polishing composition containing benzotriazole (BTA) and its derivatives, it was found that BTA and its derivatives were altered during the storage period after preparation. From the viewpoint of quality stability, it has been desired to improve the storage stability of the polishing composition.
そこで、本開示は、一態様において、貯蔵安定性を向上しうる、ＢＴＡ又はその誘導体を含有する研磨液組成物、該研磨液組成物の保存方法、更にこの組成物を用いた磁気ディスク基板の製造方法、及びこれを用いた研磨方法を提供する。 Accordingly, in one aspect, the present disclosure provides a polishing liquid composition containing BTA or a derivative thereof, which can improve storage stability, a method for storing the polishing liquid composition, and a magnetic disk substrate using the composition. A manufacturing method and a polishing method using the same are provided.
本開示は、一又は複数の実施形態において、シリカ粒子、酸、酸化剤、ベンゾトリアゾール（ＢＴＡ）及びその誘導体からなる群から選ばれる少なくとも一種、ジアミン及びトリアミンからなる群から選ばれる少なくとも一種、ＢＴＡ又はその誘導体の変質抑制物質、及び水を含有し、前記変質抑制物質が、分子内に窒素原子を含まない、有機ホスホン酸又は縮合リン酸の少なくとも一方である、Ｎｉ−Ｐメッキされたアルミニウム合金基板用の研磨液組成物に関する。 In one or a plurality of embodiments, the present disclosure provides at least one selected from the group consisting of silica particles, acids, oxidizing agents, benzotriazole (BTA) and derivatives thereof, at least one selected from the group consisting of diamines and triamines, BTA Alternatively, a Ni-P plated aluminum alloy containing an alteration inhibiting substance of a derivative thereof and water, wherein the alteration inhibiting substance does not contain a nitrogen atom in the molecule and is at least one of an organic phosphonic acid or a condensed phosphoric acid. The present invention relates to a polishing liquid composition for a substrate.
本開示は、一又は複数の実施形態において、シリカ粒子、酸、酸化剤、ベンゾトリアゾール（ＢＴＡ）及びその誘導体からなる群から選ばれる少なくとも一種、ジアミン及びトリアミンからなる群から選ばれる少なくとも一種、及び水を含有する研磨液組成物に対し、分子内に窒素原子を含まない、有機ホスホン酸及び縮合リン酸からなる群から選ばれる少なくとも一種からなるＢＴＡ又はその誘導体の変質抑制物質を添加することによるＮｉ−Ｐメッキされたアルミニウム合金基板用の研磨液組成物の保存方法に関する。 In one or more embodiments of the present disclosure, at least one selected from the group consisting of silica particles, acids, oxidizing agents, benzotriazole (BTA) and derivatives thereof, at least one selected from the group consisting of diamines and triamines, and By adding an alteration inhibiting substance of BTA or a derivative thereof containing at least one selected from the group consisting of organic phosphonic acid and condensed phosphoric acid, which does not contain a nitrogen atom in the molecule, to a polishing composition containing water The present invention relates to a method for storing a polishing composition for an Ni-P plated aluminum alloy substrate.
本開示は、一又は複数の実施形態において、本開示に係る研磨液組成物を用いてＮｉ−Ｐメッキされたアルミニウム合金基板を研磨する工程を有する磁気ディスク基板の製造方法に関する。また、本開示は、一又は複数の実施形態において、本開示に係る研磨液組成物を用いてＮｉ−Ｐメッキされたアルミニウム合金基板を研磨する工程を有する、Ｎｉ−Ｐメッキされたアルミニウム合金基板の研磨方法に関する。 In one or a plurality of embodiments, the present disclosure relates to a method for manufacturing a magnetic disk substrate, which includes a step of polishing an Ni-P plated aluminum alloy substrate using the polishing composition according to the present disclosure. In one or more embodiments of the present disclosure, the Ni-P plated aluminum alloy substrate includes a step of polishing the Ni-P plated aluminum alloy substrate using the polishing composition according to the present disclosure. The present invention relates to a polishing method.
本開示によれば、一又は複数の実施形態において、ＢＴＡ又はその誘導体を含有する研磨液組成物におけるＢＴＡ及びその誘導体の変質が抑制され、貯蔵安定性が向上するという効果が奏されうる。また、本開示によれば、一又は複数の実施形態において、ＢＴＡ又はその誘導体に加えてジアミン又はトリアミンが添加された研磨液組成物の研磨後の基板表面のスクラッチ及びナノ突起欠陥の抑制効果を損なうことなく、該研磨液組成物の貯蔵安定性を向上しうるという効果を奏し得る。さらにまた、本開示によれば、一又は複数の実施形態において、スクラッチ及びナノ突起欠陥の抑制効果を損なうことなく、かつ、フィルター通液量を低下させることなく、該研磨液組成物の貯蔵安定性を向上しうるという効果を奏し得る。 According to the present disclosure, in one or a plurality of embodiments, alteration of BTA and a derivative thereof in a polishing liquid composition containing BTA or a derivative thereof is suppressed, and an effect that storage stability is improved can be achieved. In addition, according to the present disclosure, in one or a plurality of embodiments, the effect of suppressing scratches and nanoprotrusion defects on the substrate surface after polishing of the polishing composition in which diamine or triamine is added in addition to BTA or a derivative thereof is added. The effect that the storage stability of this polishing liquid composition can be improved without impairing can be produced. Furthermore, according to the present disclosure, in one or a plurality of embodiments, the storage stability of the polishing liquid composition can be maintained without impairing the suppression effect of scratches and nanoprotrusion defects and without reducing the amount of liquid passing through the filter. The effect that it can improve property can be produced.
本開示は、ＢＴＡ又はその誘導体に加えて、ジアミン又はトリアミンを含有する研磨液組成物により、スクラッチ及びナノ突起欠陥の抑制効果を損なうことなく、かつ、フィルター通液量を低下させることなく、研磨できるという知見に基づく。また、ＢＴＡ又はその誘導体に加えて、ジアミン又はトリアミンを含有する研磨液組成物が調製後の貯蔵期間にＢＴＡ又はその誘導体が変質しているという貯蔵不安定性を見出し、そのＢＴＡ又はその誘導体の変質が、所定の有機ホスホン酸又は縮合リン酸によって抑制され、研磨液組成物の貯蔵安定性が飛躍的に向上するという知見に基づく。 The present disclosure is a polishing liquid composition containing diamine or triamine in addition to BTA or a derivative thereof, without impairing the suppression effect of scratches and nanoprotrusions defects, and without reducing the filter flow rate. Based on the knowledge that it can. Further, in addition to BTA or a derivative thereof, a polishing liquid composition containing a diamine or a triamine has found a storage instability that BTA or a derivative thereof has deteriorated during the storage period after preparation. However, it is suppressed by a predetermined organic phosphonic acid or condensed phosphoric acid, and is based on the knowledge that the storage stability of the polishing composition is dramatically improved.
すなわち、ＢＴＡ又はその誘導体の芳香環が、研磨液組成物中の過酸化水素と微量のＦｅイオンとの反応で発生するラジカルにより開環して水カルボン酸に変質（分解）すると考えられる。ＢＴＡ又はその誘導体の変質は、しばしば、研磨液組成物の黄変及び沈殿を引き起こすと考えられる。そして、該Ｆｅイオンが所定の有機ホスホン酸又は縮合リン酸により安定化されることにより、ＢＴＡ又はその誘導体の変質（分解）が抑制され、研磨液組成物の貯蔵安定性が向上すると考えられる。但し、本開示はこのメカニズムに限定して解釈されなくてもよい。 In other words, it is considered that the aromatic ring of BTA or a derivative thereof is opened by radicals generated by the reaction between hydrogen peroxide and a small amount of Fe ions in the polishing composition, and is transformed (decomposed) into water carboxylic acid. Alteration of BTA or its derivatives is often thought to cause yellowing and precipitation of the polishing composition. Then, it is considered that the Fe ions are stabilized by a predetermined organic phosphonic acid or condensed phosphoric acid, whereby alteration (decomposition) of BTA or a derivative thereof is suppressed, and the storage stability of the polishing composition is improved. However, the present disclosure is not limited to this mechanism.
［ＢＴＡ、その誘導体］
本開示に係る研磨液組成物は、研磨後の基板表面のスクラッチ低減の観点から、ベンゾトリアゾール（ＢＴＡ）及びその誘導体からなる群から選ばれる少なくとも一種を含む。本開示において、ＢＴＡは、１Ｈ−ベンゾトリアゾールである。本開示において、ＢＴＡ誘導体としては、一又は複数の実施形態において、１Ｈ−トリルトリアゾール、２−アミノベンゾトリアゾール、３−アミノベンゾトリアゾール、１−[Ｎ，Ｎ−ビス（ヒドロキシエチレン）アミノメチル]ベンゾトリアゾール、及び、１−[Ｎ，Ｎ−ビス（ヒドロキシエチレン）アミノメチル]トリルトリアゾールが挙げられ、貯蔵安定性向上の観点、及び、研磨後の基板表面欠陥の低減の観点から、１Ｈ−トリルトリアゾールが好ましい。
[BTA and its derivatives]
The polishing composition according to the present disclosure contains at least one selected from the group consisting of benzotriazole (BTA) and its derivatives from the viewpoint of reducing scratches on the substrate surface after polishing. In the present disclosure, BTA is 1H-benzotriazole. In the present disclosure, as the BTA derivative, in one or more embodiments, 1H-tolyltriazole, 2-aminobenzotriazole, 3-aminobenzotriazole, 1- [N, N-bis (hydroxyethylene) aminomethyl] benzo Examples include triazole and 1- [N, N-bis (hydroxyethylene) aminomethyl] tolyltriazole. From the viewpoint of improving the storage stability and reducing the surface defect of the substrate after polishing, 1H-tolyltriazole Is preferred.
本開示に係る研磨液組成物におけるＢＴＡ及びその誘導体の合計の含有量は、研磨後の基板表面のスクラッチ及びナノ突起欠陥の低減の観点、及び、貯蔵安定性向上の観点から、一又は複数の実施形態において、研磨液組成物全体の質量に対して好ましくは０．０１質量％以上１０質量％以下、より好ましくは０．０５質量％以上５質量％以下、更に好ましくは０．１質量％以上１質量％以下である。なお、研磨液組成物中のＢＴＡ又はその誘導体はいずれか１種類であってもよく、２種類以上であってもよい。 The total content of BTA and its derivatives in the polishing composition according to the present disclosure is one or more from the viewpoint of reducing scratches and nanoprotrusion defects on the substrate surface after polishing, and improving storage stability. In the embodiment, it is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.05% by mass or more and 5% by mass or less, and further preferably 0.1% by mass or more with respect to the total mass of the polishing composition. 1% by mass or less. In addition, any one kind or two or more kinds of BTA or a derivative thereof may be contained in the polishing composition.
また、研磨液組成物中における、シリカ粒子とＢＴＡ及びその誘導体の合計との濃度比［シリカの濃度（質量％）／ＢＴＡ及びその誘導体の合計の濃度（質量％）］は、研磨後の基板表面のスクラッチ及びナノ突起欠陥の低減の観点、及び、貯蔵安定性向上の観点から、好ましくは１以上２００以下、より好ましくは５以上１００以下、更に好ましくは１０以上７５以下である。 Further, the concentration ratio [silica concentration (mass%) / total concentration of BTA and derivatives (mass%)] of the silica particles and the total of BTA and derivatives thereof in the polishing composition is the substrate after polishing. From the viewpoint of reducing surface scratches and nanoprotrusion defects, and from the viewpoint of improving storage stability, it is preferably 1 or more and 200 or less, more preferably 5 or more and 100 or less, and still more preferably 10 or more and 75 or less.
［ジアミン、トリアミン］
本開示に係る研磨液組成物は、研磨後の基板表面のスクラッチ及びナノ突起欠陥の低減の観点から、ジアミン及びトリアミンからなる群から選ばれる少なくとも一種を含む。本開示において、ジアミン及びトリアミンとしては、一又は複数の実施形態において、エチレンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルエチレンジアミン、１，２-ジアミノプロパン、１，３−ジアミノプロパン、１，４−ジアミノブタン、ヘキサメチレンジアミン、３−（ジエチルアミノ）プロピルアミン、３−（ジブチルアミノ）プロピルアミン、３−（メチルアミノ）プロピルアミン、３−（ジメチルアミノ）プロピルアミン、Ｎ−（２−アミノエチル）エタノールアミン、Ｎ−（２−アミノエチル）イソプロパノールアミン、Ｎ−メチル−Ｎ−（２−アミノエチル）エタノールアミン、ジエチレントリアミン、ピペラジン、２−メチルピペラジン、２、５−ジメチルピペラジン、１−アミノ−４−メチルピペラジン、Ｎ−メチルピペラジン、１−（２−アミノエチル）ピペラジン、及びヒドロキシエチルピペラジンが挙げられる。本開示において、ジアミン及びトリアミンとしては、一又は複数の実施形態において、研磨後の基板表面のスクラッチ及びナノ突起欠陥の低減の観点、及び、貯蔵安定性向上の観点から、好ましくは親水基を有するものであり、より好ましくはヒドロキシ基を有するものであり、更に好ましくはＮ−（２−アミノエチル）エタノールアミン、Ｎ−（２−アミノエチル）イソプロパノールアミン、Ｎ−メチル−Ｎ−（２−アミノエチル）エタノールアミン、及びＮ−（２−ヒドロキシエチル）ピペラジンが挙げられる。
[Diamine, Triamine]
The polishing composition according to the present disclosure contains at least one selected from the group consisting of diamines and triamines from the viewpoint of reducing scratches and nanoprotrusion defects on the substrate surface after polishing. In the present disclosure, the diamine and triamine may be ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1, in one or more embodiments. 4-diaminobutane, hexamethylenediamine, 3- (diethylamino) propylamine, 3- (dibutylamino) propylamine, 3- (methylamino) propylamine, 3- (dimethylamino) propylamine, N- (2-amino Ethyl) ethanolamine, N- (2-aminoethyl) isopropanolamine, N-methyl-N- (2-aminoethyl) ethanolamine, diethylenetriamine, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, 1-amino -4-methylpiperazine, N-methylpiperazine Rajin, 1- (2-aminoethyl) piperazine, and include hydroxyethyl piperazine. In the present disclosure, the diamine and the triamine preferably have a hydrophilic group in one or a plurality of embodiments from the viewpoint of reducing scratches and nanoprotrusion defects on the substrate surface after polishing and improving storage stability. More preferably, those having a hydroxy group, more preferably N- (2-aminoethyl) ethanolamine, N- (2-aminoethyl) isopropanolamine, N-methyl-N- (2-amino) Ethyl) ethanolamine, and N- (2-hydroxyethyl) piperazine.
本開示に係る研磨液組成物におけるジアミン及びトリアミンの合計の含有量は、研磨後の基板表面のスクラッチ及びナノ突起欠陥の低減の観点、及び、貯蔵安定性向上の観点から、研磨液組成物全体の質量に対して好ましくは０．０１質量％以上１０質量％以下、より好ましくは０．０２質量％以上５質量％以下、更に好ましくは０．０５質量％以上１質量％以下である。なお、研磨液組成物中のジアミン及びトリアミンはいずれか１種類であってもよく、２種類以上であってもよい。 The total content of diamine and triamine in the polishing liquid composition according to the present disclosure is the entire polishing liquid composition from the viewpoint of reducing scratches and nanoprotrusion defects on the substrate surface after polishing, and improving the storage stability. Preferably, they are 0.01 mass% or more and 10 mass% or less, More preferably, they are 0.02 mass% or more and 5 mass% or less, More preferably, they are 0.05 mass% or more and 1 mass% or less. In addition, any one kind of diamine and triamine in the polishing composition may be used, or two or more kinds may be used.
また、研磨液組成物中における、シリカ粒子とジアミン及びトリアミンの合計との濃度比［シリカ粒子の濃度（質量％）／ジアミン及びトリアミンの合計の濃度（質量％）］は、研磨後の基板表面のスクラッチ及びナノ突起欠陥の低減の観点、及び、貯蔵安定性向上の観点から、好ましくは１以上１０００以下、より好ましくは２５以上５００以下、更に好ましくは５０以上２５０以下である。 The concentration ratio of silica particles to the total of diamine and triamine [concentration of silica particles (% by mass) / total concentration of diamine and triamine (% by mass)] in the polishing liquid composition is the substrate surface after polishing. From the viewpoint of reducing scratches and nanoprotrusion defects and from the viewpoint of improving storage stability, it is preferably 1 or more and 1000 or less, more preferably 25 or more and 500 or less, and further preferably 50 or more and 250 or less.
さらに、研磨液組成物中における、ＢＴＡ及びその誘導体の合計とジアミン及びトリアミンの合計との濃度比［ＢＴＡ及びその誘導体の合計の濃度（質量％）／ジアミン及びトリアミンの合計の濃度（質量％）］は、研磨後の基板表面のスクラッチ及びナノ突起欠陥低減の観点、及び、貯蔵安定性向上の観点から、好ましくは０．１以上５０以下、より好ましくは１以上２５以下、更に好ましくは２以上１０以下である。 Furthermore, the concentration ratio of the total of BTA and its derivatives and the total of diamine and triamine in the polishing composition [the total concentration of BTA and its derivatives (mass%) / the total concentration of diamine and triamine (mass%) ] Is preferably 0.1 or more and 50 or less, more preferably 1 or more and 25 or less, and still more preferably 2 or more, from the viewpoint of reducing scratches and nanoprotrusion defects on the substrate surface after polishing and improving the storage stability. 10 or less.
［ＢＴＡ又はその誘導体の変質抑制物質］
本開示に係る研磨液組成物は、貯蔵安定性向上の観点から、ＢＴＡ又はその誘導体の変質抑制物質を含有する。前記変質抑制物質は、貯蔵安定性向上の観点から、分子内に窒素原子を含まない有機ホスホン酸、及び、分子内に窒素原子を含まない縮合リン酸からなる群から選ばれる少なくとも一種である。前記変質抑制物質は、一又は複数の実施形態において、貯蔵安定性向上の観点から、１−ヒドロキシエチリデン−１’１−ジホスホン酸（ＨＥＤＰ）、ヒドロキシホスホノ酢酸（ＨＰＡＡ）、ホスホノブタントリカルボン酸（ＰＢＴＣ）、ピロリン酸、及びポリリン酸からなる群から選ばれる少なくとも一種であることが好ましく、ＨＥＤＰ、ＨＰＡＡ及び１−ホスホノブタン−２，３，４−トリカルボン酸からなる群から選ばれる少なくとも一種であることがより好ましい。
[BTA or its degradation inhibitor]
The polishing liquid composition according to the present disclosure contains BTA or a derivative thereof that inhibits alteration from the viewpoint of improving storage stability. From the viewpoint of improving storage stability, the alteration inhibitor is at least one selected from the group consisting of an organic phosphonic acid containing no nitrogen atom in the molecule and a condensed phosphoric acid containing no nitrogen atom in the molecule. In one or a plurality of embodiments, the alteration inhibitor is 1-hydroxyethylidene-1′1-diphosphonic acid (HEDP), hydroxyphosphonoacetic acid (HPAA), phosphonobutanetricarboxylic acid, from the viewpoint of improving storage stability. Preferably, it is at least one selected from the group consisting of (PBTC), pyrophosphoric acid, and polyphosphoric acid, and is at least one selected from the group consisting of HEDP, HPAA, and 1-phosphonobutane-2,3,4-tricarboxylic acid It is more preferable.
本開示に係る研磨液組成物におけるＢＴＡ又はその誘導体の変質抑制物質の含有量は、貯蔵安定性向上の観点から、研磨液組成物全体の質量に対して好ましくは０．００１質量％以上１質量％以下、より好ましくは０．０１質量％以上０．５質量％以下、更に好ましくは０．０１質量％以上０．１質量％以下である。なお、研磨液組成物中の前記変質抑制物質はいずれか１種類であってもよく、２種類以上であってもよい。 The content of the alteration inhibitor of BTA or a derivative thereof in the polishing liquid composition according to the present disclosure is preferably 0.001% by mass or more and 1% by mass with respect to the total mass of the polishing liquid composition from the viewpoint of improving storage stability. % Or less, more preferably 0.01% by mass or more and 0.5% by mass or less, and still more preferably 0.01% by mass or more and 0.1% by mass or less. In addition, any one type may be sufficient as the said quality-change suppression substance in polishing liquid composition, and two or more types may be sufficient as it.
また、研磨液組成物中における、シリカ粒子と前記変質抑制物質との濃度比［シリカ粒子の濃度（質量％）／変質抑制物質の濃度（質量％）］は、貯蔵安定性向上の観点から、好ましくは５０以上１０００以下、より好ましくは１００以上６００以下である。 In the polishing composition, the concentration ratio between the silica particles and the alteration inhibiting substance [silica particle concentration (mass%) / alteration inhibiting substance concentration (mass%)] is from the viewpoint of improving storage stability. Preferably they are 50 or more and 1000 or less, More preferably, they are 100 or more and 600 or less.
さらに、研磨液組成物中における、ＢＴＡ及びその誘導体の合計と前記変質抑制物質との濃度比［ＢＴＡ及びその誘導体の合計の濃度（質量％）／変質抑制物質の濃度（質量％）］は、貯蔵安定性向上の観点から、好ましくは０．１以上５０以下、より好ましくは１以上２５以下、更に好ましくは２．５以上１５以下、更により好ましくは３以上８以下である。 Further, in the polishing composition, the concentration ratio of the total of BTA and its derivative and the alteration inhibiting substance [the total concentration of BTA and its derivative (mass%) / the concentration of the alteration inhibiting substance (mass%)] is: From the viewpoint of improving storage stability, it is preferably 0.1 or more and 50 or less, more preferably 1 or more and 25 or less, still more preferably 2.5 or more and 15 or less, and even more preferably 3 or more and 8 or less.
［シリカ粒子］
本開示に係る研磨液組成物は、研磨材としてシリカ粒子を含有する。本開示に係る研磨液組成物に用いられるシリカ粒子は、例えばコロイダルシリカ、ヒュームドシリカ、表面修飾したシリカ等が挙げられるが、研磨後の基板のスクラッチ及びナノ突起欠陥の低減の観点から、コロイダルシリカが好ましい。コロイダルシリカは、１種類からなるものであっても、２種類以上のコロイダルシリカを混合したものであってもよい。
[Silica particles]
The polishing liquid composition according to the present disclosure contains silica particles as an abrasive. Examples of the silica particles used in the polishing composition according to the present disclosure include colloidal silica, fumed silica, surface-modified silica, and the like. From the viewpoint of reducing scratches on the substrate after polishing and nanoprotrusion defects, colloidal. Silica is preferred. The colloidal silica may be composed of one type or a mixture of two or more types of colloidal silica.
〔散乱強度分布に基づく平均粒径〕
コロイダルシリカの散乱強度分布に基づく平均粒径は、研磨後の基板表面のスクラッチ及びナノ突起欠陥を低減する観点から、１ｎｍ以上４０ｎｍ以下が好ましく、より好ましくは５ｎｍ以上３７ｎｍ以下、さらに好ましくは１０ｎｍ以上３５ｎｍ以下である。コロイダルシリカの散乱強度分布に基づく平均粒径は、動的光散乱法において検出角９０°で測定される散乱強度分布に基づく平均粒径をいい、実施例に記載の方法で測定できる。
[Average particle diameter based on scattering intensity distribution]
The average particle size based on the scattering intensity distribution of colloidal silica is preferably 1 nm or more and 40 nm or less, more preferably 5 nm or more and 37 nm or less, and further preferably 10 nm or more, from the viewpoint of reducing scratches and nanoprotrusion defects on the substrate surface after polishing. 35 nm or less. The average particle diameter based on the scattering intensity distribution of colloidal silica refers to the average particle diameter based on the scattering intensity distribution measured at a detection angle of 90 ° in the dynamic light scattering method, and can be measured by the method described in the examples.
研磨液組成物中におけるシリカ粒子の含有量は、一又は複数の実施形態において、研磨速度向上と、貯蔵安定性向上の観点から、好ましくは０．５質量％以上、より好ましくは１質量％以上、更に好ましくは３質量％以上、更により好ましくは４質量％以上である。また、研磨後の基板表面のスクラッチ及びナノ突起欠陥低減と、貯蔵安定性向上の観点からは、好ましくは２０質量％以下、より好ましくは１５質量％以下、更に好ましくは１３質量％以下、更により好ましくは１０質量％以下である。研磨液組成物中におけるシリカ粒子の含有量は、好ましくは０．５質量％以上２０質量％以下、より好ましくは１質量％以上１５質量％以下、更に好ましくは３質量％以上１３質量％以下、更により好ましくは４質量％以上１０質量％以下である。 In one or a plurality of embodiments, the content of silica particles in the polishing composition is preferably 0.5% by mass or more, more preferably 1% by mass or more, from the viewpoint of improving the polishing rate and improving the storage stability. More preferably, it is 3% by mass or more, and still more preferably 4% by mass or more. Further, from the viewpoint of reducing scratches and nanoprotrusion defects on the substrate surface after polishing and improving storage stability, it is preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 13% by mass or less, and even more. Preferably it is 10 mass% or less. The content of silica particles in the polishing composition is preferably 0.5% by mass or more and 20% by mass or less, more preferably 1% by mass or more and 15% by mass or less, and further preferably 3% by mass or more and 13% by mass or less. More preferably, it is 4 mass% or more and 10 mass% or less.
［酸］
本開示に係る研磨液組成物は、酸を含有する。本開示において、酸の使用は、酸及び又はその塩の使用を含む。本開示に係る研磨液組成物に使用される酸としては、研磨速度の向上の観点から、その酸のｐＫ１が２以下の化合物が好ましく、研磨後の基板表面のスクラッチ及びナノ突起欠陥の低減の観点から、好ましくはｐＫ１が１．５以下、より好ましくは１以下、さらに好ましくはｐＫ１で表せない程の強い酸性を示す化合物である。好ましい酸は、硝酸、硫酸、亜硫酸、過硫酸、塩酸、過塩素酸、リン酸、ホスホン酸、ホスフィン酸、ピロリン酸、トリポリリン酸、アミド硫酸等の無機酸、２−アミノエチルホスホン酸、１−ヒドロキシエチリデン−１，１−ジホスホン酸、アミノトリ（メチレンホスホン酸）、エチレンジアミンテトラ（メチレンホスホン酸）、ジエチレントリアミンペンタ（メチレンホスホン酸）、エタン−１，１，−ジホスホン酸、エタン−１，１，２−トリホスホン酸、エタン−１−ヒドロキシ−１，１−ジホスホン酸、エタン−１−ヒドロキシ−１，１，２−トリホスホン酸、エタン−１，２−ジカルボキシ−１，２−ジホスホン酸、メタンヒドロキシホスホン酸、２−ホスホノブタン−１，２−ジカルボン酸、１−ホスホノブタン−２，３，４−トリカルボン酸、α−メチルホスホノコハク酸等の有機ホスホン酸、グルタミン酸、ピコリン酸、アスパラギン酸等のアミノカルボン酸、クエン酸、酒石酸、シュウ酸、ニトロ酢酸、マレイン酸、オキサロ酢酸等のカルボン酸等が挙げられる。中でも、スクラッチ低減の観点から、無機酸、カルボン酸、有機ホスホン酸が好ましく、酸化剤の安定性向上及び廃液処理性向上の観点から、無機酸、有機ホスホン酸がより好ましい。また、無機酸の中では、硝酸、硫酸、塩酸、過塩素酸がより好ましく、リン酸、硫酸がさらに好ましい。カルボン酸の中では、クエン酸、酒石酸、マレイン酸がより好ましく、クエン酸がさらに好ましい。有機ホスホン酸の中では、１−ヒドロキシエチリデン−１，１−ジホスホン酸、アミノトリ（メチレンホスホン酸）、ヒドロキシホスホノ酢酸、１−ホスホノブタン−２，３，４−トリカルボン酸、エチレンジアミンテトラ（メチレンホスホン酸）、ジエチレントリアミンペンタ（メチレンホスホン酸）及びそれらの塩がより好ましく、１−ヒドロキシエチリデン−１，１−ジホスホン酸、ヒドロキシホスホノ酢酸、１−ホスホノブタン−２，３，４−トリカルボン酸がさらに好ましい。これらの酸及びその塩は単独で又は２種以上を混合して用いてもよいが、研磨速度の向上、ナノ突起低減及び基板の洗浄性向上の観点から、２種以上を混合して用いることが好ましく、研磨後の基板表面のスクラッチ及びナノ突起欠陥低減、貯蔵安定性向上、酸化剤の安定性向上及び廃液処理性向上の観点から、リン酸、硫酸、クエン酸及び１−ヒドロキシエチリデン−１，１−ジホスホン酸からなる群から選択される２種以上の酸を混合して用いることがさらに好ましい。ここで、ｐＫ１とは有機化合物又は無機化合物の第一酸解離定数（２５℃）の逆数の対数値である。各化合物のｐＫ１は例えば改訂４版化学便覧（基礎編）ＩＩ、ｐｐ３１６−３２５（日本化学会編）等に記載されている。
[acid]
The polishing liquid composition according to the present disclosure contains an acid. In the present disclosure, the use of an acid includes the use of an acid and / or a salt thereof. The acid used in the polishing composition according to the present disclosure is preferably a compound having an acid pK1 of 2 or less from the viewpoint of improving the polishing rate, and reduces scratches and nanoprotrusion defects on the substrate surface after polishing. From the viewpoint, it is preferably a compound having a pK1 of 1.5 or less, more preferably 1 or less, and still more preferably a strong acidity that cannot be expressed by pK1. Preferred acids are inorganic acids such as nitric acid, sulfuric acid, sulfurous acid, persulfuric acid, hydrochloric acid, perchloric acid, phosphoric acid, phosphonic acid, phosphinic acid, pyrophosphoric acid, tripolyphosphoric acid, amidosulfuric acid, 2-aminoethylphosphonic acid, 1- Hydroxyethylidene-1,1-diphosphonic acid, aminotri (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), ethane-1,1, -diphosphonic acid, ethane-1,1,2 -Triphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acid, ethane-1-hydroxy-1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxy Phosphonic acid, 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2,3,4 Organic phosphonic acids such as tricarboxylic acid and α-methylphosphonosuccinic acid, aminocarboxylic acids such as glutamic acid, picolinic acid and aspartic acid, carboxylic acids such as citric acid, tartaric acid, oxalic acid, nitroacetic acid, maleic acid and oxaloacetic acid Is mentioned. Among these, inorganic acids, carboxylic acids, and organic phosphonic acids are preferable from the viewpoint of reducing scratches, and inorganic acids and organic phosphonic acids are more preferable from the viewpoint of improving the stability of the oxidizing agent and improving the waste liquid processability. Among inorganic acids, nitric acid, sulfuric acid, hydrochloric acid, and perchloric acid are more preferable, and phosphoric acid and sulfuric acid are more preferable. Among the carboxylic acids, citric acid, tartaric acid, and maleic acid are more preferable, and citric acid is more preferable. Among organic phosphonic acids, 1-hydroxyethylidene-1,1-diphosphonic acid, aminotri (methylenephosphonic acid), hydroxyphosphonoacetic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid, ethylenediaminetetra (methylenephosphonic acid) ), Diethylenetriaminepenta (methylenephosphonic acid) and salts thereof are more preferable, and 1-hydroxyethylidene-1,1-diphosphonic acid, hydroxyphosphonoacetic acid, and 1-phosphonobutane-2,3,4-tricarboxylic acid are more preferable. These acids and salts thereof may be used alone or in combination of two or more, but from the viewpoint of improving the polishing rate, reducing nanoprotrusions and improving the cleaning property of the substrate, use two or more in combination. From the viewpoints of reducing scratches and nanoprotrusion defects on the substrate surface after polishing, improving storage stability, improving the stability of the oxidizing agent, and improving the waste liquid processability, it is preferable to use phosphoric acid, sulfuric acid, citric acid, and 1-hydroxyethylidene-1 More preferably, a mixture of two or more acids selected from the group consisting of 1,1-diphosphonic acid is used. Here, pK1 is a logarithmic value of the reciprocal of the first acid dissociation constant (25 ° C.) of the organic compound or inorganic compound. The pK1 of each compound is described in, for example, the revised 4th edition, Chemical Handbook (Basic Edition) II, pp316-325 (Edited by Chemical Society of Japan).
これらの酸の塩を用いる場合の対イオンとしては、特に限定はなく、具体的には、金属、アンモニウム、アルキルアンモニウム等のイオンが挙げられる。上記金属の具体例としては、周期律表（長周期型）１Ａ、１Ｂ、２Ａ、２Ｂ、３Ａ、３Ｂ、４Ａ、６Ａ、７Ａ又は８族に属する金属が挙げられる。これらの中でも、研磨後の基板表面のスクラッチ及びナノ突起欠陥の低減の観点から１Ａ族に属する金属又はアンモニウムとの塩が好ましい。 There are no particular limitations on the counter ion when these acid salts are used, and specific examples include ions of metals, ammonium, alkylammonium, and the like. Specific examples of the metal include metals belonging to the periodic table (long-period type) 1A, 1B, 2A, 2B, 3A, 3B, 4A, 6A, 7A, or Group 8. Among these, from the viewpoint of reducing scratches on the substrate surface after polishing and nanoprotrusion defects, salts belonging to Group 1A metals or ammonium are preferable.
研磨液組成物中における前記酸及びその塩の含有量は、研磨速度向上、並びに研磨後の基板表面のスクラッチ及びナノ突起欠陥低減の観点から、好ましくは０．００１質量％以上５質量％以下、より好ましくは０．０１質量％以上４質量％以下であり、更に好ましくは０．０５質量％以上３質量％以下、更により好ましくは０．１質量％以上２．０質量％以下である。 The content of the acid and the salt thereof in the polishing composition is preferably 0.001% by mass or more and 5% by mass or less from the viewpoint of improving the polishing rate and reducing scratches and nanoprotrusion defects on the substrate surface after polishing. More preferably, it is 0.01 mass% or more and 4 mass% or less, More preferably, it is 0.05 mass% or more and 3 mass% or less, More preferably, it is 0.1 mass% or more and 2.0 mass% or less.
なお、本開示に係る研磨液組成物中の酸は、前記「分子内に窒素原子を含まない有機ホスホン酸及び縮合リン酸」と全部又は一部は同一であってもよい。変質抑制物質として用いる場合には、その量は０．００１質量％以上１質量％以下で用いることができる。 The acid in the polishing composition according to the present disclosure may be the same as the whole or a part of the “organic phosphonic acid and condensed phosphoric acid not containing a nitrogen atom in the molecule”. When used as an alteration inhibiting substance, the amount can be 0.001% by mass or more and 1% by mass or less.
［酸化剤］
本開示に係る研磨液組成物は、酸化剤を含む。本開示に係る研磨液組成物に使用できる酸化剤としては、研磨速度向上、並びに研磨後の基板表面のスクラッチ及びナノ突起欠陥の低減の観点から、過酸化物、過マンガン酸又はその塩、クロム酸又はその塩、ペルオキソ酸又はその塩、酸素酸又はその塩、金属塩類、硝酸類、硫酸類等が挙げられる。
[Oxidant]
The polishing liquid composition according to the present disclosure contains an oxidizing agent. The oxidizing agent that can be used in the polishing composition according to the present disclosure includes peroxide, permanganic acid or a salt thereof, chromium, from the viewpoint of improving the polishing rate and reducing scratches and nanoprotrusion defects on the substrate surface after polishing. Examples thereof include acids or salts thereof, peroxo acids or salts thereof, oxyacids or salts thereof, metal salts, nitric acids, and sulfuric acids.
前記過酸化物としては、過酸化水素、過酸化ナトリウム、過酸化バリウム等が挙げられ、過マンガン酸又はその塩としては、過マンガン酸カリウム等が挙げられ、クロム酸又はその塩としては、クロム酸金属塩、重クロム酸金属塩等が挙げられ、ペルオキソ酸又はその塩としては、ペルオキソ二硫酸、ペルオキソ二硫酸アンモニウム、ペルオキソ二硫酸金属塩、ペルオキソリン酸、ペルオキソ硫酸、ペルオキソホウ酸ナトリウム、過ギ酸、過酢酸、過安息香酸、過フタル酸等が挙げられ、酸素酸又はその塩としては、次亜塩素酸、次亜臭素酸、次亜ヨウ素酸、塩素酸、臭素酸、ヨウ素酸、次亜塩素酸ナトリウム、次亜塩素酸カルシウム等が挙げられ、金属塩類としては、塩化鉄（ＩＩＩ）、硝酸鉄（ＩＩＩ）、硫酸鉄（ＩＩＩ）、クエン酸鉄（ＩＩＩ）、硫酸アンモニウム鉄（ＩＩＩ）等が挙げられる。 Examples of the peroxide include hydrogen peroxide, sodium peroxide, barium peroxide, etc., examples of the permanganic acid or salt thereof include potassium permanganate, and examples of the chromic acid or salt thereof include chromium. Acid metal salts, metal dichromates, and the like. Peroxo acids or salts thereof include peroxodisulfuric acid, ammonium peroxodisulfate, peroxodisulfate metal salts, peroxophosphoric acid, peroxosulfuric acid, sodium peroxoborate, and performic acid. Peroxyacetic acid, perbenzoic acid, perphthalic acid, etc., and oxygen acids or salts thereof include hypochlorous acid, hypobromite, hypoiodous acid, chloric acid, bromic acid, iodic acid, hypochlorous acid. Examples include sodium chlorate, calcium hypochlorite, and metal salts include iron (III) chloride, iron (III) nitrate, iron (III) sulfate, and iron citrate. III), ammonium iron (III), and the like.
研磨後の基板表面のスクラッチ及びナノ突起欠陥低減と、貯蔵安定性向上の観点から好ましい酸化剤としては、過酸化水素、硝酸鉄（ＩＩＩ）、過酢酸、ペルオキソ二硫酸アンモニウム、硫酸鉄（ＩＩＩ）及び硫酸アンモニウム鉄（ＩＩＩ）等が挙げられる。より好ましい酸化剤としては、表面に金属イオンが付着せず汎用に使用され安価であるという観点から過酸化水素が挙げられる。これらの酸化剤は、単独で又は２種以上を混合して使用してもよい。 Preferred oxidizing agents from the viewpoint of reducing scratches and nanoprotrusion defects on the substrate surface after polishing and improving storage stability include hydrogen peroxide, iron (III) nitrate, peracetic acid, ammonium peroxodisulfate, iron (III) sulfate and Examples include ammonium iron (III) sulfate. As a more preferable oxidizing agent, hydrogen peroxide is mentioned from the viewpoint that metal ions do not adhere to the surface and are generally used and inexpensive. These oxidizing agents may be used alone or in admixture of two or more.
研磨液組成物中における前記酸化剤の含有量は、研磨速度向上の観点から、好ましくは０．０１質量％以上、より好ましくは０．０５質量％以上、更に好ましくは０．１質量％以上であり、研磨後の基板表面のスクラッチ及びナノ突起欠陥低減、貯蔵安定性向上の観点からから、好ましくは４質量％以下、より好ましくは２質量％以下、更に好ましくは１質量％以下である。表面品質を保ちつつ研磨速度を向上させるためには、上記含有量は、好ましくは０．０１質量％以上４質量％以下、より好ましくは０．０５質量％以上２質量％以下、更に好ましくは０．１質量％以上１質量％以下である。 The content of the oxidizing agent in the polishing liquid composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and further preferably 0.1% by mass or more from the viewpoint of improving the polishing rate. From the viewpoint of reducing scratches and nanoprotrusion defects on the substrate surface after polishing and improving storage stability, it is preferably 4% by mass or less, more preferably 2% by mass or less, and still more preferably 1% by mass or less. In order to improve the polishing rate while maintaining the surface quality, the content is preferably 0.01% by mass to 4% by mass, more preferably 0.05% by mass to 2% by mass, and still more preferably 0%. It is 1 mass% or more and 1 mass% or less.
［水］
本開示に係る研磨液組成物中の水は、媒体として使用されるものであり、蒸留水、イオン交換水、超純水等が挙げられる。被研磨基板の表面清浄性の観点からイオン交換水及び超純水が好ましく、超純水がより好ましい。研磨液組成物中の水の含有量は、好ましくは６０質量％以上９９．４質量％以下、より好ましくは７０質量％以上９８．９質量％以下である。また、本開示の効果を阻害しない範囲内でアルコール等の有機溶剤を配合してもよい。
[water]
Water in the polishing composition according to the present disclosure is used as a medium, and examples thereof include distilled water, ion exchange water, and ultrapure water. From the viewpoint of the surface cleanliness of the substrate to be polished, ion exchange water and ultrapure water are preferable, and ultrapure water is more preferable. The water content in the polishing composition is preferably 60% by mass or more and 99.4% by mass or less, more preferably 70% by mass or more and 98.9% by mass or less. Moreover, you may mix | blend organic solvents, such as alcohol, in the range which does not inhibit the effect of this indication.
［アニオン性基を有する水溶性高分子］
本開示に係る研磨液組成物は、研磨後の基板表面のスクラッチ及びナノ突起欠陥の低減の観点から、アニオン性基を有する水溶性高分子を含有してもよい。前記水溶性高分子のアニオン性基としては、カルボン酸基、スルホン酸基、硫酸エステル基、リン酸エステル基、ホスホン酸基等が挙げられる。これらのアニオン性基は中和された塩の形態を取ってもよい。スクラッチ及びナノ突起低減の観点から、スルホン酸基及びカルボン酸基の少なくとも一方を有するアニオン性高分子が好ましく、スルホン酸基を有するアニオン性高分子がより好ましい。
[Water-soluble polymer having an anionic group]
The polishing liquid composition according to the present disclosure may contain a water-soluble polymer having an anionic group from the viewpoint of reducing scratches on the substrate surface after polishing and reducing nanoprotrusion defects. Examples of the anionic group of the water-soluble polymer include a carboxylic acid group, a sulfonic acid group, a sulfate ester group, a phosphate ester group, and a phosphonic acid group. These anionic groups may take the form of neutralized salts. From the viewpoint of reducing scratches and nanoprotrusions, an anionic polymer having at least one of a sulfonic acid group and a carboxylic acid group is preferable, and an anionic polymer having a sulfonic acid group is more preferable.
［その他の成分］
本開示に係る研磨液組成物には、必要に応じて他の成分を配合することができる。他の成分としては、増粘剤、分散剤、防錆剤、塩基性物質、界面活性剤等が挙げられる。研磨液組成物中のこれら他の任意成分の含有量は、０〜１０質量％が好ましく、０〜５質量％がより好ましい。但し、本開示に係る研磨液組成物は、他の成分、とりわけ界面活性剤を含むことなく、研磨後の基板表面のスクラッチ及びナノ突起欠陥の低減効果を発揮し得る。さらに、本開示に係る研磨液組成物は、アルミナ砥粒を含ませることができ、最終研磨工程より前の粗研磨工程に使用することもできる。
[Other ingredients]
In the polishing composition according to the present disclosure, other components can be blended as necessary. Examples of other components include a thickener, a dispersant, a rust inhibitor, a basic substance, and a surfactant. 0-10 mass% is preferable and, as for content of these other arbitrary components in polishing liquid composition, 0-5 mass% is more preferable. However, the polishing composition according to the present disclosure can exhibit the effect of reducing scratches and nanoprotrusion defects on the substrate surface after polishing without including other components, particularly surfactants. Furthermore, the polishing composition according to the present disclosure can contain alumina abrasive grains, and can also be used in a rough polishing step prior to the final polishing step.
［研磨液組成物のｐＨ］
本開示に係る研磨液組成物のｐＨは、研磨速度向上、貯蔵安定性向上の観点から３．５以下が好ましく、より好ましくは３．０以下、さらに好ましくは２．５以下、さらにより好ましくは２．０以下である。また研磨後の基板表面のスクラッチ及びナノ突起欠陥を低減する観点から、０．５以上が好ましく、より好ましくは０．８以上、さらに好ましくは１．０以上、さらにより好ましくは１．２以上である。また、研磨液組成物の廃液ｐＨは、研磨速度向上の観点から３以下が好ましく、より好ましくは２．５以下、さらに好ましくは２．２以下、さらにより好ましくは２．０以下である。また、研磨後の基板表面のスクラッチ及びナノ突起欠陥低減、貯蔵安定性向上の観点から、研磨液組成物の廃液ｐＨは、０．８以上が好ましく、より好ましくは１．０以上、さらに好ましくは１．２以上、さらにより好ましくは１．５以上である。なお、廃液ｐＨとは、研磨液組成物を用いた研磨工程における研磨廃液、即ち、研磨機より排出された直後の研磨液組成物のｐＨをいう。
[PH of polishing composition]
The pH of the polishing composition according to the present disclosure is preferably 3.5 or less, more preferably 3.0 or less, still more preferably 2.5 or less, and even more preferably from the viewpoint of improving polishing rate and storage stability. 2.0 or less. Further, from the viewpoint of reducing scratches and nanoprotrusion defects on the substrate surface after polishing, 0.5 or more is preferable, more preferably 0.8 or more, still more preferably 1.0 or more, and even more preferably 1.2 or more. is there. In addition, the waste liquid pH of the polishing composition is preferably 3 or less, more preferably 2.5 or less, still more preferably 2.2 or less, and even more preferably 2.0 or less, from the viewpoint of improving the polishing rate. In addition, from the viewpoint of reducing scratches and nanoprotrusion defects on the substrate surface after polishing and improving storage stability, the waste liquid pH of the polishing composition is preferably 0.8 or more, more preferably 1.0 or more, and still more preferably. 1.2 or more, and even more preferably 1.5 or more. The waste liquid pH refers to the polishing waste liquid in the polishing step using the polishing liquid composition, that is, the pH of the polishing liquid composition immediately after being discharged from the polishing machine.
［研磨液組成物の調製方法］
本開示に係る研磨液組成物は、例えば、研磨材（シリカ粒子を含む）、酸、酸化剤、複素環芳香族化合物（ベンゾトリアゾール又はその誘導体を含む）、脂肪族アミン化合物（ジアミン及びトリアミンを含む）、及び水を、さらに所望により他の成分を含めて、公知の方法で混合することにより調製できる。この際、研磨材は、濃縮されたスラリーの状態で混合されてもよいし、水等で希釈してから混合されてもよい。本開示に係る研磨液組成物中における各成分の含有量や濃度は、上述した範囲であるが、その他の態様として、本開示に係る研磨液組成物を濃縮物として調製してもよい。
[Method for preparing polishing liquid composition]
The polishing liquid composition according to the present disclosure includes, for example, an abrasive (including silica particles), an acid, an oxidizing agent, a heterocyclic aromatic compound (including benzotriazole or a derivative thereof), an aliphatic amine compound (diamine and triamine). And other components may be added by mixing in a known manner if desired. At this time, the abrasive may be mixed in a concentrated slurry state or may be mixed after being diluted with water or the like. The content and concentration of each component in the polishing liquid composition according to the present disclosure are in the above-described ranges, but as another aspect, the polishing liquid composition according to the present disclosure may be prepared as a concentrate.
［研磨液組成物の保存方法］
上記の様に調製された研磨液組成物は、組成物として安定であり、研磨液組成物の保存方法を提供することにもなる。保存方法の条件としては研磨液組成物として上述したシリカ濃度やｐＨ以外に以下の態様が挙げられる。
保持温度： シリカの凝集抑制又は安定性、研磨後の基板表面のスクラッチ及びナノ突起欠陥低減、貯蔵安定性向上の観点から研磨剤組成物の温度は、１℃以上５０℃以下が好ましい。より好ましくは５℃以上４５℃以下であり、更に好ましくは１０℃以上４０℃以下である。また、同様の観点から温度変化は、５０℃以内に抑えるのが好ましく、より好ましくは４０℃以下であり、更に好ましくは３０℃以下である。
容器： 研磨剤組成物の保存に用いる容器の材質は拘らないが、シリカの凝集抑制又は安定性、研磨後の基板表面のスクラッチ及びナノ突起欠陥低減、貯蔵安定性向上の観点からＵＶ遮断能を有する容器、温度変化を受けにくい容器が挙げられる。具体的には、高分子樹脂材料（ポリエチレン、ポリプロピレン、ポリ（テトラフルオロイチレン）等）や金属性材料（ＳＵＳ等）が挙げられる。また、容器形態についても拘らないが、シリカ凝集抑制、研磨後の表面欠陥のスクラッチ及びナノ突起欠陥低減、貯蔵安定性向上の観点から、蓋付きの密閉できる容器が好ましい。
[Preservation method of polishing composition]
The polishing composition prepared as described above is stable as a composition, and also provides a method for storing the polishing composition. As the conditions for the storage method, the following aspects may be mentioned in addition to the silica concentration and pH described above as the polishing composition.
Holding temperature: The temperature of the abrasive composition is preferably 1 ° C. or higher and 50 ° C. or lower from the viewpoint of suppressing or stabilizing the aggregation of silica, reducing scratches and nanoprotrusion defects on the substrate surface after polishing, and improving storage stability. More preferably, it is 5 degreeC or more and 45 degrees C or less, More preferably, it is 10 degreeC or more and 40 degrees C or less. Moreover, it is preferable to suppress a temperature change within 50 degreeC from the same viewpoint, More preferably, it is 40 degrees C or less, More preferably, it is 30 degrees C or less.
Container: Regardless of the material of the container used for storage of the abrasive composition, it has UV blocking ability from the viewpoint of suppressing or stabilizing the aggregation of silica, reducing scratches and nanoprotrusions on the surface of the substrate after polishing, and improving storage stability. And a container that is less susceptible to temperature changes. Specific examples include polymer resin materials (polyethylene, polypropylene, poly (tetrafluoroethylene), etc.) and metallic materials (SUS, etc.). Moreover, although it does not concern about a container form, the container which can be sealed with a lid | cover is preferable from a viewpoint of silica aggregation suppression, a scratch of the surface defect after grinding | polishing, a nanoprotrusion defect reduction, and a storage stability improvement.
［被研磨基板］
本開示に係る研磨液組成物が研磨の対象とする被研磨基板は、Ｎｉ−Ｐメッキされたアルミニウム合金基板である。本開示において「Ｎｉ−Ｐメッキされたアルミニウム合金基板」とは、磁気ディスク基板用アルミニウム合金板材の表面を研削後、無電解Ｎｉ−Ｐメッキ処理したものをいう。Ｎｉ−Ｐメッキされたアルミニウム合金基板の表面を本開示に係る研磨液組成物で研磨することを含む研磨工程の後、さらに、スパッタ等でその基板表面に磁性膜を形成する工程を行うことにより磁気ディスク基板を製造することができる。本開示に係る研磨液組成物をＮｉ−Ｐメッキされたアルミニウム合金基板の研磨に使用することで、研磨後の基板表面のスクラッチの低減とともに、研磨後の基板表面のナノ突起欠陥の低減という効果を奏する。
[Polished substrate]
The substrate to be polished by the polishing composition according to the present disclosure is a Ni-P plated aluminum alloy substrate. In the present disclosure, the “Ni—P plated aluminum alloy substrate” means a surface of an aluminum alloy plate material for a magnetic disk substrate that has been subjected to electroless Ni—P plating after being ground. By performing a step of forming a magnetic film on the surface of the substrate by sputtering or the like after a polishing step including polishing the surface of the Ni-P plated aluminum alloy substrate with the polishing composition according to the present disclosure. A magnetic disk substrate can be manufactured. By using the polishing composition according to the present disclosure for polishing an aluminum alloy substrate plated with Ni-P, the effect of reducing scratches on the surface of the substrate after polishing and reducing nanoprotrusion defects on the surface of the substrate after polishing. Play.
［磁気ディスク基板の製造方法］
本開示は、その他の態様として、磁気ディスク基板の製造方法（以下、本開示に係る製造方法ともいう。）に関する。本開示に係る製造方法は、上述した本開示に係る研磨液組成物を用いて被研磨基板を研磨する工程を含む磁気ディスク基板の製造方法である。これにより、研磨後の基板表面のスクラッチに加えて、研磨後の基板表面のナノ突起欠陥が低減された磁気ディスク基板を好ましくは提供できる。本開示に係る製造方法は、とりわけ、垂直磁気記録方式用磁気ディスク基板の製造方法に適している。
[Method of manufacturing magnetic disk substrate]
As another aspect, the present disclosure relates to a method for manufacturing a magnetic disk substrate (hereinafter also referred to as a manufacturing method according to the present disclosure). The manufacturing method according to the present disclosure is a method for manufacturing a magnetic disk substrate including a step of polishing a substrate to be polished using the polishing liquid composition according to the present disclosure described above. Thereby, in addition to scratches on the substrate surface after polishing, a magnetic disk substrate in which nanoprojection defects on the substrate surface after polishing are reduced can be preferably provided. The manufacturing method according to the present disclosure is particularly suitable for a method of manufacturing a magnetic disk substrate for perpendicular magnetic recording.
本開示に係る研磨液組成物を用いて被研磨基板を研磨する方法の具体例としては、不織布状の有機高分子系研磨布等の研磨パッドを貼り付けた定盤で被研磨基板を挟み込み、本開示に係る研磨液組成物を研磨機に供給しながら、定盤や被研磨基板を動かして被研磨基板を研磨する方法が挙げられる。 As a specific example of a method for polishing a substrate to be polished using the polishing liquid composition according to the present disclosure, the substrate to be polished is sandwiched between a surface plate to which a polishing pad such as a non-woven organic polymer polishing cloth is attached, A method of polishing a substrate to be polished by moving a surface plate or a substrate to be polished while supplying the polishing composition according to the present disclosure to a polishing machine can be mentioned.
被研磨基板の研磨工程が多段階で行われる場合は、本開示に係る研磨液組成物を用いた研磨工程は２段階目以降に行われるのが好ましく、最終研磨工程で行われるのがより好ましい。その際、前工程の研磨材や研磨液組成物の混入を避けるために、それぞれ別の研磨機を使用してもよく、またそれぞれ別の研磨機を使用した場合では、研磨工程毎に被研磨基板を洗浄することが好ましい。なお、研磨機としては、特に限定されず、磁気ディスク基板研磨用の公知の研磨機が使用できる。 When the polishing process of the substrate to be polished is performed in multiple stages, the polishing process using the polishing composition according to the present disclosure is preferably performed in the second stage or more, and more preferably performed in the final polishing process. . At that time, in order to avoid mixing of the polishing material and polishing liquid composition in the previous process, different polishing machines may be used, and in the case of using different polishing machines, polishing is performed for each polishing process. It is preferable to clean the substrate. The polishing machine is not particularly limited, and a known polishing machine for polishing a magnetic disk substrate can be used.
［研磨パッド］
本開示で使用される研磨パッドとしては、特に制限はなく、スエードタイプ、不織布タイプ、ポリウレタン独立発泡タイプ、又はこれらを積層した二層タイプ等の研磨パッドを使用することができるが、研磨速度の観点から、スエードタイプの研磨パッドが好ましい。
[Polishing pad]
The polishing pad used in the present disclosure is not particularly limited, and a suede type, a nonwoven fabric type, a polyurethane closed-cell foam type, or a two-layer type laminated with these can be used. From the viewpoint, a suede type polishing pad is preferable.
研磨パッドの表面部材の平均気孔径は、スクラッチ低減及びパッド寿命の観点から、５０μｍ以下が好ましく、より好ましくは４５μｍ以下、さらに好ましくは４０μｍ以下、さらにより好ましくは３５μｍ以下である。パッドの研磨液保持性の観点から、気孔で研磨液を保持し液切れを起こさないようにするために、平均気孔径は０．０１μｍ以上が好ましく、より好ましくは０．１μｍ以上、さらに好ましくは１μｍ以上、さらにより好ましくは２．５μｍ以上である。また、研磨パッドの気孔径の最大値は、研磨速度維持の観点から、１００μｍ以下が好ましく、より好ましくは５０μｍ以下、さらに好ましくは２５μｍ以下、特に好ましくは２０μｍ以下である。 The average pore diameter of the surface member of the polishing pad is preferably 50 μm or less, more preferably 45 μm or less, still more preferably 40 μm or less, and even more preferably 35 μm or less, from the viewpoint of scratch reduction and pad life. From the viewpoint of holding the polishing liquid of the pad, the average pore diameter is preferably 0.01 μm or more, more preferably 0.1 μm or more, and still more preferably, in order to keep the polishing liquid in the pores and prevent the liquid from running out. It is 1 μm or more, and more preferably 2.5 μm or more. Further, the maximum value of the pore size of the polishing pad is preferably 100 μm or less, more preferably 50 μm or less, further preferably 25 μm or less, and particularly preferably 20 μm or less from the viewpoint of maintaining the polishing rate.
［研磨荷重］
本開示に係る研磨液組成物を用いた研磨工程における研磨荷重は、好ましくは５．９ｋＰａ以上、より好ましくは６．９ｋＰａ以上、さらに好ましくは７．５ｋＰａ以上である。これにより、研磨速度の低下を抑制できるため、生産性の向上が可能となる。なお、本開示に係る製造方法において研磨荷重とは、研磨時に被研磨基板の研磨面に加えられる定盤の圧力をいう。また、本開示に係る研磨液組成物を用いた研磨工程において、研磨荷重は２０ｋＰａ以下が好ましく、より好ましくは１８ｋＰａ以下、さらに好ましくは１６ｋＰａ以下である。これにより、スクラッチの発生を抑制することができる。したがって、本開示に係る研磨液組成物を用いた研磨工程において研磨荷重は５．９〜２０ｋＰａが好ましく、６．９〜１８ｋＰａがより好ましく、７．５〜１６ｋＰａがさらに好ましい。研磨荷重の調整は、定盤及び被研磨基板のうち少なくとも一方に空気圧や重りを負荷することにより行うことができる。
[Polishing load]
The polishing load in the polishing step using the polishing composition according to the present disclosure is preferably 5.9 kPa or more, more preferably 6.9 kPa or more, and further preferably 7.5 kPa or more. Thereby, since the fall of a grinding | polishing speed | rate can be suppressed, productivity can be improved. In the manufacturing method according to the present disclosure, the polishing load refers to the pressure of the surface plate applied to the polishing surface of the substrate to be polished during polishing. Further, in the polishing step using the polishing composition according to the present disclosure, the polishing load is preferably 20 kPa or less, more preferably 18 kPa or less, and further preferably 16 kPa or less. Thereby, generation | occurrence | production of a scratch can be suppressed. Therefore, in the polishing process using the polishing composition according to the present disclosure, the polishing load is preferably 5.9 to 20 kPa, more preferably 6.9 to 18 kPa, and further preferably 7.5 to 16 kPa. The polishing load can be adjusted by applying air pressure or weight to at least one of the surface plate and the substrate to be polished.
［研磨液組成物の供給］
本開示に係る研磨液組成物を用いた研磨工程における研磨液組成物の供給速度は、スクラッチ低減の観点から、被研磨基板１ｃｍ2当たり、好ましくは０．０５〜１５ｍＬ／分であり、より好ましくは０．０６〜１０ｍＬ／分であり、さらに好ましくは０．０７〜１ｍＬ／分、さらにより好ましくは０．０８〜０．５ｍＬ／分、さらにより好ましくは０．１２〜０．５ｍＬ／分である。
[Supply of polishing liquid composition]
The feed rate of the polishing composition in the polishing process using the polishing composition according to the present disclosure, from the viewpoint of reducing scratches, the substrate to be polished 1 cm 2 per preferably 0.05～15ML / min, more preferably Is 0.06 to 10 mL / min, more preferably 0.07 to 1 mL / min, even more preferably 0.08 to 0.5 mL / min, even more preferably 0.12 to 0.5 mL / min. is there.
本開示に係る研磨液組成物を研磨機へ供給する方法としては、例えばポンプ等を用いて連続的に供給を行う方法が挙げられる。研磨液組成物を研磨機へ供給する際は、全ての成分を含んだ１液で供給する方法の他、研磨液組成物の安定性等を考慮して、複数の配合用成分液に分け、２液以上で供給することもできる。後者の場合、例えば供給配管中又は被研磨基板上で、上記複数の配合用成分液が混合され、本開示に係る研磨液組成物となる。 As a method of supplying the polishing composition according to the present disclosure to a polishing machine, for example, a method of continuously supplying using a pump or the like can be mentioned. When supplying the polishing composition to the polishing machine, in addition to the method of supplying one component containing all the components, considering the stability of the polishing composition, etc., it is divided into a plurality of compounding component liquids, Two or more liquids can be supplied. In the latter case, for example, the plurality of compounding component liquids are mixed in the supply pipe or on the substrate to be polished to obtain the polishing liquid composition according to the present disclosure.
上記被研磨基板の形状には特に制限はなく、例えば、ディスク状、プレート状、スラブ状、プリズム状等の平面部を有する形状や、レンズ等の曲面部を有する形状であればよい。中でも、ディスク状の被研磨基板が適している。ディスク状の被研磨基板の場合、その外径は例えば２〜９５ｍｍ程度であり、その厚みは例えば０．５〜２ｍｍ程度である。 There is no restriction | limiting in particular in the shape of the said to-be-polished substrate, For example, what is necessary is just the shape which has planar parts, such as a disk shape, plate shape, slab shape, prism shape, and the shape which has curved surface parts, such as a lens. Of these, a disk-shaped substrate to be polished is suitable. In the case of a disk-shaped substrate to be polished, the outer diameter is, for example, about 2 to 95 mm, and the thickness is, for example, about 0.5 to 2 mm.
［研磨方法］
本開示は、その他の態様として、本開示に係る研磨液組成物を用いて被研磨基板であるＮｉ−Ｐメッキされたアルミニウム合金基板を研磨する工程を有する研磨方法に関する。該研磨方法は、一又は複数の実施形態において、研磨パッドに接触させながら被研磨基板を研磨することを含む被研磨基板の研磨方法が挙げられる。具体的な研磨の方法及び条件は、上述のとおりとすることができる。
[Polishing method]
As another aspect, the present disclosure relates to a polishing method including a step of polishing a Ni—P plated aluminum alloy substrate, which is a substrate to be polished, using the polishing composition according to the present disclosure. In one or a plurality of embodiments, the polishing method includes a method for polishing a substrate to be polished, including polishing the substrate to be polished while being in contact with a polishing pad. Specific polishing methods and conditions may be as described above.
［実施例３〜５、８、参考例１〜２、６〜７、９〜１４、及び比較例１〜６］
実施例３〜５、８、参考例１〜２、６〜７、９〜１４、及び比較例１〜６の研磨液組成物を調製し、６０℃で１日保存した後に、貯蔵安定性及びフィルター通液量を評価するとともに、被研磨基板の研磨を行って研磨後の基板のスクラッチ及びナノ突起欠陥を評価した。評価結果を下記表１に示す。使用した重合体、研磨液組成物の調製方法、各パラメータの測定方法、研磨条件（研磨方法）及び評価方法は以下のとおりである。なお、下記表１において、ＢＴＡは１Ｈ−ベンゾトリアゾール、ＴＴＡはトリルトリアゾール、ＡＥＥＡはＮ−（２−アミノエチル）エタノールアミン、ＤＥＴＡはジエチレントリアミン、ＴＥＡはトリエタノールアミン、ＡＥＰは、Ｎ−（２−アミノエチル）ピペラジン、ＨＥＤＰはヒドロキシエチリデン−１，１−ジホスホン酸、ＨＰＡＡはヒドロキシホスホノ酢酸、ＰＢＴＣは１−ホスホノブタン−２，３，４−トリカルボン酸、ＡＴＭＰはニトリロトリス（メチレンホスホン酸）、ＨＱＳはヒドロキノンスルホン酸カリウム塩を表す。
[Examples 3-5, 8, Reference Examples 1-2 , 6-7 , 9-14 , and Comparative Examples 1-6]
After preparing the polishing liquid composition of Examples 3-5 , 8, Reference Examples 1-2 , 6-7 , 9-14 , and Comparative Examples 1-6, and storing at 60 degreeC for 1 day, storage stability and The amount of liquid passing through the filter was evaluated, and the substrate to be polished was polished to evaluate scratches and nanoprotrusion defects of the substrate after polishing. The evaluation results are shown in Table 1 below. The polymer used, the method for preparing the polishing composition, the method for measuring each parameter, the polishing conditions (polishing method) and the evaluation method are as follows. In Table 1 below, BTA is 1H-benzotriazole, TTA is tolyltriazole, AEEA is N- (2-aminoethyl) ethanolamine, DETA is diethylenetriamine, TEA is triethanolamine, and AEP is N- (2- Aminoethyl) piperazine, HEDP is hydroxyethylidene-1,1-diphosphonic acid, HPAA is hydroxyphosphonoacetic acid, PBTC is 1-phosphonobutane-2,3,4-tricarboxylic acid, ATMP is nitrilotris (methylenephosphonic acid), HQS Represents hydroquinonesulfonic acid potassium salt.
［研磨液組成物の調製方法］
下記表１に記載のコロイダルシリカ（平均粒径＝２５ｎｍ、日揮触媒化成社製）、酸、酸化剤、ＢＴＡ、アミン、有機ホスホン酸／縮合リン酸、及び水を用いて実施例３〜５、８、参考例１〜２、６〜７、９〜１４、及び比較例１〜６の研磨液組成物を調製した（ｐＨ＝１．５）。
[Method for preparing polishing liquid composition]
Examples 3-5 using colloidal silica (average particle size = 25 nm, manufactured by JGC Catalysts & Chemicals Co., Ltd.), acid, oxidizing agent, BTA, amine, organic phosphonic acid / condensed phosphoric acid, and water listed in Table 1 below 8, polishing composition of Reference Examples 1-2 , 6-7 , 9-14 and Comparative Examples 1-6 were prepared (pH = 1.5).
コロイダルシリカの散乱強度分布に基づく平均粒径は下記方法で測定した。
コロイダルシリカと、硫酸と、過酸化水素水とをイオン交換水に添加し、これらを混合することにより、標準試料を作製した。標準試料中におけるコロイダルシリカ、硫酸、過酸化水素の含有量は、それぞれ５．０質量％、０．５質量％、０．４質量％であった。この標準試料を大塚電子社製動的光散乱装置ＤＬＳ−６５００により、同メーカーが添付した説明書に従って、２００回積算した際の検出角９０°におけるＣｕｍｕｌａｎｔ法によって得られる散乱強度分布の面積が全体の５０％となる粒径を求め、シリカ粒子の平均粒径とした。
（ＤＬＳ−６５００の測定条件）
検出角：９０°
Ｓａｍｐｌｉｎｇ ｔｉｍｅ ： ４（μｍ）
Ｃｏｒｒｅｌａｔｉｏｎ Ｃｈａｎｎｅｌ ： ２５６（ｃｈ）
Ｃｏｒｒｅｌａｔｉｏｎ Ｍｅｔｈｏｄ ： ＴＩ
Ｓａｍｐｌｉｎｇ ｔｅｍｐｅｒａｔｕｒｅ： ２６．０（℃）
検出角：３０°
Ｓａｍｐｌｉｎｇ ｔｉｍｅ ： １０（μｍ）
Ｃｏｒｒｅｌａｔｉｏｎ Ｃｈａｎｎｅｌ ： １０２４（ｃｈ）
Ｃｏｒｒｅｌａｔｉｏｎ Ｍｅｔｈｏｄ ： ＴＩ
Ｓａｍｐｌｉｎｇ ｔｅｍｐｅｒａｔｕｒｅ： ２６．０（℃）
The average particle diameter based on the scattering intensity distribution of colloidal silica was measured by the following method.
Colloidal silica, sulfuric acid, and hydrogen peroxide water were added to ion exchange water, and these were mixed to prepare a standard sample. The contents of colloidal silica, sulfuric acid, and hydrogen peroxide in the standard sample were 5.0 mass%, 0.5 mass%, and 0.4 mass%, respectively. The area of the scattering intensity distribution obtained by the Cumulant method at a detection angle of 90 ° when this standard sample is accumulated 200 times according to the instructions attached by the manufacturer using the dynamic light scattering device DLS-6500 manufactured by Otsuka Electronics Co., Ltd. The average particle size of the silica particles was determined.
(Measurement conditions for DLS-6500)
Detection angle: 90 °
Sampling time: 4 (μm)
Correlation Channel: 256 (ch)
Correlation Method: TI
Sampling temperature: 26.0 (° C.)
Detection angle: 30 °
Sampling time: 10 (μm)
Correlation Channel: 1024 (ch)
Correlation Method: TI
Sampling temperature: 26.0 (° C.)
［研磨］
上記のように調製した実施例３〜５、８、参考例１〜２、６〜７、９〜１４及び比較例１〜６の研磨液組成物（それぞれ、下記貯蔵安定性評価試験（６０℃、２４ｈ保存）の前後のもの）を用いて、以下に示す研磨条件にて下記被研磨基板を研磨した。次いで、研磨された基板のナノ突起欠陥、及びスクラッチを以下に示す条件に基づいて測定し、評価を行った。結果を下記表１に示す。下記表１に示すデータは、各実施例及び各比較例につき４枚の被研磨基板を研磨した後、各被研磨基板の両面について測定し、４枚（表裏合わせて計８面）のデータの平均とした。
[Polishing]
Polishing liquid compositions of Examples 3 to 5, 8 and Reference Examples 1 to 2, 6 to 7, 9 to 14 and Comparative Examples 1 to 6 prepared as described above (respectively, storage stability evaluation tests described below (60 ° C. , The substrate to be polished was polished under the following polishing conditions. Next, the nanoprojection defects and scratches on the polished substrate were measured and evaluated based on the following conditions. The results are shown in Table 1 below. The data shown in the following Table 1 is obtained by polishing four substrates for each example and each comparative example, and then measuring both surfaces of each substrate to be polished. Averaged.
［被研磨基板］
被研磨基板としては、Ｎｉ−Ｐメッキされたアルミニウム合金基板を予めアルミナ研磨材を含有する研磨液組成物で粗研磨した基板を用いた。なお、この被研磨基板は、厚さが１．２７ｍｍ、外径が９５ｍｍ、内径が２５ｍｍであり、ＡＦＭ（Ｄｉｇｉｔａｌ Ｉｎｓｔｒｕｍｅｎｔ ＮａｎｏＳｃｏｐｅ ＩＩＩａ Ｍｕｌｔｉ Ｍｏｄｅ ＡＦＭ）により測定した中心線平均粗さＲａが１ｎｍ、長波長うねり（波長０．４〜２ｍｍ）の振幅は２ｎｍ、短波長うねり（波長５０〜４００μｍ）の振幅は２ｎｍであった。
[Polished substrate]
As the substrate to be polished, a substrate obtained by rough polishing an aluminum alloy substrate plated with Ni-P in advance with a polishing composition containing an alumina abrasive was used. The substrate to be polished has a thickness of 1.27 mm, an outer diameter of 95 mm, an inner diameter of 25 mm, a center line average roughness Ra measured by AFM (Digital Instrument Nanoscope IIIa Multi Mode AFM), 1 nm, and a long wavelength. The amplitude of the undulation (wavelength 0.4 to 2 mm) was 2 nm, and the amplitude of the short wavelength undulation (wavelength 50 to 400 μm) was 2 nm.
［研磨条件］
研磨試験機：スピードファム社製「両面９Ｂ研磨機」
研磨パッド：フジボウ社製スエードタイプ（厚さ０．９ｍｍ、平均開孔径１０μｍ）
研磨液組成物供給量：１００ｍＬ／分（被研磨基板１ｃｍ2あたりの供給速度：０．０７２ｍＬ／分）
下定盤回転数：３２．５ｒｐｍ
研磨荷重：１２．０ｋＰａ
研磨時間：６分間
[Polishing conditions]
Polishing tester: "Fast double-sided 9B polishing machine" manufactured by Speedfam
Polishing pad: Fujibow Suede type (thickness 0.9mm, average hole diameter 10μm)
Polishing liquid composition supply amount: 100 mL / min (supply rate per 1 cm 2 of polishing substrate: 0.072 mL / min)
Lower platen rotation speed: 32.5 rpm
Polishing load: 12.0kPa
Polishing time: 6 minutes
［研磨速度の測定方法］
研磨前後の各基板の重さを質量計（Ｓａｒｔｏｒｉｕｓ社製「ＢＰ−２１０Ｓ」）を用いて測定し、各基板の質量変化を求め、１０枚の平均値を質量減少量とし、それを研磨時間で割った値を質量減少速度とした。この質量減少速度を下記の式に導入し、研磨速度（μｍ／ｍｉｎ）に変換した。
研磨速度（μｍ／ｍｉｎ）＝質量減少速度（ｇ／ｍｉｎ）／基板片面面積（ｍｍ2）／Ｎｉ−Ｐメッキ密度（ｇ／ｃｍ3）×１０6
（基板片面面積：６５９７ｍｍ2、Ｎｉ−Ｐメッキ密度：７．９９ｇ／ｃｍ3として算出）
[Measurement method of polishing rate]
The weight of each substrate before and after polishing was measured using a mass meter (“BP-210S” manufactured by Sartorius) to determine the mass change of each substrate, and the average value of 10 substrates was used as the mass reduction amount, which was used as the polishing time. The value divided by was taken as the mass reduction rate. This mass reduction rate was introduced into the following formula and converted into a polishing rate (μm / min).
Polishing rate (μm / min) = mass reduction rate (g / min) / substrate single-sided area (mm 2 ) / Ni-P plating density (g / cm 3 ) × 10 6
(Substrate single-sided area: 6597 mm 2 , Ni—P plating density: calculated as 7.9 g / cm 3 )
［ナノ突起欠陥及びスクラッチの評価方法］
測定機器：ＫＬＡ Ｔｅｎｃｏｒ社製、ＯＳＡ７１００
評価：研磨試験機に投入した基板の中、無作為に４枚を選択し、各々の基板を１００００ｒｐｍにてレーザーを照射してナノ突起欠陥及びスクラッチを測定した。その４枚の基板の各々両面にあるスクラッチ数（本）の合計を８で除して、基板面当たりのナノ突起欠陥及びスクラッチの数を算出した。その結果を、下記表１に、比較例１を１００とした相対値として示す。なお、下記表１において、「測定不能」とは、研磨速度が低いために粗研磨で発生した傷や研磨剤残渣が除去しきれなかったことに起因し、ナノ突起欠陥又はスクラッチの数が測定上限を超えたことを示す。
[Evaluation method of nanoprotrusion defects and scratches]
Measuring instrument: OSA7100, manufactured by KLA Tencor
Evaluation: Four substrates were randomly selected from the substrates put in the polishing tester, and each substrate was irradiated with a laser at 10,000 rpm to measure nanoprotrusion defects and scratches. The total number of scratches (lines) on each of the four substrates was divided by 8 to calculate the number of nanoprotrusion defects and scratches per substrate surface. The results are shown in Table 1 below as relative values with Comparative Example 1 taken as 100. In Table 1 below, “impossible to measure” means that the number of nanoprotrusion defects or scratches was measured because the scratches and abrasive residues generated by rough polishing could not be removed because the polishing rate was low. Indicates that the upper limit has been exceeded.
［貯蔵安定性の評価］
調製した研磨液を６０℃の恒温槽中に２４時間保管し、保管前後のＢＴＡ，ＢＴＡ誘導体の含有量をＨＰＬＣ（日立製作所製 型番：ＬａＣｈｒｏｍ Ｅｌｉｔｅ）にて測定し、下記式により残存率の算出を実施した。
＜残存率の算出方法＞
残存率（％）＝（保管後のＢＴＡ（誘導体）/保管前のＢＴＡ（誘導体））ｘ１００
＜測定条件＞
カラム： Ｌ−ｃｏｌｕｍｎ ＯＤＳ
カラム温度： ４０℃
溶離液： トリフルオロ酢酸０．１％、メタノール３０％ 水溶液
測定時間： ２０分
流量： １.０ｍｌ/ｍｉｎ
注入量： ２０μｌ
検出： ＵＶ２７５ｎｍ
[Evaluation of storage stability]
The prepared polishing liquid is stored in a constant temperature bath at 60 ° C. for 24 hours, and the contents of BTA and BTA derivatives before and after storage are measured with HPLC (manufactured by Hitachi, Ltd., model number: LaChrom Elite), and the residual ratio is calculated by the following formula. Carried out.
<Calculation method of residual rate>
Residual rate (%) = (BTA (derivative) after storage / BTA (derivative) before storage) × 100
<Measurement conditions>
Column: L-column ODS
Column temperature: 40 ° C
Eluent: 0.1% trifluoroacetic acid, 30% methanol Aqueous solution Measurement time: 20 minutes Flow rate: 1.0 ml / min
Injection volume: 20 μl
Detection: UV275nm
［フィルター通液量の評価］
調製した研磨液を一定圧力（０．３ＭＰａ）の下、シリンジフィルター（アドバンテック東洋社製：親水性ＰＴＦＥ ０．４５μｍ）に通液し、閉塞するまで通液させ、通液量を測定することにより評価した。
[Evaluation of filter flow rate]
By passing the prepared polishing liquid through a syringe filter (manufactured by Advantech Toyo Co., Ltd .: hydrophilic PTFE 0.45 μm) under a constant pressure (0.3 MPa), allowing the liquid to pass through and measuring the amount of liquid passed evaluated.
上記表１に示すように、実施例３〜５、８、参考例１〜２、６〜７、９〜１４の研磨液組成物では、比較例１のそれに比べ、研磨後の基板表面のスクラッチ及びナノ突起欠陥が同程度に抑えられつつ、該研磨液組成物の貯蔵安定性が向上し、フィルター通液量も増加した。なお、ＡＴＭＰを使用した比較例５では、貯蔵安定性は発揮されたが、フィルター通液量が著しく低下した。
As shown in Table 1 above, the polishing liquid compositions of Examples 3 to 5, 8 and Reference Examples 1 to 2, 6 to 7, and 9 to 14 were scratched on the substrate surface after polishing as compared with Comparative Example 1. In addition, while the nanoprotrusion defects were suppressed to the same extent, the storage stability of the polishing composition was improved, and the amount of filtered liquid was increased. In Comparative Example 5 using ATMP, the storage stability was exhibited, but the filter flow rate was significantly reduced.
Claims (12)
前記変質抑制物質が、ヒドロキシホスホノ酢酸及びホスホノブタントリカルボン酸から選ばれる少なくとも一種である、Ｎｉ−Ｐメッキされたアルミニウム合金基板用の研磨液組成物。 Contains at least one selected from the group consisting of silica particles, acids, oxidants, benzotriazole (BTA) and derivatives thereof, at least one selected from the group consisting of diamines and triamines, BTA or a derivative thereof, and water And
A polishing composition for an Ni-P plated aluminum alloy substrate, wherein the alteration inhibiting substance is at least one selected from hydroxyphosphonoacetic acid and phosphonobutanetricarboxylic acid .
前記変質抑制物質が、分子内に窒素原子を含まない、有機ホスホン酸及び縮合リン酸からなる群から選ばれる少なくとも一種である、Ｎｉ−Ｐメッキされたアルミニウム合金基板用の研磨液組成物。 Containing at least one selected from the group consisting of silica particles, acid, oxidizing agent, tolyltriazole , diamine and triamine, a tolyltriazole alteration inhibitor, and water,
A polishing liquid composition for an Ni-P plated aluminum alloy substrate, wherein the alteration inhibiting substance is at least one selected from the group consisting of organic phosphonic acid and condensed phosphoric acid that does not contain a nitrogen atom in the molecule.
前記変質抑制物質が、分子内に窒素原子を含まない、有機ホスホン酸及び縮合リン酸からなる群から選ばれる少なくとも一種であり、
前記ＢＴＡの含有量が０．２質量％以上１質量％以下である、Ｎｉ−Ｐメッキされたアルミニウム合金基板用の研磨液組成物。 Silica particles, acid, oxidizing agent, contain benzotriazole (BTA), at least one, alteration inhibitor of BTA selected from the group consisting of diamines and triamines, and water,
The alteration inhibitor does not include a nitrogen atom in the molecule, Ri least one Der selected from the group consisting of organic phosphonic acids and condensed phosphoric acid,
A polishing composition for a Ni—P plated aluminum alloy substrate, wherein the BTA content is 0.2 mass% or more and 1 mass% or less .
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