JP6925958B2 - Abrasive liquid composition - Google Patents
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- NLKRQAPJSUYLGD-BRGXGPIHSA-N CC/C(/C=C)=C/C(/C(C)(C)C(C)(C)Cc1cccc(C)c1)=C\C Chemical compound CC/C(/C=C)=C/C(/C(C)(C)C(C)(C)Cc1cccc(C)c1)=C\C NLKRQAPJSUYLGD-BRGXGPIHSA-N 0.000 description 1
Description
本開示は、研磨液組成物、並びにこれを用いた基板の製造方法及び研磨方法に関する。 The present disclosure relates to a polishing liquid composition, and a method for producing a substrate and a polishing method using the same.
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、表面粗さ、うねり、端面ダレの低減に代表される平滑性・平坦性の向上とスクラッチ、突起、ピット等の低減に代表される欠陥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て、カルボキシル基やスルホン酸基などの官能基を有する共重合体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及び２）。 In recent years, magnetic disk drives have become smaller and larger in capacity, and higher recording densities are required. In order to increase the recording density, the unit recording area is reduced, and the detection sensitivity of the weakened magnetic signal is improved. Therefore, technological development for lowering the floating height of the magnetic head is underway. For magnetic disk substrates, in order to reduce the levitation of the magnetic head and secure the recording area, improvement of smoothness and flatness represented by reduction of surface roughness, waviness, and end face sagging, and scratches, protrusions, pits, etc. The demand for defect reduction represented by the reduction of defects is becoming stricter. In response to such demands, polishing liquid compositions containing a copolymer having a functional group such as a carboxyl group or a sulfonic acid group have been proposed (for example, Patent Documents 1 and 2).
特許文献１は、分子中に繰り返し単位と、スルホン酸（塩）基とを有し、さらに繰り返し単位の主鎖中に芳香族基を有する陰イオン性界面活性剤を用いることにより、スクラッチ等の欠陥を低減することができ、研磨工程において発泡が少なく、効率よく研磨することができる研磨剤組成物を開示する。 Patent Document 1 describes scratches and the like by using an anionic surfactant having a repeating unit and a sulfonic acid (salt) group in the molecule and further having an aromatic group in the main chain of the repeating unit. Disclosed is a polishing agent composition which can reduce defects, has less foaming in the polishing process, and can be efficiently polished.
特許文献２は、スルホン酸基を有し、主鎖及び側鎖のそれぞれに芳香族環を有する水溶性重合体を用いることにより、生産性を損なうことなく、スクラッチやうねりを低減できる研磨液組成物を開示する。 Patent Document 2 describes a polishing solution composition capable of reducing scratches and waviness without impairing productivity by using a water-soluble polymer having a sulfonic acid group and having an aromatic ring in each of the main chain and the side chain. Disclose the thing.
磁気ディスクドライブの大容量化に伴い、基板の表面品質に対する要求特性はさらに厳しくなっており、基板表面のスクラッチ及びうねりを低減できる研磨液組成物の開発が求められている。 As the capacity of magnetic disk drives increases, the required characteristics for the surface quality of the substrate are becoming more stringent, and the development of a polishing liquid composition capable of reducing scratches and waviness on the surface of the substrate is required.
そこで、本開示は、一態様において、研磨後の基板表面のスクラッチ及び研磨パッドの継続使用における短波長うねりを低減できる研磨液組成物を提供する。 Therefore, the present disclosure provides, in one aspect, a polishing liquid composition capable of reducing scratches on the surface of the substrate after polishing and short-wavelength waviness in continuous use of the polishing pad.
本開示は、一態様において、研磨材、水溶性重合体、及び水系媒体を含有する研磨液組成物であって、前記水溶性重合体が、下記一般式（Ｉ）で表される構成を有する、研磨液組成物に関する。
本開示は、その他の態様において、本開示の研磨液組成物を被研磨基板の研磨対象面に供給し、前記研磨対象面に研磨パッドを接触させ、前記研磨パッド及び／又は前記被研磨基板を動かして研磨する工程を含む、基板の製造方法に関する。 In another aspect of the present disclosure, the polishing liquid composition of the present disclosure is supplied to the surface to be polished of the substrate to be polished, the polishing pad is brought into contact with the surface to be polished, and the polishing pad and / or the substrate to be polished is brought into contact with the surface to be polished. The present invention relates to a method for manufacturing a substrate, which comprises a step of moving and polishing.
本開示は、その他の態様において、本開示の研磨液組成物を被研磨基板の研磨対象面に供給し、前記研磨対象面に研磨パッドを接触させ、前記研磨パッド及び／又は前記被研磨基板を動かして研磨することを含む、基板の研磨方法に関する。 In another aspect of the present disclosure, the polishing liquid composition of the present disclosure is supplied to the surface to be polished of the substrate to be polished, the polishing pad is brought into contact with the surface to be polished, and the polishing pad and / or the substrate to be polished is brought into contact with the surface to be polished. It relates to a method of polishing a substrate, including moving and polishing.
本開示の研磨液組成物によれば、研磨後の基板表面のスクラッチ及び研磨パッドの継続使用における短波長うねりが低減された基板、好ましくは磁気ディスク基板、さらに好ましくは垂直磁気記録方式の磁気ディスク基板を製造できるという効果が奏されうる。 According to the polishing liquid composition of the present disclosure, a substrate in which scratches on the surface of the substrate after polishing and short wavelength waviness in continuous use of the polishing pad are reduced, preferably a magnetic disk substrate, and more preferably a magnetic disk of a perpendicular magnetic recording method. The effect of being able to manufacture a substrate can be achieved.
本開示は、所定の水溶性重合体を含有する研磨液組成物を使用すれば、研磨後の基板表面のスクラッチ及び研磨パッドの継続使用における短波長うねりを低減できるという知見に基づく。 The present disclosure is based on the finding that by using a polishing liquid composition containing a predetermined water-soluble polymer, scratches on the surface of a substrate after polishing and short-wavelength waviness in continuous use of a polishing pad can be reduced.
すなわち、本開示は、一態様において、研磨材、水溶性重合体、及び水系媒体を含有する研磨液組成物であって、前記水溶性重合体が、上記一般式（Ｉ）で表される構成を有する、研磨液組成物（以下、「本開示の研磨液組成物」ともいう）に関する。 That is, the present disclosure is, in one aspect, a polishing liquid composition containing an abrasive, a water-soluble polymer, and an aqueous medium, wherein the water-soluble polymer is represented by the general formula (I). (Hereinafter, also referred to as "abrasive liquid composition of the present disclosure").
本開示の効果発現のメカニズムは明らかではないが、以下のように推察される。
通常、研磨パッドを軟質化すればスクラッチを低減できる。しかし、研磨パッドは、一般的に、硬さの異なる部分が混在するものであり、柔らかい部分が過度に軟質化すると、ポア径が大きくなって圧力分布が不均一となり、研磨パッドの磨耗が促進し、短波長うねりの悪化につながると考えられる。
これに対し、本開示では、研磨液組成物中の所定の水溶性重合体によって、研磨パッドの硬い部分が選択的に軟質化され、柔らかい部分が過度に軟質化するのが抑制され、研磨パッドの磨耗が抑制されると考えられる。その結果、スクラッチを低減しつつ、研磨パッドの継続使用における基板表面の短波長うねりを低減できると考えられる。
但し、本開示はこれらのメカニズムに限定して解釈されなくてもよい。
The mechanism of the manifestation of the effects of the present disclosure is not clear, but it is inferred as follows.
Usually, scratches can be reduced by softening the polishing pad. However, the polishing pad generally contains a mixture of parts having different hardness, and when the soft part is excessively softened, the pore diameter becomes large and the pressure distribution becomes uneven, which accelerates the wear of the polishing pad. However, it is thought that it will lead to worsening of short wavelength swell.
On the other hand, in the present disclosure, the predetermined water-soluble polymer in the polishing liquid composition selectively softens the hard portion of the polishing pad and suppresses the soft portion from being excessively softened, so that the polishing pad is prevented from being excessively softened. It is considered that the wear of the material is suppressed. As a result, it is considered that short-wavelength waviness on the substrate surface during continuous use of the polishing pad can be reduced while reducing scratches.
However, the present disclosure may not be construed as limited to these mechanisms.
本開示において基板の「うねり」とは、粗さよりも波長の長い基板表面の凹凸をいう。本開示において「短波長うねり」とは、例えば、８０〜５００ｎｍの波長により観測されるうねりをいう。研磨後の基板表面の短波長うねりが低減されることにより、磁気ディスクドライブにおいて磁気ヘッドの浮上高さを低くすることができ、磁気ディスクの記録密度の向上が可能となる。基板表面の短波長うねりは、例えば、実施例に記載の方法により測定できる。 In the present disclosure, the "waviness" of the substrate means the unevenness of the substrate surface having a wavelength longer than the roughness. In the present disclosure, the "short wavelength swell" means a swell observed at a wavelength of, for example, 80 to 500 nm. By reducing the short-wavelength waviness of the surface of the substrate after polishing, the floating height of the magnetic head can be lowered in the magnetic disk drive, and the recording density of the magnetic disk can be improved. The short wavelength swell on the surface of the substrate can be measured, for example, by the method described in Examples.
［研磨材（成分Ａ）］
本開示の研磨液組成物に含まれる研磨材（以下、「成分Ａ」ともいう）としては、研磨用に一般的に使用されている研磨材を使用することができ、金属、金属若しくは半金属の炭化物、窒化物、酸化物、又はホウ化物、ダイヤモンド等が挙げられる。金属又は半金属元素は、周期律表（長周期型）の２Ａ、２Ｂ、３Ａ、３Ｂ、４Ａ、４Ｂ、５Ａ、６Ａ、７Ａ又は８族由来のものである。成分Ａの具体例としては、酸化珪素（以下、シリカという）、酸化アルミニウム（以下、アルミナという）、炭化珪素、ダイヤモンド、酸化マンガン、酸化マグネシウム、酸化亜鉛、酸化チタン、酸化セリウム（以下、セリアという）、酸化ジルコニウム等が挙げられ、これらの１種以上を使用することは研磨速度を向上させる観点から好ましい。中でも、シリカ、アルミナ、酸化チタン、セリア、酸化ジルコニウム等が、半導体素子用基板や磁気ディスク基板等の精密部品用基板の研磨に適している。スクラッチ及び短波長うねり低減の観点から、成分Ａとしては、コロイダルシリカ、コロイダルセリア、及びコロイダルアルミナから選ばれる少なくとも１種が好ましく、コロイダルシリカがより好ましい。成分Ａは、１種単独であってもよいし、２種以上の組合せであってもよい。成分Ａは、一又は複数の実施形態において、レーザー光回折・散乱を測定原理とした粒度分布計で測定したときのメジアン径が４〜１００ｎｍであるダイヤモンド構造を有する微粒子を実質的に含まないものであってもよい。前記ダイヤモンド構造を有する微粒子を実質的に含まないとは、スクラッチ低減の観点から、成分Ａ中の前記微粒子の含有量が、１．０質量％以下、好ましくは０．１質量％以下、より好ましくは実質的に０質量％をいう。
[Abrasive (Component A)]
As the polishing material (hereinafter, also referred to as “component A”) contained in the polishing liquid composition of the present disclosure, a polishing material generally used for polishing can be used, and a metal, metal or semi-metal can be used. Carbides, nitrides, oxides, boroides, diamonds and the like. The metal or metalloid element is derived from Group 8 of 2A, 2B, 3A, 3B, 4A, 4B, 5A, 6A, 7A or 8 of the periodic table (long periodic table). Specific examples of component A include silicon oxide (hereinafter referred to as silica), aluminum oxide (hereinafter referred to as alumina), silicon carbide, diamond, manganese oxide, magnesium oxide, zinc oxide, titanium oxide, and cerium oxide (hereinafter referred to as ceria). ), Zirconium oxide and the like, and it is preferable to use one or more of these from the viewpoint of improving the polishing rate. Among them, silica, alumina, titanium oxide, ceria, zirconium oxide and the like are suitable for polishing substrates for precision parts such as substrates for semiconductor devices and magnetic disk substrates. From the viewpoint of reducing scratches and short wavelength waviness, as the component A, at least one selected from colloidal silica, colloidal ceria, and colloidal alumina is preferable, and colloidal silica is more preferable. The component A may be one kind alone or a combination of two or more kinds. Component A substantially does not contain fine particles having a diamond structure having a median diameter of 4 to 100 nm when measured with a particle size distribution meter based on laser light diffraction / scattering in one or more embodiments. It may be. The fact that the fine particles having the diamond structure are not substantially contained means that the content of the fine particles in the component A is 1.0% by mass or less, preferably 0.1% by mass or less, more preferably from the viewpoint of scratch reduction. Is substantially 0% by mass.
成分Ａの平均粒径は、スクラッチ及び短波長うねり低減の観点から、１ｎｍ以上が好ましく、５ｎｍ以上がより好ましく、１０ｎｍ以上が更に好ましく、そして、同様の観点から、１００ｎｍ以下が好ましく、７０ｎｍ以下がより好ましく、４０ｎｍ以下が更に好ましい。さらに、同様の観点から、成分Ａの平均粒径は、１ｎｍ以上１００ｎｍ以下が好ましく、５ｎｍ以上７０ｎｍ以下がより好ましく、１０ｎｍ以上４０ｎｍ以下が更に好ましい。本開示において、「研磨材の平均粒径」とは、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う。研磨材の平均粒径は、具体的には実施例に記載の方法により求めることができる。 The average particle size of the component A is preferably 1 nm or more, more preferably 5 nm or more, further preferably 10 nm or more, and from the same viewpoint, preferably 100 nm or less, preferably 70 nm or less, from the viewpoint of reducing scratches and short wavelength waviness. More preferably, 40 nm or less is further preferable. Further, from the same viewpoint, the average particle size of the component A is preferably 1 nm or more and 100 nm or less, more preferably 5 nm or more and 70 nm or less, and further preferably 10 nm or more and 40 nm or less. In the present disclosure, the "average particle size of the abrasive" means the average particle size based on the scattering intensity distribution measured at a detection angle of 90 ° in the dynamic light scattering method. Specifically, the average particle size of the abrasive can be determined by the method described in Examples.
本開示の研磨液組成物中における成分Ａの含有量は、研磨速度を向上させる観点から、０．１質量％以上が好ましく、１質量％以上がより好ましく、３質量％以上が更に好ましく、そして、スクラッチ及び短波長うねり低減の観点から、２０質量％以下が好ましく、１５質量％以下がより好ましく、１０質量％以下が更に好ましい。さらに、成分Ａの含有量は、研磨速度の向上、スクラッチ及び短波長うねり低減の観点から、０．１質量％以上２０質量％以下が好ましく、１質量％以上１５質量％以下がより好ましく、３質量％以上１０質量％以下が更に好ましい。成分Ａが２種以上の研磨材の組合せである場合、成分Ａの含有量は、それらの合計含有量をいう。 The content of component A in the polishing liquid composition of the present disclosure is preferably 0.1% by mass or more, more preferably 1% by mass or more, further preferably 3% by mass or more, and more preferably 3% by mass or more, from the viewpoint of improving the polishing rate. From the viewpoint of reducing scratches and short wavelength waviness, 20% by mass or less is preferable, 15% by mass or less is more preferable, and 10% by mass or less is further preferable. Further, the content of the component A is preferably 0.1% by mass or more and 20% by mass or less, more preferably 1% by mass or more and 15% by mass or less, from the viewpoint of improving the polishing rate and reducing scratches and short wavelength waviness. More preferably, it is by mass% or more and 10% by mass or less. When the component A is a combination of two or more kinds of abrasives, the content of the component A means the total content thereof.
［水溶性重合体（成分Ｂ）］
本開示の研磨液組成物に用いられる水溶性重合体（以下、「成分Ｂ」ともいう）は、スクラッチ及び短波長うねり低減の観点から、下記式（Ｉ）で表される構成を有する化合物である。成分Ｂは単独で又は２種以上を混合して用いてもよい。
[Water-soluble polymer (component B)]
The water-soluble polymer (hereinafter, also referred to as “component B”) used in the polishing liquid composition of the present disclosure is a compound having a composition represented by the following formula (I) from the viewpoint of reducing scratches and short wavelength waviness. be. Component B may be used alone or in combination of two or more.
式（Ｉ）中、Ｒ1は、ＣＨ3、ＣＯＯＨ及びＨから選ばれる少なくとも１種である。ｋは、１〜２である。Ｘは、アルカリ金属、アルカリ土類金属、有機カチオン、及び水素原子から選ばれる少なくとも１種である。有機カチオンとしては、アンモニウムや、テトラメチルアンモニウム、テトラエチルアンモニウム、テトラブチルアンモニウム等のアルキルアンモニウムが挙げられる。これらの中でも、スクラッチ及び短波長うねり低減の観点から、アルカリ金属、アンモニウム及び水素原子から選ばれる少なくとも１種が好ましく、ナトリウム、カリウム、アンモニウム及び水素原子から選ばれる少なくとも１種がより好ましく、水素原子が更に好ましい。ｍ、ｎは、ｍ＋ｎ＝１とした場合のモル分率であり、ｍは、スクラッチ低減、短波長うねり低減及び水溶性の観点から、０≦ｍ≦０．４であって、０≦ｍ≦０．３が好ましく、０≦ｍ≦０．２５がより好ましく、０．１≦ｍ≦０．２が更に好ましい。 In formula (I), R 1 is at least one selected from CH 3, COOH and H. k is 1 to 2. X is at least one selected from alkali metals, alkaline earth metals, organic cations, and hydrogen atoms. Examples of the organic cation include ammonium and alkylammonium such as tetramethylammonium, tetraethylammonium and tetrabutylammonium. Among these, at least one selected from alkali metal, ammonium and hydrogen atoms is preferable, and at least one selected from sodium, potassium, ammonium and hydrogen atoms is more preferable, and hydrogen atoms are more preferable from the viewpoint of reducing scratches and short wavelength waviness. Is more preferable. m and n are mole fractions when m + n = 1, and m is 0 ≦ m ≦ 0.4 and 0 ≦ m ≦ from the viewpoint of scratch reduction, short wavelength swell reduction and water solubility. 0.3 is preferable, 0 ≦ m ≦ 0.25 is more preferable, and 0.1 ≦ m ≦ 0.2 is further preferable.
成分Ｂは、一又は複数の実施形態において、スクラッチ及び短波長うねり低減の観点から、２０℃でｐＨ３の水溶液１００ｇに対する溶解度が０．０１ｇ以上であり、２０℃でｐＨ３以下の水溶液１００ｇに対する溶解度が０．０１ｇ以上であることが好ましい。 In one or more embodiments, component B has a solubility of 0.01 g or more in 100 g of an aqueous solution having a pH of 3 at 20 ° C. and a solubility in 100 g of an aqueous solution having a pH of 3 or less at 20 ° C. from the viewpoint of reducing scratches and short wavelength waviness. It is preferably 0.01 g or more.
本開示において、「水溶性」とは、２０℃の水１００ｇに対する溶解度が０．０１ｇ以上であることをいう。 In the present disclosure, "water-soluble" means that the solubility in 100 g of water at 20 ° C. is 0.01 g or more.
成分Ｂは、例えば、主鎖中にフェノール骨格を有するモノマーを、ホルムアルデヒド存在下で付加縮合法等の公知の手段により重合することにより製造することができる。耐加水分解性の向上及び酸性研磨液中での保存安定性の向上の観点から、付加縮合法により製造されることが好ましい。したがって、成分Ｂの一実施形態としては、主鎖中にフェノール骨格を有する構成単位を有する水溶性重合体が挙げられる。 Component B can be produced, for example, by polymerizing a monomer having a phenol skeleton in the main chain by a known means such as an addition condensation method in the presence of formaldehyde. From the viewpoint of improving hydrolysis resistance and storage stability in an acidic polishing solution, it is preferably produced by an addition condensation method. Therefore, one embodiment of component B includes a water-soluble polymer having a structural unit having a phenol skeleton in the main chain.
成分Ｂを構成する全構成単位中に占める式（Ｉ）で表される構成の含有量は、一又は複数の実施形態において、スクラッチ低減及び短波長うねり低減の観点から、５モル％以上が好ましく、１０モル％以上がより好ましく、２０モル％以上が更に好ましく、そして、同様の観点から、１００モル％以下が好ましく、９５モル％以下がより好ましく、９０モル％以下が更に好ましく、８０モル％以下が更に好ましい。さらに、同様の観点から、成分Ｂの全構成単位中に示す式（Ｉ）で表される構成の含有量は、５モル％以上１００モル％以下が好ましく、５モル％以上９５モル％以下がより好ましく、１０モル％以上９０モル％以下が更に好ましく、２０モル％以上８０モル％以下が更に好ましい。 The content of the configuration represented by the formula (I) in all the constituent units constituting the component B is preferably 5 mol% or more from the viewpoint of scratch reduction and short wavelength swell reduction in one or more embodiments. 10 mol% or more is more preferable, 20 mol% or more is further preferable, and from the same viewpoint, 100 mol% or less is more preferable, 95 mol% or less is more preferable, 90 mol% or less is further preferable, and 80 mol% is more preferable. The following is more preferable. Further, from the same viewpoint, the content of the composition represented by the formula (I) represented by the formula (I) in all the constituent units of the component B is preferably 5 mol% or more and 100 mol% or less, and 5 mol% or more and 95 mol% or less. More preferably, 10 mol% or more and 90 mol% or less is further preferable, and 20 mol% or more and 80 mol% or less is further preferable.
本開示において、成分Ｂを構成する全構成単位中に占めるある構成単位の含有量（モル％）として、合成条件によっては、成分Ｂの合成の全工程で反応槽に仕込まれた全構成単位を導入するための化合物中に占める前記反応槽に仕込まれた該構成単位を導入するための化合物量（モル％）を使用してもよい。また、本開示において、成分Ｂが２種以上の構成単位を含む場合、２つの構成単位の構成比（モル比）として、合成条件によっては、前記成分Ｂの合成の全工程で反応槽に仕込まれた該２つの構成単位を導入するための化合物量比（モル比）を使用してもよい。 In the present disclosure, as the content (mol%) of a certain constituent unit in all the constituent units constituting the component B, depending on the synthesis conditions, all the constituent units charged in the reaction vessel in all the steps of the synthesis of the component B are used. The amount of the compound (mol%) for introducing the structural unit charged in the reaction vessel in the compound for introduction may be used. Further, in the present disclosure, when the component B contains two or more kinds of constituent units, as the constituent ratio (molar ratio) of the two constituent units, depending on the synthesis conditions, the component B is charged into the reaction tank in all the steps of the synthesis of the component B. The compound amount ratio (molar ratio) for introducing the two constituent units may be used.
成分Ｂは、式（Ｉ）に含まれないその他の構成単位を有していてもよい。成分Ｂを構成する全構成単位中に占めるその他の構成単位の含有率は、スクラッチ及び短波長うねり低減の観点から、１０モル％以下が好ましく、５モル％以下がより好ましく、３モル％以下が更に好ましく、１モル％以下が更に好ましく、実質的に０モル％が更に好ましい。成分Ｂが、その他の構成単位として、主鎖中のフェノール骨格の側鎖に芳香族環を有する構成単位を含む場合、該構成単位の含有量は、５モル％以下が好ましく、４モル％以下がより好ましく、３モル％以下が更に好ましく、２モル％以下が更に好ましく、１モル％以下が更に好ましく、実質的に０モル％が更に好ましい。 Component B may have other structural units not included in formula (I). The content of other constituent units in all the constituent units constituting the component B is preferably 10 mol% or less, more preferably 5 mol% or less, and 3 mol% or less from the viewpoint of reducing scratches and short wavelength waviness. More preferably, 1 mol% or less is further preferable, and substantially 0 mol% is further preferable. When the component B contains, as another structural unit, a structural unit having an aromatic ring in the side chain of the phenol skeleton in the main chain, the content of the structural unit is preferably 5 mol% or less, preferably 4 mol% or less. Is more preferable, 3 mol% or less is further preferable, 2 mol% or less is further preferable, 1 mol% or less is further preferable, and substantially 0 mol% is further preferable.
成分Ｂを構成する各構成単位の配列は、ランダム、ブロック、又はグラフトのいずれでもよい。 The sequence of each structural unit constituting the component B may be random, block, or graft.
成分Ｂの重量平均分子量は、スクラッチ及び短波長うねり低減の観点から、５００以上が好ましく、１,０００以上がより好ましく、１，４００以上が更に好ましく、１,５００以上が更に好ましく、３,０００以上が更に好ましく、４,５００以上が更に好ましく、５,０００以上が更に好ましく、８,０００以上が更に好ましく、１０,０００以上が更に好ましく、そして、同様の観点から、１，０００，０００以下が好ましく、７５０,０００以下がより好ましく、５００,０００以下が更に好ましく、２５０,０００以下が更に好ましく、１２０,０００以下が更に好ましく、１００,０００以下が更に好ましく、７５,０００以下が更に好ましく、５０,０００以下が更に好ましく、４０,０００以下が更に好ましく、３０,０００以下が更に好ましく、２５,０００以下が更に好ましく、２０,０００以下が更に好ましい。さらに、同様の観点から、成分Ｂの重量平均分子量は、５００以上１，０００，０００以下が好ましく、１,０００以上７５０,０００以下がより好ましく、１，４００以上５００,０００以下が更に好ましく、１,５００以上２５０,０００以下が更に好ましく、３,０００以上１００,０００以下が更に好ましく、４,５００以上７５,０００以下が更に好ましく、５,０００以上５０,０００以下が更に好ましく、８,０００以上３０,０００以下が更に好ましく、１０,０００以上２０,０００以下が更に好ましい。本開示において、重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）を用いて実施例に記載の条件で測定した値とする。 The weight average molecular weight of the component B is preferably 500 or more, more preferably 1,000 or more, further preferably 1,400 or more, further preferably 1,500 or more, and 3,000 or more, from the viewpoint of reducing scratches and short wavelength waviness. The above is more preferable, 4,500 or more is further preferable, 5,000 or more is further preferable, 8,000 or more is further preferable, 10,000 or more is further preferable, and from the same viewpoint, 1,000,000 or less. Is more preferable, 75,000,000 or less is more preferable, 500,000 or less is further preferable, 250,000 or less is further preferable, 120,000 or less is further preferable, 100,000 or less is further preferable, and 75,000 or less is further preferable. , 50,000 or less is further preferable, 40,000 or less is further preferable, 30,000 or less is further preferable, 25,000 or less is further preferable, and 20,000 or less is further preferable. Further, from the same viewpoint, the weight average molecular weight of the component B is preferably 500 or more and 1,000,000 or less, more preferably 1,000 or more and 750,000 or less, and further preferably 1,400 or more and 500,000 or less. More preferably 1,500 or more and 250,000 or less, further preferably 3,000 or more and 100,000 or less, further preferably 4,500 or more and 75,000 or less, further preferably 5,000 or more and 50,000 or less, 8, It is more preferably 000 or more and 30,000 or less, and further preferably 10,000 or more and 20,000 or less. In the present disclosure, the weight average molecular weight is a value measured by gel permeation chromatography (GPC) under the conditions described in Examples.
成分Ｂの表面張力は、スクラッチ及び短波長うねり低減の観点から、４５ｍＮ／ｍ以上が好ましく、５５ｍＮ／ｍ以上がより好ましく、６５ｍＮ／ｍ以上が更に好ましく、７１ｍＮ／ｍ以上が更に好ましく、７２ｍＮ／ｍ以上が更に好ましく、そして、同様の観点から、９０ｍＮ／ｍ以下が好ましく、８０ｍＮ／ｍ以下がより好ましく、７７ｍＮ／ｍ以下が更に好ましく、７４ｍＮ／ｍ以下が更に好ましい。さらに、同様の観点から、成分Ｂの表面張力は、４５ｍＮ／ｍ以上９０ｍＮ／ｍ以下が好ましく、５５ｍＮ／ｍ以上８０ｍＮ／ｍ以下がより好ましく、６５ｍＮ／ｍ以上７７ｍＮ／ｍ以下が更に好ましく、７１ｍＮ／ｍ以上７４ｍＮ／ｍ以下が更に好ましく、７２ｍＮ／ｍ以上７４ｍＮ／ｍ以下が更に好ましい。本開示において、成分Ｂの表面張力は、成分Ｂの０．００５質量％水溶液の２０℃、ｐＨ１．５における表面張力であり、実施例に記載の方法により求めることができる。 The surface tension of component B is preferably 45 mN / m or more, more preferably 55 mN / m or more, further preferably 65 mN / m or more, further preferably 71 mN / m or more, and even more preferably 72 mN / m, from the viewpoint of reducing scratches and short wavelength waviness. M or more is more preferable, and from the same viewpoint, 90 mN / m or less is preferable, 80 mN / m or less is more preferable, 77 mN / m or less is further preferable, and 74 mN / m or less is further preferable. Further, from the same viewpoint, the surface tension of the component B is preferably 45 mN / m or more and 90 mN / m or less, more preferably 55 mN / m or more and 80 mN / m or less, further preferably 65 mN / m or more and 77 mN / m or less, and 71 mN. It is more preferably / m or more and 74 mN / m or less, and further preferably 72 mN / m or more and 74 mN / m or less. In the present disclosure, the surface tension of component B is the surface tension of a 0.005 mass% aqueous solution of component B at 20 ° C. and pH 1.5, and can be determined by the method described in Examples.
成分Ｂに浸潤させた研磨パッドの貯蔵弾性率は、短波長うねり低減の観点から、０．１５ＭＰa以上が好ましく、０．２５ＭＰa以上がより好ましく、０．３０ＭＰa以上が更に好ましく、そして、スクラッチ低減の観点から、０．５０ＭＰa以下が好ましく、０．４０ＭＰa以下がより好ましく、０．３５ＭＰa以下が更に好ましい。さらに、スクラッチ及び短波長うねり低減の観点から、成分Ｂを浸潤させた研磨パッドの貯蔵弾性率は、０．１５ＭＰa以上０．５０ＭＰa以下が好ましく、０．２５ＭＰa以上０．４０ＭＰa以下がより好ましく、０．３０ＭＰa以上０．３５ＭＰa以下が更に好ましい。本開示において、貯蔵弾性率は、実施例に記載の方法により求めることができる。 The storage elastic modulus of the polishing pad infiltrated with component B is preferably 0.15 MPa or more, more preferably 0.25 MPa or more, further preferably 0.30 MPa or more, and scratch reduction from the viewpoint of reducing short wavelength swell. From the viewpoint, 0.50 MPa or less is preferable, 0.40 MPa or less is more preferable, and 0.35 MPa or less is further preferable. Further, from the viewpoint of reducing scratches and short wavelength waviness, the storage elastic modulus of the polishing pad infiltrated with component B is preferably 0.15 MPa or more and 0.50 MPa or less, more preferably 0.25 MPa or more and 0.40 MPa or less, and 0. .30 MPa or more and 0.35 MPa or less is more preferable. In the present disclosure, the storage elastic modulus can be determined by the method described in Examples.
本開示の研磨液組成物中の成分Ｂの含有量は、スクラッチ及び短波長うねり低減の観点から、０．００１質量％以上が好ましく、０．００３質量％以上がより好ましく、０．００６質量％以上が更に好ましく、そして、研磨速度向上の観点から、１０質量％以下が好ましく、１質量％以下がより好ましく、０．１質量％以下が更に好ましい。さらに、スクラッチ及び短波長うねり低減、研磨速度向上の観点から、成分Ｂの含有量は、０．００１質量％以上１０質量％以下が好ましく、０．００３質量％以上１質量％以下がより好ましく、０．００６質量％以上０．１質量％以下が更に好ましい。 The content of component B in the polishing liquid composition of the present disclosure is preferably 0.001% by mass or more, more preferably 0.003% by mass or more, and 0.006% by mass from the viewpoint of reducing scratches and short wavelength waviness. The above is more preferable, and from the viewpoint of improving the polishing speed, 10% by mass or less is preferable, 1% by mass or less is more preferable, and 0.1% by mass or less is further preferable. Further, from the viewpoint of reducing scratches and short wavelength waviness and improving the polishing speed, the content of component B is preferably 0.001% by mass or more and 10% by mass or less, and more preferably 0.003% by mass or more and 1% by mass or less. More preferably, it is 0.006% by mass or more and 0.1% by mass or less.
本開示の研磨液組成物中の成分Ａに対する成分Ｂの質量比（成分Ｂの含有量／成分Ａの含有量）は、スクラッチ及び短波長うねり低減の観点から、０．０００１以上が好ましく、０．０００５以上がより好ましく、０．００１以上が更に好ましく、そして、同様の観点から、０．２以下が好ましく、０．０５以下がより好ましく、０．０１以下が更に好ましい。さらに、同様の観点から、成分Ａに対する成分Ｂの質量比は、０．０００１以上０．２以下が好ましく、０．０００５以上０．０５以下がより好ましく、０．００１以上０．０１以下が更に好ましい。 The mass ratio of component B to component A in the polishing liquid composition of the present disclosure (content of component B / content of component A) is preferably 0.0001 or more, preferably 0, from the viewpoint of reducing scratches and short wavelength waviness. More preferably .0005 or more, further preferably 0.001 or more, and from the same viewpoint, 0.2 or less is more preferable, 0.05 or less is more preferable, and 0.01 or less is further preferable. Further, from the same viewpoint, the mass ratio of the component B to the component A is preferably 0.0001 or more and 0.2 or less, more preferably 0.0005 or more and 0.05 or less, and further preferably 0.001 or more and 0.01 or less. preferable.
[水溶性重合体における残存モノマー含有量]
成分Ｂにおける残存モノマーであるホルムアルデヒド含有量は、スクラッチ及び短波長うねり低減の観点から、０ｐｐｍ又は０ｐｐｍを超え１００００ｐｐｍ以下が好ましく、より好ましくは０ｐｐｍ又は０ｐｐｍを超え６０００ｐｐｍ以下、更に好ましくは０ｐｐｍ又は０ｐｐｍを超え５０００ｐｐｍ以下、更により好ましくは０ｐｐｍ又は０ｐｐｍを超え３０００ｐｐｍ以下、更により好ましくは０ｐｐｍ又は０ｐｐｍを超え２０００ｐｐｍ以下、更により好ましくは０ｐｐｍ又は０ｐｐｍを超え１０００ｐｐｍ以下である。該残存ホルムアルデヒド含有量は高速液体クロマトグラフィー（ＨＰＬＣ）を用いて実施例に記載の条件で測定した値とする。また、残存ホルムアルデヒドを亜硫酸塩、シアン化水素またはその塩、水酸化アンモニウム、アルコール等と公知の手法により反応させることにより低減してもよい。
[Residual monomer content in water-soluble polymer]
The content of formaldehyde, which is a residual monomer in component B, is preferably 0 ppm or more than 0 ppm and 10000 ppm or less, more preferably 0 ppm or more than 0 ppm and 6000 ppm or less, and further preferably 0 ppm or 0 ppm, from the viewpoint of reducing scratches and short wavelength waviness. It is more than 5000 ppm or less, more preferably 0 ppm or more than 0 ppm and 3000 ppm or less, still more preferably 0 ppm or more than 0 ppm and 2000 ppm or less, still more preferably 0 ppm or more than 0 ppm and 1000 ppm or less. The residual formaldehyde content shall be a value measured under the conditions described in Examples using high performance liquid chromatography (HPLC). Further, the residual formaldehyde may be reduced by reacting with sulfite, hydrogen cyanide or a salt thereof, ammonium hydroxide, alcohol or the like by a known method.
［水系媒体］
本開示の研磨液組成物に含まれる水系媒体としては、蒸留水、イオン交換水、純水及び超純水等の水、又は、水と溶媒との混合溶媒等が挙げられる。上記溶媒としては、水と混合可能な溶媒（例えば、エタノール等のアルコール）が挙げられる。水系媒体が、水と溶媒との混合溶媒の場合、混合媒体全体に対する水の割合は、本開示の効果が妨げられない範囲であれば特に限定されなくてもよく、経済性の観点から、例えば、９５質量％以上が好ましく、９８質量％以上がより好ましく、実質的に１００質量％が更に好ましい。被研磨基板の表面清浄性の観点から、水系媒体としては、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。本開示の研磨液組成物中の水系媒体の含有量は、成分Ａ及び成分Ｂ、並びに必要に応じて配合される後述の任意成分の残余とすることができる。
[Aqueous medium]
Examples of the aqueous medium contained in the polishing liquid composition of the present disclosure include distilled water, ion-exchanged water, water such as pure water and ultrapure water, or a mixed solvent of water and a solvent. Examples of the solvent include a solvent that can be mixed with water (for example, an alcohol such as ethanol). When the aqueous medium is a mixed solvent of water and a solvent, the ratio of water to the entire mixed medium may not be particularly limited as long as the effects of the present disclosure are not hindered, and from the viewpoint of economy, for example, , 95% by mass or more is preferable, 98% by mass or more is more preferable, and substantially 100% by mass is further preferable. From the viewpoint of surface cleanliness of the substrate to be polished, ion-exchanged water and ultrapure water are preferable, and ultrapure water is more preferable as the water-based medium. The content of the aqueous medium in the polishing liquid composition of the present disclosure can be the residue of component A and component B, and any component described below, which is blended as needed.
［酸（成分Ｃ）］
本開示の研磨液組成物は、研磨速度向上の観点から、酸及びその塩から選ばれる少なくとも１種（以下、「成分Ｃ」ともいう）をさらに含有してもよい。成分Ｃは単独で又は２種以上を混合して用いてもよい。成分Ｃとしては、例えば、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、スクラッチ及び短波長うねり低減の観点から、無機酸及び有機ホスホン酸の少なくとも一方が好ましい。無機酸の中では、硝酸、硫酸、塩酸、過塩素酸及びリン酸から選ばれる少なくとも１種が好ましく、リン酸及び硫酸の少なくとも一方がより好ましい。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）、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）及びそれらの塩から選ばれる少なくとも１種が好ましく、１−ヒドロキシエチリデン−１，１−ジホスホン酸及びアミノトリ（メチレンホスホン酸）の少なくとも一方がより好ましい。
[Acid (component C)]
The polishing liquid composition of the present disclosure may further contain at least one selected from an acid and a salt thereof (hereinafter, also referred to as "component C") from the viewpoint of improving the polishing speed. Component C may be used alone or in combination of two or more. The component C includes, for example, an inorganic acid such as nitrate, sulfuric acid, sulfite, persulfate, hydrochloric acid, perchloric acid, phosphoric acid, phosphonic acid, phosphinic acid, pyrophosphate, tripolyphosphate, and amide sulfate, and 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 , Methanhydroxyphosphonic acid, 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid, organic phosphonic acid such as α-methylphosphonosuccinic acid, glutamate, picolinic acid, aspartic acid Aminocarboxylic acids such as citric acid, tartaric acid, oxalic acid, nitroacetic acid, maleic acid, carboxylic acids such as oxaloacetate and the like can be mentioned. Of these, at least one of an inorganic acid and an organic phosphonic acid is preferable from the viewpoint of reducing scratches and short-wavelength waviness. Among the inorganic acids, at least one selected from nitric acid, sulfuric acid, hydrochloric acid, perchloric acid and phosphoric acid is preferable, and at least one of phosphoric acid and sulfuric acid is more preferable. Among organic phosphonic acids, at least one selected from 1-hydroxyethylidene-1,1-diphosphonic acid, aminotri (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) and salts thereof. Species are preferred, with at least one of 1-hydroxyethylidene-1,1-diphosphonic acid and aminotri (methylenephosphonic acid) being more preferred.
前記酸の塩を用いる場合の塩としては、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。 The salt when the salt of the acid is used is not particularly limited, and specific examples thereof include metal, ammonium, and alkylammonium. Specific examples of the metal include metals belonging to Group 8 of the periodic table (long-period type) 1A, 1B, 2A, 2B, 3A, 3B, 4A, 6A, 7A. Among these, a salt with a metal belonging to Group 1A or ammonium is preferable from the viewpoint of reducing scratches on the surface of the substrate after polishing.
本開示の研磨液組成物中における成分Ｃの含有量は、研磨速度向上、スクラッチ及び短波長うねり低減の観点から、０．００１質量％以上が好ましく、０．０１質量％以上がより好ましく、０．０５質量％以上が更に好ましく、そして、５質量％以下が好ましく、４質量％以下がより好ましく、３質量％以下が更に好ましい。さらに、同様の観点から、成分Ｃの含有量は、０．００１質量％以上５質量％以下が好ましく、０．０１質量％以上４質量％以下がより好ましく、０．０５質量％以上３質量％以下が更に好ましい。 The content of component C in the polishing liquid composition of the present disclosure is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and 0, from the viewpoint of improving the polishing speed, reducing scratches and short wavelength waviness. It is more preferably 0.05% by mass or more, preferably 5% by mass or less, more preferably 4% by mass or less, still more preferably 3% by mass or less. Further, from the same viewpoint, the content of the component C is preferably 0.001% by mass or more and 5% by mass or less, more preferably 0.01% by mass or more and 4% by mass or less, and 0.05% by mass or more and 3% by mass or less. The following is more preferable.
［酸化剤（成分Ｄ）］
本開示の研磨液組成物は、研磨速度の向上、スクラッチ及び短波長うねり低減の観点から、酸化剤（以下、「成分Ｄ」ともいう）をさらに含有してもよい。成分Ｄは、単独で又は２種以上を混合して使用してもよい。成分Ｄとしては、例えば、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。
[Oxidizing agent (component D)]
The polishing liquid composition of the present disclosure may further contain an oxidizing agent (hereinafter, also referred to as “component D”) from the viewpoint of improving the polishing rate, reducing scratches and short-wavelength waviness. Component D may be used alone or in combination of two or more. Examples of the component D include peroxides, permanganic acid or salts thereof, chromic acid or salts thereof, peroxo acid or salts thereof, oxygen acid or salts thereof, metal salts, nitric acids, sulfuric acids and the like.
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る。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る。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る。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る。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る。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 and the like. Examples of permanganate or a salt thereof include potassium permanganate and the like. Examples of chromic acid or a salt thereof include chromic acid metal salt, dichromic acid metal salt and the like. Examples of peroxoic acid or a salt thereof include peroxodisulfuric acid, ammonium peroxodisulfate, metal salt peroxodisulfate, peroxophosphate, peroxosulfate, sodium peroxoborate, peroxy acid, peracetic acid, perbenzoic acid, perphthalic acid and the like. Be done. Examples of the oxygen acid or a salt thereof include hypochlorous acid, hypobromous acid, hypobromous acid, chloric acid, bromic acid, iodic acid, sodium hypochlorite, calcium hypochlorite and the like. Examples of the metal salts include iron (III) chloride, iron (III) nitrate, iron (III) sulfate, iron (III) citrate, iron (III) ammonium sulfate and the like.
成分Ｄとしては、スクラッチ及び短波長うねりの低減の観点から、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）から選ばれる少なくとも１種が好ましい。中でも、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、過酸化水素がより好ましい。 As the component D, at least one selected from hydrogen peroxide, iron nitrate (III), peracetic acid, ammonium peroxodisulfate, iron (III) sulfate and iron (III) sulfate from the viewpoint of reducing scratches and short-wavelength waviness. Is preferable. Of these, hydrogen peroxide is more preferable from the viewpoint that metal ions do not adhere to the surface, it is used for general purposes, and it is inexpensive.
本開示の研磨液組成物中の成分Ｄの含有量は、研磨速度向上の観点から、０．０１質量％以上が好ましく、０．０５質量％以上がより好ましく、０．１質量％以上が更に好ましく、そして、スクラッチ及び短波長うねり低減の観点から、４質量％以下が好ましく、２質量％以下がより好ましく、１質量％以下が更に好ましい。さらに、研磨速度向上、スクラッチ及び短波長うねり低減の観点から、成分Ｄの含有量は、０．０１質量％以上４質量％以下が好ましく、０．０５質量％以上２質量％以下がより好ましく、０．１質量％以上１質量％以下が更に好ましい。 The content of component D in the polishing liquid composition of the present disclosure 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 speed. It is preferable, and from the viewpoint of scratch and reduction of short wavelength waviness, 4% by mass or less is preferable, 2% by mass or less is more preferable, and 1% by mass or less is further preferable. Further, from the viewpoint of improving the polishing speed and reducing scratches and short wavelength waviness, the content of the component D is preferably 0.01% by mass or more and 4% by mass or less, and more preferably 0.05% by mass or more and 2% by mass or less. It is more preferably 0.1% by mass or more and 1% by mass or less.
［その他の成分］
本開示の研磨液組成物は、必要に応じてその他の成分を含有してもよい。その他の成分としては、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。本開示の研磨液組成物中の前記その他の成分の含有量は、０質量％以上が好ましく、０質量％超がより好ましく、０．１質量％以上が更に好ましく、そして、１０質量％以下が好ましく、５質量％以下がより好ましい。より具体的には、その他の成分の含有量は、０質量％以上１０質量％以下が好ましく、０質量％超１０質量％以下がより好ましく、０．１質量％以上５質量％以下が更に好ましい。但し、本開示の研磨液組成物は、その他の成分、とりわけ界面活性剤を含むことなく、スクラッチ及び短波長うねりの低減効果を発揮し得る。さらに、本開示の研磨液組成物は、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]
The polishing liquid composition of the present disclosure may contain other components if necessary. Examples of other components include thickeners, dispersants, rust inhibitors, basic substances, surfactants and the like. The content of the other components in the polishing liquid composition of the present disclosure is preferably 0% by mass or more, more preferably more than 0% by mass, further preferably 0.1% by mass or more, and 10% by mass or less. It is preferably 5% by mass or less, and more preferably 5% by mass or less. More specifically, the content of other components is preferably 0% by mass or more and 10% by mass or less, more preferably more than 0% by mass and 10% by mass or less, still more preferably 0.1% by mass or more and 5% by mass or less. .. However, the polishing liquid composition of the present disclosure can exhibit the effect of reducing scratches and short-wavelength waviness without containing other components, particularly a surfactant. Further, the polishing liquid composition of the present disclosure can contain alumina abrasive grains and can be used in a rough polishing step prior to the final polishing step.
[研磨液組成物中のホルムアルデヒド含有量]
本開示の研磨液組成物中のホルムアルデヒド含有量は、スクラッチ及び短波長うねり低減の観点から、０．００ｐｐｍ又は０．００ｐｐｍを超え１０．０ｐｐｍ以下が好ましく、より好ましくは０．００ｐｐｍ又は０．００ｐｐｍを超え５．０ｐｐｍ以下、更に好ましくは０．００ｐｐｍ又は０．００ｐｐｍを超え４．０ｐｐｍ以下、更により好ましくは０．００ｐｐｍ又は０．００ｐｐｍを超え３．０ｐｐｍ以下、更により好ましくは０．００ｐｐｍ又は０．００ｐｐｍを超え１．０ｐｐｍ以下、更により好ましくは０．００ｐｐｍ又は０．００ｐｐｍを超え０．５５ｐｐｍ以下、更により好ましくは０．００ｐｐｍ又は０．００ｐｐｍを超え０．５ｐｐｍ以下、更により好ましくは０．００ｐｐｍ又は０．００ｐｐｍを超え０．４ｐｐｍ以下、更により好ましくは０．００ｐｐｍ又は０．００ｐｐｍを超え０．１ｐｐｍ以下である。研磨液組成物中のホルムアルデヒド含有量は、上述した成分Ｂにおける残存モノマーであるホルムアルデヒド含有量と同様に高速液体クロマトグラフィー（ＨＰＬＣ）を用いて測定できる。
[Formaldehyde content in polishing liquid composition]
The formaldehyde content in the polishing liquid composition of the present disclosure is preferably more than 0.00 ppm or 0.00 ppm and 10.0 ppm or less, more preferably 0.00 ppm or 0.00 ppm, from the viewpoint of reducing scratches and short wavelength waviness. More than 5.0 ppm or less, more preferably 0.00 ppm or more than 0.00 ppm and 4.0 ppm or less, still more preferably 0.00 ppm or more than 0.00 ppm and 3.0 ppm or less, still more preferably 0.00 ppm or More than 0.00 ppm and 1.0 ppm or less, even more preferably 0.00 ppm or more than 0.00 ppm and 0.55 ppm or less, even more preferably 0.00 ppm or more than 0.00 ppm and 0.5 ppm or less, even more preferably. It is more than 0.00 ppm or 0.00 ppm and 0.4 ppm or less, and even more preferably more than 0.00 ppm or 0.00 ppm and 0.1 ppm or less. The formaldehyde content in the polishing liquid composition can be measured by using high performance liquid chromatography (HPLC) in the same manner as the formaldehyde content which is a residual monomer in the above-mentioned component B.
［研磨液組成物のｐＨ］
本開示の研磨液組成物のｐＨは、研磨速度向上の観点から、４以下が好ましく、３．５以下がより好ましく、３以下が更に好ましく、２．５以下が更に好ましく、そして、スクラッチ及び短波長うねり低減の観点から、０．５以上が好ましく、０．８以上がより好ましく、１以上が更に好ましく、１．２以上が更に好ましい。さらに、研磨速度向上、スクラッチ及び短波長うねり低減の観点から、ｐＨは、０．５以上４以下が好ましく、０．８以上３．５以下がより好ましく、１以上３以下が更に好ましく、１．２以上２．５以下が更に好ましい。ｐＨは、上述した酸（成分Ｃ）や公知のｐＨ調整剤等を用いて調整することができる。本開示において、上記ｐＨは、２５℃における研磨液組成物のｐＨであり、ｐＨメータを用いて測定でき、例えば、ｐＨメータの電極を研磨液組成物へ浸漬して２分後の数値とすることができる。
[PH of polishing liquid composition]
From the viewpoint of improving the polishing rate, the pH of the polishing liquid composition of the present disclosure is preferably 4 or less, more preferably 3.5 or less, further preferably 3 or less, further preferably 2.5 or less, and scratch and short. From the viewpoint of reducing wavelength swell, 0.5 or more is preferable, 0.8 or more is more preferable, 1 or more is further preferable, and 1.2 or more is further preferable. Further, from the viewpoint of improving the polishing speed and reducing scratches and short wavelength waviness, the pH is preferably 0.5 or more and 4 or less, more preferably 0.8 or more and 3.5 or less, further preferably 1 or more and 3 or less. More preferably 2 or more and 2.5 or less. The pH can be adjusted by using the above-mentioned acid (component C), a known pH adjuster, or the like. In the present disclosure, the pH is the pH of the polishing liquid composition at 25 ° C. and can be measured using a pH meter. For example, the pH is set to a value 2 minutes after the electrode of the pH meter is immersed in the polishing liquid composition. be able to.
［研磨液組成物の製造方法］
本開示の研磨液組成物は、例えば、成分Ａ、成分Ｂ及び水系媒体と、さらに所望により、成分Ｃ、成分Ｄ及びその他の成分とを公知の方法で配合することにより製造できる。すなわち、本開示は、その他の態様において、少なくとも成分Ａ、成分Ｂ及び水系媒体を配合する工程を含む、研磨液組成物の製造方法に関する。本開示において「配合する」とは、成分Ａ，成分Ｂ及び水系媒体、並びに必要に応じて成分Ｃ、成分Ｄ及びその他の成分を同時に又は任意の順に混合することを含む。前記配合は、例えば、ホモミキサー、ホモジナイザー、超音波分散機及び湿式ボールミル等の混合器を用いて行うことができる。成分Ａの研磨材は、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。研磨材スラリー及び研磨液組成物の製造方法における各成分の好ましい配合量は、上述した本開示の研磨液組成物中の各成分の好ましい含有量と同じとすることができる。
[Manufacturing method of polishing liquid composition]
The polishing liquid composition of the present disclosure can be produced, for example, by blending component A, component B and an aqueous medium, and if desired, component C, component D and other components by a known method. That is, the present disclosure relates to a method for producing an abrasive liquid composition, which comprises, in other embodiments, at least a step of blending component A, component B and an aqueous medium. In the present disclosure, "blending" includes mixing component A, component B and an aqueous medium, and optionally component C, component D and other components simultaneously or in any order. The compounding can be performed using, for example, a mixer such as a homomixer, a homogenizer, an ultrasonic disperser, and a wet ball mill. The abrasive of component A may be mixed in the state of a concentrated slurry, or may be diluted with water or the like and then mixed. The preferable blending amount of each component in the method for producing the abrasive slurry and the polishing liquid composition can be the same as the preferable content of each component in the polishing liquid composition of the present disclosure described above.
本開示において「研磨液組成物中の各成分の含有量」とは、研磨液組成物を研磨に使用する時点における前記各成分の含有量をいう。本開示の研磨液組成物は、保存安定性が損なわれない範囲で濃縮された状態で保存及び供給されてもよい。この場合、製造及び輸送コストを更に低くできる点で好ましい。本開示の研磨液組成物の濃縮物は、使用時に、必要に応じて前述の水系媒体で適宜希釈して使用すればよい。 In the present disclosure, the "content of each component in the polishing liquid composition" means the content of each component at the time when the polishing liquid composition is used for polishing. The polishing liquid composition of the present disclosure may be stored and supplied in a concentrated state as long as the storage stability is not impaired. In this case, it is preferable in that the manufacturing and transportation costs can be further reduced. The concentrate of the polishing liquid composition of the present disclosure may be appropriately diluted with the above-mentioned aqueous medium at the time of use, if necessary.
本開示の研磨液組成物は、精密部品用基板の製造に好適に使用できる。例えば磁気ディスク、光磁気ディスク、光ディスク等の磁気ディスク基板、フォトマスク基板、光学レンズ、光学ミラー、光学プリズム、半導体基板などの精密部品用基板の研磨に適しており、とりわけ、磁気ディスク基板の研磨に適している。半導体基板の製造においては、シリコンウエハ（ベアウエハ）のポリッシング工程、埋め込み素子分離膜の形成工程、層間絶縁膜の平坦化工程、埋め込み金属配線の形成工程、埋め込みキャパシタ形成工程等において本開示の研磨液組成物を用いることができる。 The polishing liquid composition of the present disclosure can be suitably used for manufacturing a substrate for precision parts. For example, it is suitable for polishing magnetic disk substrates such as magnetic disks, magneto-optical disks, optical disks, photomask substrates, optical lenses, optical mirrors, optical prisms, semiconductor substrates, etc., and in particular, polishing magnetic disk substrates. Suitable for. In the manufacture of a semiconductor substrate, the polishing liquid of the present disclosure is used in a silicon wafer (bare wafer) polishing step, an embedded element separation membrane forming step, an interlayer insulating film flattening step, an embedded metal wiring forming step, an embedded capacitor forming step, and the like. The composition can be used.
［研磨液キット］
本開示は、その他の態様において、本開示の研磨液組成物を製造するためのキット（以下、「本開示の研磨液キット」ともいう）に関する。本開示の研磨液キットの一実施形態としては、例えば、成分Ａ及び水系媒体を含む研磨材分散液と、成分Ｂを含む添加剤水溶液と、を相互に混合されない状態で含む、研磨液キット（２液型研磨液組成物）が挙げられる。前記研磨材分散液と添加剤水溶液とは、使用時に混合され、必要に応じて水系媒体を用いて希釈される。前記研磨材分散液及び前記添加剤水溶液にはそれぞれ必要に応じて、上述した任意成分（成分Ｃ、成分Ｄ及びその他の成分）が含まれていてもよい。
[Abrasive liquid kit]
The present disclosure relates to a kit for producing the polishing liquid composition of the present disclosure (hereinafter, also referred to as "polishing liquid kit of the present disclosure") in another aspect. As one embodiment of the polishing liquid kit of the present disclosure, for example, a polishing liquid kit containing a polishing material dispersion liquid containing the component A and an aqueous medium and an additive aqueous solution containing the component B in a state where they are not mixed with each other. Two-component abrasive liquid composition) can be mentioned. The abrasive dispersion and the additive aqueous solution are mixed at the time of use and diluted with an aqueous medium if necessary. The abrasive dispersion liquid and the additive aqueous solution may each contain the above-mentioned optional components (component C, component D and other components), if necessary.
［被研磨基板］
本開示の研磨液組成物が研磨の対象とする被研磨基板の材質としては、例えばシリコン、アルミニウム、ニッケル、タングステン、銅、タンタル、チタン等の金属若しくは半金属、又はこれらの合金や、ガラス、ガラス状カーボン、アモルファスカーボン等のガラス状物質や、アルミナ、二酸化珪素、窒化珪素、窒化タンタル、炭化チタン等のセラミック材料や、ポリイミド樹脂等の樹脂等が挙げられる。中でも、アルミニウム、ニッケル、タングステン、銅等の金属や、これらの金属を主成分とする合金を含有する被研磨基板、ガラス基板が好適である。中でも、Ｎｉ−Ｐメッキされたアルミニウム合金基板や、アルミノシリケートガラス基板に適しており、Ｎｉ−Ｐメッキされたアルミニウム合金基板がさらに適している。アルミノシリケートガラス基板には、結晶構造を有しているもの、化学強化処理を施したものが含まれる。化学強化処理は研磨後に行ってもよい。
[Substrate to be polished]
Examples of the material of the substrate to be polished by the polishing liquid composition of the present disclosure include metals or semi-metals such as silicon, aluminum, nickel, tungsten, copper, tantalum, and titanium, alloys thereof, glass, and the like. Examples thereof include glassy substances such as glassy carbon and amorphous carbon, ceramic materials such as alumina, silicon dioxide, silicon nitride, tantalum nitride and titanium carbide, and resins such as polyimide resin. Of these, metals such as aluminum, nickel, tungsten, and copper, and substrates to be polished and glass substrates containing alloys containing these metals as main components are preferable. Among them, it is suitable for a Ni-P-plated aluminum alloy substrate and an electroless silicate glass substrate, and a Ni-P-plated aluminum alloy substrate is more suitable. The aluminosilicate glass substrate includes those having a crystal structure and those having undergone a chemical strengthening treatment. The chemical strengthening treatment may be performed after polishing.
また、本開示によれば、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うねりが低減された基板を提供できるため、高度の表面平滑性が要求される磁気ディスク基板、とりわけ垂直磁気記録方式の磁気ディスク基板の製造に好適に用いることができる。よって、本開示の研磨液組成物は、一又は複数の実施形態において、磁気ディスク基板用研磨液組成物であってもよい。本開示の研磨液組成物が磁気ディスク基板用研磨液組成物である場合、被研磨基板としては、磁気ディスク基板の製造に用いられる基板が挙げられ、具体的には、Ｎｉ−Ｐメッキされたアルミニウム合金基板が好ましく挙げられる。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、アルミニウム合金基材の表面を研削後、無電解Ｎｉ−Ｐメッキ処理したものをいう。一般に、磁気ディスクは、研削工程を経た被研磨基板が、粗研磨工程、仕上げ研磨工程を経て研磨され、磁性層形成工程を経て製造される。磁気ディスク基板を製造する場合、本開示の研磨液組成物は、仕上げ研磨工程における研磨に使用されることが好ましい。 Further, according to the present disclosure, in addition to scratching the surface of the substrate after polishing, it is possible to provide a substrate in which the waviness of the surface of the substrate after polishing is reduced, so that a magnetic disk substrate that requires a high degree of surface smoothness, particularly It can be suitably used for manufacturing a magnetic disk substrate of a perpendicular magnetic recording system. Therefore, the polishing liquid composition of the present disclosure may be a polishing liquid composition for a magnetic disk substrate in one or more embodiments. When the polishing liquid composition of the present disclosure is a polishing liquid composition for a magnetic disk substrate, the substrate to be polished includes a substrate used for manufacturing a magnetic disk substrate, and specifically, Ni-P plated. An aluminum alloy substrate is preferably mentioned. In the present disclosure, the "Ni-P plated aluminum alloy substrate" refers to an aluminum alloy substrate surface that has been ground and then electroless Ni-P plated. Generally, a magnetic disk is manufactured by polishing a substrate to be polished that has undergone a grinding step through a rough polishing step and a finish polishing step, and then through a magnetic layer forming step. When manufacturing a magnetic disk substrate, the polishing liquid composition of the present disclosure is preferably used for polishing in the finish polishing step.
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。 The shape of the substrate to be polished is not particularly limited, and may be, for example, a shape having a flat portion such as a disk shape, a plate shape, a slab shape, or a prism shape, or a shape having a curved surface portion such as a lens. Above all, a disk-shaped substrate to be polished is suitable. In the case of a disk-shaped substrate to be polished, its outer diameter is, for example, about 2 to 95 mm, and its thickness is, for example, about 0.5 to 2 mm.
［基板の製造方法］
本開示は、その他の態様において、上述した本開示の研磨液組成物を研磨パッドに接触させながら被研磨基板を研磨する工程（以下、「本開示の研磨液組成物を用いた研磨工程」ともいう。）を含む、基板の製造方法（以下、「本開示の基板製造方法」ともいう。）に関する。これにより、研磨後の基板表面のスクラッチに加えて、研磨後の基板表面うねりが低減された基板を提供できる。本開示の基板製造方法は、磁気ディスク基板の製造方法に適しており、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。よって、本開示の基板製造方法は、その他の態様として、本開示の研磨液組成物を用いた研磨工程を含む基板の製造方法であり、好ましくは磁気ディスク基板の製造方法であり、より好ましくは垂直磁気記録方式用磁気ディスク基板の製造方法である。
[Substrate manufacturing method]
In another aspect, the present disclosure is also referred to as a step of polishing a substrate to be polished while bringing the above-mentioned polishing liquid composition of the present disclosure into contact with a polishing pad (hereinafter, "polishing step using the polishing liquid composition of the present disclosure"). The present invention relates to a substrate manufacturing method (hereinafter, also referred to as “the substrate manufacturing method of the present disclosure”) including the above. This makes it possible to provide a substrate in which the surface waviness of the substrate after polishing is reduced in addition to the scratches on the surface of the substrate after polishing. The substrate manufacturing method of the present disclosure is suitable for a method for manufacturing a magnetic disk substrate, and is particularly suitable for a method for manufacturing a magnetic disk substrate for a perpendicular magnetic recording method. Therefore, the substrate manufacturing method of the present disclosure is, as another aspect, a method of manufacturing a substrate including a polishing step using the polishing liquid composition of the present disclosure, preferably a method of manufacturing a magnetic disk substrate, and more preferably. This is a method for manufacturing a magnetic disk substrate for a perpendicular magnetic recording method.
本開示の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、本開示の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 the method of polishing the substrate to be polished using the polishing liquid composition of the present disclosure, the substrate to be polished is sandwiched between a platen to which a polishing pad such as a non-woven organic polymer-based polishing cloth is attached. Examples thereof include a method of polishing the substrate to be polished by moving the platen or the substrate to be polished while supplying the disclosed polishing liquid composition to the polishing machine.
被研磨基板の研磨工程が多段階で行われる場合は、本開示の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（例えば、仕上げ研磨工程）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。また使用した研磨液を再利用する循環研磨においても、本開示の研磨液組成物は使用できる。研磨機としては、特に限定されず、基板研磨用の公知の研磨機が使用できる。 When the polishing step of the substrate to be polished is performed in multiple steps, the polishing step using the polishing liquid composition of the present disclosure is preferably performed in the second and subsequent steps, and in the final polishing step (for example, the finish polishing step). More preferably done. At that time, in order to avoid mixing of the abrasive material and the polishing liquid composition in the previous process, different polishing machines may be used, and when different polishing machines are used, each polishing process is to be polished. It is preferable to clean the substrate. The polishing liquid composition of the present disclosure can also be used in circulation polishing in which the used polishing liquid is reused. The polishing machine is not particularly limited, and a known polishing machine for polishing a substrate can be used.
本開示の研磨液組成物を用いた研磨工程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できる。 The polishing pad used in the polishing process using the polishing liquid composition of the present disclosure is not particularly limited, and a suede type, a non-woven fabric type, a polyurethane independent foam type, or a two-layer type in which these are laminated may be used. Can be used.
研磨パッドの表面部材の平均開孔径は、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、４５μｍ以下がより好ましく、４０μｍ以下が更に好ましく、３５μｍ以下が更に好ましいそして、パッドの研磨液保持性の観点から、０．０１μｍ以上が好ましく、０．１μｍ以上がより好ましく、１μｍ以上が更に好ましく、１０μｍ以上が更に好ましい。研磨パッドの開孔径の最大値は、研磨速度維持の観点から、１００μｍ以下が好ましく、７０μｍ以下がより好ましく、６０μｍ以下が更に好ましく、５０μｍ以下が更に好ましい。 The average opening diameter of the surface member of the polishing pad is preferably 50 μm or less, more preferably 45 μm or less, further preferably 40 μm or less, further preferably 35 μm or less, and the polishing liquid retention of the pad from the viewpoint of scratch reduction and pad life. From the above viewpoint, 0.01 μm or more is preferable, 0.1 μm or more is more preferable, 1 μm or more is further preferable, and 10 μm or more is further preferable. The maximum value of the opening diameter of the polishing pad is preferably 100 μm or less, more preferably 70 μm or less, further preferably 60 μm or less, still more preferably 50 μm or less, from the viewpoint of maintaining the polishing rate.
本開示の研磨液組成物を用いた研磨工程における研磨荷重は、研磨速度確保及び短波長うねり低減の観点から、５．９ｋＰａ以上が好ましく、６．９ｋＰａ以上がより好ましく、７．５ｋＰａ以上が更に好ましく、そして、スクラッチ低減の観点から、２０ｋＰａ以下が好ましく、１８ｋＰａ以下がより好ましく、１６ｋＰａ以下が更に好ましい。本開示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。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。 The polishing load in the polishing process using the polishing liquid composition of 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, from the viewpoint of ensuring the polishing rate and reducing short wavelength waviness. It is preferable, and from the viewpoint of scratch reduction, 20 kPa or less is preferable, 18 kPa or less is more preferable, and 16 kPa or less is further preferable. In the present disclosure, the polishing load means the pressure of the surface plate applied to the polishing surface of the substrate to be polished during polishing. The polishing load can be adjusted by applying an air pressure or a weight to at least one of the surface plate and the substrate to be polished.
本開示の研磨液組成物を用いた研磨工程における、本開示の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／分が好ましく、０．０６〜１０ｍＬ／分がより好ましく、０．０７〜１ｍＬ／分が更に好ましく、０．０７〜０．５ｍＬ／分が更に好ましい。 In the polishing process using the polishing liquid composition of the present disclosure, the supply speed of the polishing liquid composition of the present disclosure is preferably 0.05 to 15 mL / min per 1 cm 2 of the substrate to be polished from the viewpoint of scratch reduction. , 0.06 to 10 mL / min, more preferably 0.07 to 1 mL / min, even more preferably 0.07 to 0.5 mL / min.
本開示の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、本開示の研磨液組成物となる。 Examples of the method of supplying the polishing liquid composition of the present disclosure to the polishing machine include a method of continuously supplying the polishing liquid composition using a pump or the like. When supplying the polishing liquid composition to the polishing machine, in addition to the method of supplying it as one liquid containing all the components, in consideration of the stability of the polishing liquid composition, etc., it is divided into a plurality of compounding component liquids. It can also be supplied in two or more liquids. 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 of the present disclosure.
［研磨方法］
本開示は、その他の態様において、上述した本開示の研磨液組成物を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、基板の研磨方法（以下、「本開示の研磨方法」ともいう）に関する。本開示の研磨方法における、本開示の研磨液組成物を用いた被研磨基板の研磨は、例えば、仕上げ研磨である。
本開示の研磨方法を使用することにより、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うねりが低減された基板が提供される。具体的な研磨の方法及び条件は、上述した本開示の基板製造方法と同じようにすることができる。
[Polishing method]
The present disclosure also includes a method for polishing a substrate (hereinafter, also referred to as "the polishing method of the present disclosure"), which comprises polishing the substrate to be polished while bringing the above-mentioned polishing liquid composition of the present disclosure into contact with a polishing pad in another aspect. Regarding). The polishing of the substrate to be polished using the polishing liquid composition of the present disclosure in the polishing method of the present disclosure is, for example, finish polishing.
By using the polishing method of the present disclosure, a substrate in which waviness of the surface of the substrate after polishing is reduced in addition to scratches on the surface of the substrate after polishing is provided. The specific polishing method and conditions can be the same as the substrate manufacturing method of the present disclosure described above.
本開示はさらに以下の一又は複数の実施形態に関する。
＜１＞ 研磨材（成分Ａ）、水溶性重合体（成分Ｂ）、及び水系媒体を含有する研磨液組成物であって、
前記水溶性重合体（成分Ｂ）が、下記一般式（Ｉ）で表される構成を有する、研磨液組成物。
<1> An abrasive liquid composition containing an abrasive (component A), a water-soluble polymer (component B), and an aqueous medium.
A polishing liquid composition in which the water-soluble polymer (component B) has a structure represented by the following general formula (I).
＜２＞ 成分Ａが、レーザー光回折・散乱を測定原理とした粒度分布計で測定したときのメジアン径が４〜１００ｎｍであるダイヤモンド構造を有する微粒子を実質的に含まない、＜１＞に記載の研磨液組成物。
＜３＞ 成分Ａの平均粒径は、１ｎｍ以上が好ましく、５ｎｍ以上がより好ましく、１０ｎｍ以上が更に好ましい、＜１＞又は＜２＞に記載の研磨液組成物。
＜４＞ 成分Ａの平均粒径は、１００ｎｍ以下が好ましく、７０ｎｍ以下がより好ましく、４０ｎｍ以下が更に好ましい、＜１＞から＜３＞のいずれかに記載の研磨液組成物。
＜５＞ 成分Ａの平均粒径は、１ｎｍ以上１００ｎｍ以下が好ましく、５ｎｍ以上７０ｎｍ以下がより好ましく、１０ｎｍ以上４０ｎｍ以下が更に好ましい、＜１＞から＜４＞のいずれかに記載の研磨液組成物。
＜６＞ 成分Ａがシリカである、＜１＞から＜５＞のいずれかに記載の研磨液組成物。
＜７＞ 成分Ａの含有量は、０．１質量％以上が好ましく、１質量％以上がより好ましく、３質量％以上が更に好ましい、＜１＞から＜６＞のいずれかに記載の研磨液組成物。
＜８＞ 成分Ａの含有量は、２０質量％以下が好ましく、１５質量％以下がより好ましく、１０質量％以下が更に好ましい、＜１＞から＜７＞のいずれかに記載の研磨液組成物。
＜９＞ 成分Ａの含有量は、０．１質量％以上２０質量％以下が好ましく、１質量％以上１５質量％以下がより好ましく、３質量％以上１０質量％以下が更に好ましい、＜１＞から＜８＞のいずれかに記載の研磨液組成物。
＜１０＞ 成分Ｂ中の、主鎖を構成するフェノール骨格の側鎖に芳香族環を有する構成単位の含有量が、５モル％以下が好ましく、４モル％以下がより好ましく、３モル％以下が更に好ましく、２モル％以下が更に好ましく、１モル％以下が更に好ましく、実質的に０モル％が更に好ましい、＜１＞から＜９＞のいずれかに記載の研磨液組成物。
＜１１＞ ｍは、０≦ｍ≦０．４であって、０≦ｍ≦０．３が好ましく、０≦ｍ≦０．２５がより好ましく、０≦ｍ≦０．２が更に好ましい、＜１＞から＜１０＞のいずれかに記載の研磨液組成物。
＜１２＞ 成分Ｂを構成する全構成単位中に占める式（Ｉ）で表される構成の含有量は、５モル％以上が好ましく、１０モル％以上がより好ましく、２０モル％以上が更に好ましい、＜１＞から＜１１＞のいずれかに記載の研磨液組成物。
＜１３＞ 成分Ｂを構成する全構成単位中に占める式（Ｉ）で表される構成の含有量は、１００モル％以下が好ましく、９５モル％以下がより好ましく、９０モル％以下が更に好ましく、８０モル％以下が更に好ましい、＜１＞から＜１２＞のいずれかに記載の研磨液組成物。
＜１４＞ 成分Ｂの全構成単位中に示す式（Ｉ）で表される構成の含有量は、５モル％以上１００モル％以下が好ましく、５モル％以上９５モル％以下がより好ましく、１０モル％以上９０モル％以下が更に好ましく、２０モル％以上８０モル％以下が更に好ましい、＜１＞から＜１３＞のいずれかに記載の研磨液組成物。
＜１５＞ 成分Ｂの重量平均分子量は、５００以上が好ましく、１,０００以上がより好ましく、１，４００以上が更に好ましく、１,５００以上が更に好ましく、３,０００以上が更に好ましく、４,５００以上が更に好ましく、５,０００以上が更に好ましく、８,０００以上が更に好ましく、１０,０００以上が更に好ましい、＜１＞から＜１４＞のいずれかに記載の研磨液組成物。
＜１６＞ 成分Ｂの重量平均分子量は、１，０００，０００以下が好ましく、７５０,０００以下がより好ましく、５００,０００以下が更に好ましく、２５０,０００以下が更に好ましく、１２０,０００以下が更に好ましく、１００,０００以下が更に好ましく、７５,０００以下が更に好ましく、５０,０００以下が更に好ましく、４０,０００以下が更に好ましく、３０,０００以下が更に好ましく、２５,０００以下が更に好ましく、２０,０００以下が更に好ましい、＜１＞から＜１５＞のいずれかに記載の研磨液組成物。
＜１７＞ 成分Ｂの重量平均分子量は、５００以上１，０００，０００以下が好ましく、１,０００以上７５０,０００以下がより好ましく、１，４００以上５００,０００以下が更に好ましく、１,５００以上２５０,０００以下が更に好ましく、３,０００以上１００,０００以下が更に好ましく、４,５００以上７５,０００以下が更に好ましく、５,０００以上５０,０００以下が更に好ましく、８,０００以上３０,０００以下が更に好ましく、１０,０００以上２０,０００以下が更に好ましい、＜１＞から＜１６＞のいずれかに記載の研磨液組成物。
＜１８＞ 成分Ｂの表面張力は、４５ｍＮ／ｍ以上が好ましく、５５ｍＮ／ｍ以上がより好ましく、６５ｍＮ／ｍ以上が更に好ましく、７１ｍＮ／ｍ以上が更に好ましく、７２ｍＮ／ｍ以上が更に好ましい、＜１＞から＜１７＞のいずれかに記載の研磨液組成物。
＜１９＞ 成分Ｂの表面張力は、９０ｍＮ／ｍ以下が好ましく、８０ｍＮ／ｍ以下がより好ましく、７７ｍＮ／ｍ以下が更に好ましく、７４ｍＮ／ｍ以下が更に好ましい、＜１＞から＜１８＞のいずれかに記載の研磨液組成物。
＜２０＞ 成分Ｂの表面張力は、４５ｍＮ／ｍ以上９０ｍＮ／ｍ以下が好ましく、５５ｍＮ／ｍ以上８０ｍＮ／ｍ以下がより好ましく、６５ｍＮ／ｍ以上７７ｍＮ／ｍ以下が更に好ましく、７１ｍＮ／ｍ以上７４ｍＮ／ｍ以下が更に好ましく、７２ｍＮ／ｍ以上７４ｍＮ／ｍ以下が更に好ましい、＜１＞から＜１９＞のいずれかに記載の研磨液組成物。
＜２１＞ 成分Ｂに浸潤させた研磨パッドの貯蔵弾性率は、０．１５ＭＰa以上が好ましく、０．２５ＭＰa以上がより好ましく、０．３０ＭＰa以上が更に好ましい、＜１＞から＜２０＞のいずれかに記載の研磨液組成物。
＜２２＞ 成分Ｂに浸潤させた研磨パッドの貯蔵弾性率は、０．５０ＭＰa以下が好ましく、０．４０ＭＰa以下がより好ましく、０．３５ＭＰa以下が更に好ましい、＜１＞から＜２１＞のいずれかに記載の研磨液組成物。
＜２３＞ 成分Ｂを浸潤させた研磨パッドの貯蔵弾性率は、０．１５ＭＰa以上０．５０ＭＰa以下が好ましく、０．２５ＭＰa以上０．４０ＭＰa以下がより好ましく、０．３０ＭＰa以上０．３５ＭＰa以下が更に好ましい、＜１＞から＜２２＞のいずれかに記載の研磨液組成物。
＜２４＞ 成分Ｂの含有量は、０．００１質量％以上が好ましく、０．００３質量％以上がより好ましく、０．００６質量％以上が更に好ましい、＜１＞から＜２３＞のいずれかに記載の研磨液組成物。
＜２５＞ 成分Ｂの含有量は、１０質量％以下が好ましく、１質量％以下がより好ましく、０．１質量％以下が更に好ましい、＜１＞から＜２４＞のいずれかに記載の研磨液組成物。
＜２６＞ 成分Ｂの含有量は、０．００１質量％以上１０質量％以下が好ましく、０．００３質量％以上１質量％以下がより好ましく、０．００６質量％以上０．１質量％以下が更に好ましい、＜１＞から＜２５＞のいずれかに記載の研磨液組成物。
＜２７＞ 成分Ａに対する成分Ｂの質量比（成分Ｂの含有量／成分Ａの含有量）は、０．０００１以上が好ましく、０．０００５以上がより好ましく、０．００１以上が更に好ましい、＜１＞から＜２６＞のいずれかに記載の研磨液組成物。
＜２８＞ 成分Ａに対する成分Ｂの質量比は、０．２以下が好ましく、０．０５以下がより好ましく、０．０１以下が更に好ましい、＜１＞から＜２７＞のいずれかに記載の研磨液組成物。
＜２９＞ 成分Ａに対する成分Ｂの質量比は、０．０００１以上０．２以下が好ましく、０．０００５以上０．０５以下がより好ましく、０．００１以上０．０１以下が更に好ましい、＜１＞から＜２８＞のいずれかに記載の研磨液組成物。
＜３０＞ 酸及びその塩から選ばれる少なくとも１種（成分Ｃ）をさらに含む、＜１＞から＜２９＞のいずれかに記載の研磨液組成物。
＜３１＞ 酸化剤（成分Ｄ）をさらに含む、＜１＞から＜３０＞のいずれかに記載の研磨液組成物。
＜３２＞ 研磨液組成物のｐＨは、４以下が好ましく、３．５以下がより好ましく、３以下が更に好ましく、２．５以下が更に好ましい、＜１＞から＜３１＞のいずれかに記載の研磨液組成物。
＜３３＞ 研磨液組成物のｐＨは、０．５以上が好ましく、０．８以上がより好ましく、１以上が更に好ましく、１．２以上が更に好ましい、＜１＞から＜３２＞のいずれかに記載の研磨液組成物。
＜３４＞ 研磨液組成物のｐＨは、０．５以上４以下が好ましく、０．８以上３．５以下がより好ましく、１以上３以下が更に好ましく、１．２以上２．５以下が更に好ましい、＜１＞から＜３３＞のいずれかに記載の研磨液組成物。
<2> Described in <1>, wherein the component A substantially does not contain fine particles having a diamond structure having a median diameter of 4 to 100 nm when measured with a particle size distribution meter based on laser light diffraction / scattering. Abrasive liquid composition.
<3> The polishing liquid composition according to <1> or <2>, wherein the average particle size of the component A is preferably 1 nm or more, more preferably 5 nm or more, still more preferably 10 nm or more.
<4> The polishing liquid composition according to any one of <1> to <3>, wherein the average particle size of the component A is preferably 100 nm or less, more preferably 70 nm or less, still more preferably 40 nm or less.
<5> The polishing liquid composition according to any one of <1> to <4>, wherein the average particle size of the component A is preferably 1 nm or more and 100 nm or less, more preferably 5 nm or more and 70 nm or less, and further preferably 10 nm or more and 40 nm or less. thing.
<6> The polishing liquid composition according to any one of <1> to <5>, wherein the component A is silica.
<7> The polishing liquid according to any one of <1> to <6>, wherein the content of the component A is preferably 0.1% by mass or more, more preferably 1% by mass or more, and further preferably 3% by mass or more. Composition.
<8> The polishing liquid composition according to any one of <1> to <7>, wherein the content of the component A is preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less. ..
<9> The content of the component A is preferably 0.1% by mass or more and 20% by mass or less, more preferably 1% by mass or more and 15% by mass or less, further preferably 3% by mass or more and 10% by mass or less, <1>. The polishing liquid composition according to any one of <8>.
<10> The content of the structural unit having an aromatic ring in the side chain of the phenol skeleton constituting the main chain in the component B is preferably 5 mol% or less, more preferably 4 mol% or less, and 3 mol% or less. The polishing liquid composition according to any one of <1> to <9>, wherein 2 mol% or less is further preferable, 1 mol% or less is further preferable, and substantially 0 mol% is further preferable.
<11> m is 0 ≦ m ≦ 0.4, preferably 0 ≦ m ≦ 0.3, more preferably 0 ≦ m ≦ 0.25, and even more preferably 0 ≦ m ≦ 0.2. The polishing liquid composition according to any one of 1> to <10>.
<12> The content of the composition represented by the formula (I) in all the constituent units constituting the component B is preferably 5 mol% or more, more preferably 10 mol% or more, still more preferably 20 mol% or more. , The polishing liquid composition according to any one of <1> to <11>.
<13> The content of the composition represented by the formula (I) in all the constituent units constituting the component B is preferably 100 mol% or less, more preferably 95 mol% or less, still more preferably 90 mol% or less. , 80 mol% or less, more preferably, the polishing liquid composition according to any one of <1> to <12>.
<14> The content of the composition represented by the formula (I) represented by the formula (I) in all the constituent units of the component B is preferably 5 mol% or more and 100 mol% or less, more preferably 5 mol% or more and 95 mol% or less, and 10 The polishing liquid composition according to any one of <1> to <13>, more preferably mol% or more and 90 mol% or less, still more preferably 20 mol% or more and 80 mol% or less.
<15> The weight average molecular weight of the component B is preferably 500 or more, more preferably 1,000 or more, further preferably 1,400 or more, further preferably 1,500 or more, further preferably 3,000 or more, 4, The polishing liquid composition according to any one of <1> to <14>, wherein 500 or more is more preferable, 5,000 or more is further preferable, 8,000 or more is further preferable, and 10,000 or more is further preferable.
<16> The weight average molecular weight of component B is preferably 1,000,000 or less, more preferably 75,000,000 or less, further preferably 500,000 or less, further preferably 250,000 or less, and further preferably 120,000 or less. Preferably, 100,000 or less is further preferable, 75,000 or less is further preferable, 50,000 or less is further preferable, 40,000 or less is further preferable, 30,000 or less is further preferable, and 25,000 or less is further preferable. The polishing liquid composition according to any one of <1> to <15>, more preferably 20,000 or less.
<17> The weight average molecular weight of component B is preferably 500 or more and 1,000,000 or less, more preferably 1,000 or more and 750,000 or less, further preferably 1,400 or more and 500,000 or less, and 1,500 or more. 250,000 or less is more preferable, 3,000 or more and 100,000 or less is further preferable, 4,500 or more and 75,000 or less is further preferable, 5,000 or more and 50,000 or less is further preferable, and 8,000 or more and 30, The polishing liquid composition according to any one of <1> to <16>, more preferably 000 or less, still more preferably 10,000 or more and 20,000 or less.
<18> The surface tension of component B is preferably 45 mN / m or more, more preferably 55 mN / m or more, further preferably 65 mN / m or more, further preferably 71 mN / m or more, further preferably 72 mN / m or more. The polishing liquid composition according to any one of 1> to <17>.
<19> The surface tension of component B is preferably 90 mN / m or less, more preferably 80 mN / m or less, further preferably 77 mN / m or less, further preferably 74 mN / m or less, any of <1> to <18>. The polishing liquid composition described in Crab.
<20> The surface tension of component B is preferably 45 mN / m or more and 90 mN / m or less, more preferably 55 mN / m or more and 80 mN / m or less, further preferably 65 mN / m or more and 77 mN / m or less, and 71 mN / m or more and 74 mN. The polishing liquid composition according to any one of <1> to <19>, wherein / m or less is more preferable, and 72 mN / m or more and 74 mN / m or less is further preferable.
<21> The storage elastic modulus of the polishing pad infiltrated with component B is preferably 0.15 MPa or more, more preferably 0.25 MPa or more, further preferably 0.30 MPa or more, any of <1> to <20>. The polishing liquid composition according to.
<22> The storage elastic modulus of the polishing pad infiltrated with component B is preferably 0.50 MPa or less, more preferably 0.40 MPa or less, further preferably 0.35 MPa or less, any of <1> to <21>. The polishing liquid composition according to.
<23> The storage elastic modulus of the polishing pad infiltrated with component B is preferably 0.15 MPa or more and 0.50 MPa or less, more preferably 0.25 MPa or more and 0.40 MPa or less, and further preferably 0.30 MPa or more and 0.35 MPa or less. The polishing liquid composition according to any one of <1> to <22>, which is preferable.
<24> The content of the component B is preferably 0.001% by mass or more, more preferably 0.003% by mass or more, still more preferably 0.006% by mass or more, any of <1> to <23>. The abrasive composition according to the above.
<25> The polishing liquid according to any one of <1> to <24>, wherein the content of the component B is preferably 10% by mass or less, more preferably 1% by mass or less, still more preferably 0.1% by mass or less. Composition.
<26> The content of component B is preferably 0.001% by mass or more and 10% by mass or less, more preferably 0.003% by mass or more and 1% by mass or less, and 0.006% by mass or more and 0.1% by mass or less. The polishing liquid composition according to any one of <1> to <25>, which is more preferable.
<27> The mass ratio of component B to component A (content of component B / content of component A) is preferably 0.0001 or more, more preferably 0.0005 or more, still more preferably 0.001 or more. The polishing liquid composition according to any one of 1> to <26>.
<28> The polishing according to any one of <1> to <27>, wherein the mass ratio of the component B to the component A is preferably 0.2 or less, more preferably 0.05 or less, still more preferably 0.01 or less. Liquid composition.
<29> The mass ratio of the component B to the component A is preferably 0.0001 or more and 0.2 or less, more preferably 0.0005 or more and 0.05 or less, further preferably 0.001 or more and 0.01 or less, <1. > To <28>.
<30> The polishing liquid composition according to any one of <1> to <29>, further comprising at least one (component C) selected from an acid and a salt thereof.
<31> The polishing liquid composition according to any one of <1> to <30>, further containing an oxidizing agent (component D).
<32> The pH of the polishing liquid composition is preferably 4 or less, more preferably 3.5 or less, further preferably 3 or less, still more preferably 2.5 or less, according to any one of <1> to <31>. Abrasive liquid composition.
<33> The pH of the polishing liquid composition is preferably 0.5 or more, more preferably 0.8 or more, further preferably 1 or more, further preferably 1.2 or more, any of <1> to <32>. The polishing liquid composition according to.
<34> The pH of the polishing liquid composition is preferably 0.5 or more and 4 or less, more preferably 0.8 or more and 3.5 or less, further preferably 1 or more and 3 or less, and further preferably 1.2 or more and 2.5 or less. The polishing liquid composition according to any one of <1> to <33>, which is preferable.
以下、実施例により本開示をさらに詳細に説明するが、これらは例示的なものであって、本開示はこれら実施例に制限されるものではない。 Hereinafter, the present disclosure will be described in more detail by way of examples, but these are exemplary and the present disclosure is not limited to these examples.
１．研磨液組成物の調製
成分Ａ（コロイダルシリカ、平均粒径２６ｎｍ）、成分Ｂ又は非成分Ｂ（表１−１及び表１−２に示す水溶性重合体Ｂ１〜１７）、成分Ｃ（硫酸）、成分Ｄ（過酸化水素水、濃度３５質量％）及びイオン交換水を混合し撹拌することにより、実施例１〜１１及び比較例１〜７の研磨液組成物（ｐＨ１．５）を調製した。研磨液組成物の２５℃におけるｐＨ値は、ｐＨメータ（東亜電波工業社製、「ＨＭ−３０Ｇ」を用いて測定した値であり、ｐＨメータの電極を研磨液組成物へ浸漬して２分後の数値を採用した。各研磨液組成物における各成分の含有量（有効分）は、成分Ａが５質量％、成分Ｂ又は非成分Ｂが０．００６質量％、成分Ｃが０．４質量％、成分Ｄが０．３質量％であった。
1. 1. Preparation of polishing liquid composition Component A (coloidal silica, average particle size 26 nm), component B or non-component B (water-soluble polymers B1 to 17 shown in Table 1-1 and Table 1-2), component C (sulfuric acid) , Component D (hydrogen peroxide solution, concentration 35% by mass) and ion-exchanged water were mixed and stirred to prepare polishing liquid compositions (pH 1.5) of Examples 1 to 11 and Comparative Examples 1 to 7. .. The pH value of the polishing liquid composition at 25 ° C. is a value measured using a pH meter (manufactured by Toa Denpa Kogyo Co., Ltd., "HM-30G", and the electrode of the pH meter is immersed in the polishing liquid composition for 2 minutes. The latter values were adopted. The content (effective content) of each component in each polishing liquid composition was 5% by mass for component A, 0.006% by mass for component B or non-component B, and 0.4 for component C. The mass% and the component D were 0.3 mass%.
研磨液組成物の調製に用いた成分Ｂ及び非成分Ｂの水溶性重合体Ｂ１〜Ｂ１７としては、以下のものを用いた。水溶性重合体Ｂ１〜Ｂ１７が有する構成を表１−１及び表１−２に示した。表１−１及び表１−２に記載の構成において、ｍ、ｎはそれぞれ、ｍ＋ｎ＝１とした場合のモル分率を示している。
＜成分Ｂ：水溶性重合体＞
Ｂ１〜Ｂ５：フェノールスルホン酸のホルムアルデヒド縮合物(アルカリ条件下にて合成) (pPhS、小西化学工業社製)
Ｂ６〜Ｂ７：フェノールスルホン酸のホルムアルデヒド縮合物(酸性条件下にて合成)(pPhS、小西化学工業社製)
Ｂ８：レゾルシノールスルホン酸のホルムアルデヒド縮合物(ResS、小西化学工業社製)
Ｂ９：フェノール/フェノールスルホン酸共重合体(Ph/PhS、小西化学工業社製)
Ｂ１０：クレゾール/フェノールスルホン酸共重合体(クレゾール/PhS、小西化学工業社製)
Ｂ１１：安息香酸/フェノールスルホン酸共重合体(安息香酸/PhS、小西化学工業社製)
＜非成分Ｂ：水溶性重合体＞
Ｂ１２：ビスフェノールＳ/フェノールスルホン酸共重合体(BisS/PhS、小西化学工業社製)
Ｂ１３：リグニンスルホン酸化合物(商品名：パールレックスNP、日本製紙ケミカル社製)
Ｂ１４：芳香族アミノスルホン酸化合物(商品名：フローリックSF200S、フローリック社製)
Ｂ１５：フェノールスルホン酸ナトリウム(モノマー)(小西化学工業社製)
Ｂ１６：フェノール樹脂粉末(p-Ph、商品名：ベルパールＳ−８９０、エア・ウオーター社製)
Ｂ１７：ポリスチレン/ポリスチレンスルホン酸共重合体ナトリウム塩(St/SS、花王社製)
ここで、２０℃でｐＨ３の水溶液１００ｇに対する溶解度は、Ｂ１〜Ｂ１５及びＢ１７が０．０１ｇ以上であり、Ｂ１６が０．０１ｇ未満である。
The following were used as the water-soluble polymers B1 to B17 of the component B and the non-component B used in the preparation of the polishing liquid composition. The configurations of the water-soluble polymers B1 to B17 are shown in Tables 1-1 and 1-2. In the configurations shown in Table 1-1 and Table 1-2, m and n indicate mole fractions when m + n = 1, respectively.
<Component B: Water-soluble polymer>
B1 to B5: Formaldehyde condensate of phenol sulfonic acid (synthesized under alkaline conditions) (pPhS, manufactured by Konishi Chemical Industry Co., Ltd.)
B6 to B7: Formaldehyde condensate of phenol sulfonic acid (synthesized under acidic conditions) (pPhS, manufactured by Konishi Chemical Industry Co., Ltd.)
B8: Formaldehyde condensate of resorcinol sulfonic acid (ResS, manufactured by Konishi Chemical Industry Co., Ltd.)
B9: Phenol / phenol sulfonic acid copolymer (Ph / PhS, manufactured by Konishi Chemical Industry Co., Ltd.)
B10: Cresol / phenol sulfonic acid copolymer (cresol / PhS, manufactured by Konishi Chemical Industry Co., Ltd.)
B11: Benzoic acid / phenol sulfonic acid copolymer (benzoic acid / PhS, manufactured by Konishi Chemical Industry Co., Ltd.)
<Non-component B: water-soluble polymer>
B12: Bisphenol S / Phenol Sulfonic Acid Copolymer (BisS / PhS, manufactured by Konishi Chemical Industry Co., Ltd.)
B13: Ligno sulfonic acid compound (trade name: Pearlex NP, manufactured by Nippon Paper Chemicals Co., Ltd.)
B14: Aromatic aminosulfonic acid compound (trade name: Floric SF200S, manufactured by Floric)
B15: Sodium phenol sulfonate (monomer) (manufactured by Konishi Chemical Industry Co., Ltd.)
B16: Phenol resin powder (p-Ph, trade name: Belpearl S-890, manufactured by Air Water Inc.)
B17: Polystyrene / polystyrene sulfonic acid copolymer sodium salt (St / SS, manufactured by Kao Corporation)
Here, the solubility of B1 to B15 and B17 in 100 g of an aqueous solution having a pH of 3 at 20 ° C. is 0.01 g or more and B16 is less than 0.01 g.
２．各種パラメータの測定方法
（１）水溶性重合体（成分Ｂ及び非成分Ｂ）の重量平均分子量
成分Ｂ及び非成分Ｂの重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）法により下記条件で測定した。測定結果を表１−１及び表１−２に示す。
＜測定条件＞
カラム：TSKgel GMPWXL+TSKgel GMPWXL（東ソー社製）
溶離液：０．２Ｍリン酸バッファー/ＣＨ3ＣＮ＝７／３（体積比）
温度：４０℃
流速：１．０ｍＬ／分
試料サイズ：２ｍｇ／ｍＬ
検出器：ＲＩ
標準物質：ポリスチレンスルホン酸ナトリウム（重量平均分子量：1,100、3,610、14,900、152,000、POLMER STANDARDS SERVICE社製）
2. Measurement method of various parameters (1) Weight average molecular weight of water-soluble polymer (component B and non-component B) The weight average molecular weight of component B and non-component B is measured by gel permeation chromatography (GPC) method under the following conditions. bottom. The measurement results are shown in Table 1-1 and Table 1-2.
<Measurement conditions>
Column: TSKgel GMPWXL + TSKgel GMPWXL (manufactured by Tosoh)
Eluent: 0.2M phosphate buffer / CH 3 CN = 7/3 (volume ratio)
Temperature: 40 ° C
Flow velocity: 1.0 mL / min Sample size: 2 mg / mL
Detector: RI
Standard substance: Sodium polystyrene sulfonate (weight average molecular weight: 1,100, 3,610, 14,900, 152,000, manufactured by POLMER STANDARDS SERVICE)
（２）水溶性重合体（成分Ｂ及び非成分Ｂ）の表面張力
水溶性重合体（成分Ｂ及び非成分Ｂ）の０．０５質量％水溶液（固形分が０．０５質量％となるように水溶性重合体を純水で希釈したもの）のｐＨを１．５に調整した。ｐＨ調整には、硫酸を用いた。そして、ｐＨ調整後の水溶液（２０℃）をシャーレに入れ、ウィルヘルミ法（白金プレートを浸漬し、一定速度で引き上げる方法）により表面張力計（協和界面化学株式会社製、「ＣＢＶＰ-Ｚ」）を用いて表面張力を測定した。結果を表１−１及び表１−２に示す。
(2) Surface tension of water-soluble polymer (component B and non-component B) A 0.05% by mass aqueous solution (solid content of 0.05% by mass) of the water-soluble polymer (component B and non-component B) The pH of the water-soluble polymer diluted with pure water) was adjusted to 1.5. Sulfuric acid was used for pH adjustment. Then, a pH-adjusted aqueous solution (20 ° C.) is placed in a chalet, and a tensiometer (“CBVP-Z” manufactured by Kyowa Surface Chemistry Co., Ltd.) is used by the Wilhelmi method (a method of immersing a platinum plate and pulling it up at a constant speed). The surface tension was measured using. The results are shown in Table 1-1 and Table 1-2.
（３）水溶性重合体（成分Ｂ及び非成分Ｂ）の残存ホルムアルデヒド、及び、研磨液組成物中のホルムアルデヒドの含有量
成分Ｂ及び非成分Ｂの水溶性重合体中に含まれる残存ホルムアルデヒド、及び、研磨液組成物中のホルムアルデヒドの含有量は、高速液体クロマトグラフィー（ＨＰＬＣ）を用いたアセチルアセトン誘導体化-ポストカラムＨＰＬＣ法により下記条件で測定した。水溶性重合体中の残存ホルムアルデヒドの結果を表１−１及び表１−２に示す。
＜測定条件＞
カラム：Hitachi-Inertsil ODS-3 (5 μm)
溶離液：Ａ：60 mmol/L Na2HPO4 (pH2.1 / H3PO4), Ｂ：80 ％アセトニトリル水溶液
傾斜条件：Ｂ：０％（0-10min）, 100% (10.1-20min), 0 %(20.1-30min)
反応溶液：Ｃ：アセチルアセトン溶液
流速：Ａ，Ｂ：１．０ｍＬ／分，Ｃ：０．５ｍＬ／分
カラム温度：２５℃
試料サイズ：５０μＬ
反応温度：９０℃
検出器：波長４１４ｎｍ 可視光
(3) Residual formaldehyde of water-soluble polymers (component B and non-component B) and content of formaldehyde in the polishing liquid composition Residual formaldehyde contained in the water-soluble polymers of component B and non-component B, and The content of formaldehyde in the polishing liquid composition was measured under the following conditions by the acetylacetone derivatization-post-column HPLC method using high performance liquid chromatography (HPLC). The results of residual formaldehyde in the water-soluble polymer are shown in Table 1-1 and Table 1-2.
<Measurement conditions>
Column: Hitachi-Inertsil ODS-3 (5 μm)
Eluent: A: 60 mmol / L Na 2 HPO 4 (pH 2.1 / H 3 PO 4 ), B: 80% acetonitrile aqueous solution Inclined condition: B: 0% (0-10min), 100% (10.1-20min) , 0% (20.1-30min)
Reaction solution: C: Acetylacetone solution Flow rate: A, B: 1.0 mL / min, C: 0.5 mL / min Column temperature: 25 ° C.
Sample size: 50 μL
Reaction temperature: 90 ° C
Detector: Wavelength 414 nm Visible light
（４）水溶性重合体（成分Ｂ及び非成分Ｂ）に浸漬させた研磨パッドの貯蔵弾性率
まず、硫酸でｐＨ１．５に調製した各水溶性重合体（成分Ｂ、非成分Ｂ）１質量％水溶液１００ｇを調製する。そして、２４φで打ち抜いたＰＥＴシートの無いＣＦ４３０１Ｎパッド（Ｆｕｊｉｂｏ社製）約０．０６ｇを、前記調製した水溶性重合体水溶液に加え、室温にて３０分間撹拌後、６０℃で２４時間静置する。その後、樹脂シートをイオン交換水シャワーにて２回（１０秒間）洗浄して乾燥後、直径８ｍｍの円盤状に打ち抜き、動的粘弾性測定により貯蔵弾性率を求める。測定結果を表２に示す。
＜測定条件＞
ＤＭＳ測定装置：ＡＲＥＳ−Ｇ２（TA Instrument Japan Inc.）
ＤＭＳ測定条件：歪み０．０１〜５０％、周波数１０Ｈｚ、変調温度領域２５℃、貯蔵弾性率Ｇ´は歪み４０％における値を読み取った。
(4) Storage elastic modulus of polishing pad immersed in water-soluble polymer (component B and non-component B) First, 1 mass of each water-soluble polymer (component B, non-component B) prepared to pH 1.5 with sulfuric acid. Prepare 100 g of% aqueous solution. Then, about 0.06 g of a CF4301N pad (manufactured by Fujibo) without a PET sheet punched out at 24φ is added to the prepared aqueous polymer solution, stirred at room temperature for 30 minutes, and allowed to stand at 60 ° C. for 24 hours. .. Then, the resin sheet is washed twice (10 seconds) with an ion-exchanged water shower, dried, punched into a disk shape having a diameter of 8 mm, and the storage elastic modulus is determined by dynamic viscoelasticity measurement. The measurement results are shown in Table 2.
<Measurement conditions>
DMS measuring device: ARES-G2 (TA Instrument Japan Inc.)
DMS measurement conditions: strain 0.01 to 50%, frequency 10 Hz, modulation temperature region 25 ° C., and storage elastic modulus G'read values at strain 40%.
（５）コロイダルシリカ（成分Ａ）の平均粒径
研磨液組成物の調製に用いた成分Ａ（コロイダルシリカ）と、硫酸とをイオン交換水に添加し、撹拌することにより、標準試料を作製した。標準試料中における成分Ａ，成分Ｃ、の含有量はそれぞれ、１重量％、０．４５重量％とした。この標準試料を動的光散乱装置（大塚電子社製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、コロイダルシリカの平均粒径とした。結果は、２６ｎｍであった。
(5) Average particle size of colloidal silica (component A) A standard sample was prepared by adding component A (colloidal silica) used for preparing the polishing liquid composition and sulfuric acid to ion-exchanged water and stirring the mixture. .. The contents of component A and component C in the standard sample were 1% by weight and 0.45% by weight, respectively. The area of the scattering intensity distribution obtained by the Cumulant method at a detection angle of 90 ° when this standard sample is integrated 200 times by a dynamic light scattering device (DLS-6500 manufactured by Otsuka Electronics Co., Ltd.) according to the instructions attached by the same manufacturer. The particle size was determined to be 50% of the total, and the average particle size of the colloidal silica was used. The result was 26 nm.
３．研磨方法
前記のように調製した実施例１〜１１及び比較例１〜７の研磨液組成物を用いて、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、研磨された基板表面のスクラッチ、基板表面うねり、研磨速度を以下に示す条件で測定し、評価を行った。
3. 3. Polishing Method Using the polishing liquid compositions of Examples 1 to 11 and Comparative Examples 1 to 7 prepared as described above, the following polishing substrate was polished under the polishing conditions shown below. Next, scratches on the polished substrate surface, substrate surface waviness, and polishing speed were measured and evaluated under the conditions shown below.
［被研磨基板］
被研磨基板として、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。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。
[Substrate to be polished]
As the substrate to be polished, a substrate obtained by roughly polishing a Ni-P-plated aluminum alloy substrate with a polishing liquid composition containing an alumina abrasive in advance was used. This substrate to be polished has a thickness of 1.27 mm, an outer diameter of 95 mm, and an inner diameter of 25 mm. The amplitude of the wavelength 0.4 to 2 mm) was 2 nm, and the amplitude of the short wavelength swell (wavelength 50 to 400 μm) was 2 nm.
［研磨条件（仕上げ研磨）］
研磨試験機：両面研磨機（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３０μｍ）
研磨液：実施例１〜１１及び比較例１〜７の研磨液組成物
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：０．０７６ｍＬ／分）
下定盤回転数：３２．５ｒｐｍ
研磨荷重：１１．８ｋＰａ
研磨時間：５分間
投入した基板の枚数：１０枚
[Polishing conditions (finish polishing)]
Polishing tester: Double-sided polishing machine (manufactured by Speedfam, "Double-sided 9B polishing machine")
Polishing pad: Fujibo suede type (thickness 0.9 mm, average opening diameter 30 μm)
Polishing liquid: Polishing liquid composition of Examples 1 to 11 and Comparative Examples 1 to 7 Polishing liquid composition Supply amount: 100 mL / min ( Supply rate per 1 cm 2 of substrate to be polished: 0.076 mL / min)
Lower platen rotation speed: 32.5 rpm
Polishing load: 11.8 kPa
Polishing time: 5 minutes Number of substrates charged: 10
４．評価方法
［スクラッチ数の測定及び評価］
測定機器：Ｃａｎｄｅｌａ Ｉｎｓｔｒｕｍｅｎｔｓ社製、「ＯＳＡ７１００」
評価：研磨試験機に投入した基板のうち、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、基板面当たりのスクラッチ数を算出した。その結果を、下記表２に、比較例１を１００とした相対値として示す。
＜評価基準＞
スクラッチ数（相対値）：評価
７０未満 ：極めて発生が抑制され、基板収率向上が期待できる
７０以上８０未満 ：実生産可能
８０以上１００未満 ：実生産には改良が必要
１００以上 ：基板収率が大幅に低下する
4. Evaluation method [Measurement and evaluation of the number of scratches]
Measuring equipment: "OSA7100" manufactured by Candela Instruments
Evaluation: Four substrates were randomly selected from the substrates put into the polishing tester, and each substrate was irradiated with a laser at 10000 rpm to measure scratches. The total number of scratches (lines) on both sides of each of the four substrates was divided by 8 to calculate the number of scratches per substrate surface. The results are shown in Table 2 below as relative values with Comparative Example 1 as 100.
<Evaluation criteria>
Number of scratches (relative value): Evaluation less than 70: Occurrence is extremely suppressed and substrate yield can be expected to improve 70 or more and less than 80: Actual production possible 80 or more and less than 100: Improvement required for actual production 100 or more: Substrate yield Will drop significantly
［短波長うねり］
研磨して減少する重量を、３５ｍｇ以上及び４５ｍｇ以下になるように研磨時間をそれぞれ設定し、研磨した基板のうねりを下記条件にて測定し、研磨量当りのうねりの値を得た。うねりは1面あたり４点、表面裏面を３枚で合計計測し、平均値を基板のうねりとして算出した。測定した試験基板は、上記研磨試験において、前記研磨条件にて研磨パッド立ち上げから５００回の研磨を行った際の基板を用いた。その結果を、下記表２に示す。
＜測定条件＞
測定機：New View 7300（Zygo社製）
レンズ：２．５倍
ズーム：０．５倍
測定波長：８０〜５００μｍ
測定位置：基板中心より半径２７ｍｍ
解析ソフト：Zygo Metro Pro（Zygo社製）
[Short wavelength swell]
The polishing time was set so that the weight reduced by polishing was 35 mg or more and 45 mg or less, respectively, and the waviness of the polished substrate was measured under the following conditions to obtain the value of the waviness per polishing amount. The swell was measured at 4 points per surface and 3 on the front and back surfaces, and the average value was calculated as the undulation of the substrate. As the measured test substrate, the substrate obtained by polishing 500 times from the start of the polishing pad under the polishing conditions was used in the above polishing test. The results are shown in Table 2 below.
<Measurement conditions>
Measuring machine: New View 7300 (manufactured by Zygo)
Lens: 2.5x Zoom: 0.5x Measurement wavelength: 80-500μm
Measurement position: 27 mm radius from the center of the board
Analysis software: Zygo Metro Pro (manufactured by Zygo)
上記表２に示すとおり、実施例１〜１１の研磨液組成物は、貯蔵弾性率を確保しつつ、基板表面のスクラッチが低減していた。実施例４と比較例１，２，７とを比較すると、貯蔵弾性率が高いほど、短波長うねりが低減されていた。通常、研磨回数が多くなるほど研磨パッドの磨耗が生じて短波長うねりが悪化するが、貯蔵弾性率が高いほど、研磨パッドの磨耗が抑制され、研磨パッドの継続使用における短波長うねりの低減につながると考えられる。
以上のことから、本開示の研磨液組成物は、スクラッチ及び研磨パッドの継続使用における短波長うねりを低減できることがわかった。
As shown in Table 2 above, in the polishing liquid compositions of Examples 1 to 11, scratches on the surface of the substrate were reduced while ensuring the storage elastic modulus. Comparing Example 4 with Comparative Examples 1, 2 and 7, the higher the storage elastic modulus, the more the short wavelength swell was reduced. Normally, as the number of polishings increases, the polishing pad wears and the short-wavelength swell worsens. However, the higher the storage elastic modulus, the more the polishing pad wear is suppressed, which leads to the reduction of the short-wavelength swell in the continuous use of the polishing pad. it is conceivable that.
From the above, it was found that the polishing liquid composition of the present disclosure can reduce short-wavelength waviness in continuous use of scratches and polishing pads.
本開示によれば、例えば、高記録密度化に適した磁気ディスク基板を提供できる。 According to the present disclosure, for example, a magnetic disk substrate suitable for increasing the recording density can be provided.
Claims (8)
前記水溶性重合体が、下記一般式（Ｉ）で表される構成を有する、研磨液組成物。
A polishing liquid composition in which the water-soluble polymer has a structure represented by the following general formula (I).
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