JP2006012969A - Silica sol for polish, and its manufacturing method - Google Patents

Silica sol for polish, and its manufacturing method Download PDF

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JP2006012969A
JP2006012969A JP2004184947A JP2004184947A JP2006012969A JP 2006012969 A JP2006012969 A JP 2006012969A JP 2004184947 A JP2004184947 A JP 2004184947A JP 2004184947 A JP2004184947 A JP 2004184947A JP 2006012969 A JP2006012969 A JP 2006012969A
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silica sol
silica
polishing
alumina
exchange resin
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Hiroyasu Nishida
広泰 西田
Yoshinori Wakamiya
義憲 若宮
Yuichiro Taguma
祐一郎 田熊
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JGC Catalysts and Chemicals Ltd
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Catalysts and Chemicals Industries Co Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To provide silica sol for polishing a base surface evenly by controlling the scratch and etch pit of the base surface, and also to provide its manufacturing method. <P>SOLUTION: The silica sol is constituted of silica sol of 5-50% of the weight of solid content concentration wherein the spherical silica particulates processed with silica and alumina disperse to a basin system dispersion medium. It meets following conditions: (a) the mean particle size of spherical silica particulates is 20-110 nm; (b) with respect to the diameter of a particle, the number of big rough particles of 800 nm or more is 3,000/ml or less per 1% of the weight of spherical silica particulate concentration; (c) the range of pH is pH 1-4 or pH 8-11; and (d) the content of inorganic negative ion is 20 ppm or less. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

本発明は研磨用シリカゾル及びその製造方法に関し、特に、シリコンウエハー、半導体デバイス基板等の表面または端面、あるいは、酸化膜等で表面を被覆した表面または端面を研磨するための研磨材として有用なシリカゾル及びその製造方法に関するものである。   The present invention relates to a silica sol for polishing and a method for producing the same, and more particularly, a silica sol useful as an abrasive for polishing a surface or end surface of a silicon wafer, a semiconductor device substrate or the like, or a surface or end surface coated with an oxide film or the like. And a manufacturing method thereof.

コンピューター、各種電子機器には各種の集積回路が用いられており、これらの小型化、高性能化に伴い回路の高密度化と高性能化が求められている。この中で、例えば半導体集積回路は、従来、半導体集積回路の集積度を高めるために多層配線が用いられており、このような多層配線は、通常、シリコンなどの基板上に、第１絶縁膜としての熱酸化膜を形成した後、アルミニウム膜などからなる第１配線層を形成し、この上にＣＶＤ法あるいはプラズマＣＶＤ法等によって、シリカ膜、窒化ケイ素膜などの層間絶縁膜を被着させ、この層間絶縁膜上に、該層間絶縁膜を平坦化するためのシリカ絶縁膜をＳＯＧ法により形成し、このシリカ絶縁膜上に必要に応じてさらに第２絶縁膜を被着させた後、第２配線層を形成することによって、製造されている。上記アルミニウム膜からなる配線は、多層配線を形成する際のスパッタリング時にアルミニウム等の配線が酸化されて抵抗値が増大して導電不良を起こすことがあった。また、配線幅を小さくすることができないためにより高密度の集積回路を形成するには限界があった。さらに、近年クロック線やデータバス線のような長距離配線では、チップサイズ増大に伴い配線抵抗が増大し電気信号の伝播遅延時間（ＲＣ遅延時間＝抵抗ラ容量）の増大が問題となっている。このため配線をより低抵抗の材料に置き換えていく必要が生じている。   Various integrated circuits are used in computers and various electronic devices, and with these miniaturization and high performance, higher density and higher performance of circuits are required. Among them, for example, a semiconductor integrated circuit conventionally uses a multilayer wiring to increase the degree of integration of the semiconductor integrated circuit. Such a multilayer wiring is usually formed on a first insulating film on a substrate such as silicon. After forming a thermal oxide film, a first wiring layer made of an aluminum film or the like is formed, and an interlayer insulating film such as a silica film or a silicon nitride film is deposited thereon by a CVD method or a plasma CVD method. A silica insulating film for planarizing the interlayer insulating film is formed on the interlayer insulating film by the SOG method, and a second insulating film is further deposited on the silica insulating film as necessary. It is manufactured by forming the second wiring layer. In the wiring made of the aluminum film, the wiring such as aluminum is oxidized at the time of sputtering when forming the multilayer wiring, and the resistance value is increased to cause a conductive failure. Further, since the wiring width cannot be reduced, there is a limit to forming a higher density integrated circuit. Further, in recent years, long-distance wiring such as a clock line and a data bus line has increased wiring resistance with an increase in chip size, and an increase in propagation delay time of electric signals (RC delay time = resistance capacity) has become a problem. . For this reason, it is necessary to replace the wiring with a material having a lower resistance.

従来のＡｌやＡｌ合金による配線に代えてＣｕ配線を行うことも提案されており、例えば、基板上の絶縁膜に予め配線溝を形成した後、電解メッキ法、ＣＶＤ法等によりＣｕ配線を形成する方法が公知である。この銅等の配線パターン形成においては、ドライエッチプロセスによる加工が困難なため、化学機械研磨方法（以下、ＣＭＰと言うこともある。）を用いたダマシンプロセスが適用されており、基板上の絶縁膜に予め配線溝を形成し、電解メッキ法やＣＶＤ法等により銅を配線溝に埋め込んだ後、ＣＭＰにより上端面を研磨し、平坦化して配線を形成している。具体的には、例えば、シリコンウェハー等の基材上に配線層間膜（絶縁膜）を成膜し、その配線層間膜（絶縁膜）上に金属配線用の溝パターンを形成し、必要に応じてスパッタリング法などによってＴａＮ等のバリアメタル層を形成し、ついで金属配線用の銅をＣＶＤ法等により成膜する。ここで、ＴａＮ等のバリアメタル層を設けた場合には層間絶縁膜への銅や不純物などの拡散や浸食に伴う層間絶縁膜の絶縁性の低下などを防止することができ、また層間絶縁膜と銅の接着性を高めることができる。   It has also been proposed to perform Cu wiring instead of conventional Al or Al alloy wiring. For example, after forming a wiring groove in an insulating film on a substrate in advance, Cu wiring is formed by electrolytic plating, CVD, or the like. Methods for doing this are known. In the formation of a wiring pattern such as copper, since a process by a dry etch process is difficult, a damascene process using a chemical mechanical polishing method (hereinafter sometimes referred to as CMP) is applied, and insulation on a substrate is performed. A wiring groove is formed in the film in advance, and copper is buried in the wiring groove by an electrolytic plating method, a CVD method or the like, and then the upper end surface is polished by CMP and flattened to form a wiring. Specifically, for example, a wiring interlayer film (insulating film) is formed on a substrate such as a silicon wafer, and a groove pattern for metal wiring is formed on the wiring interlayer film (insulating film). Then, a barrier metal layer such as TaN is formed by sputtering or the like, and then copper for metal wiring is formed by CVD or the like. Here, when a barrier metal layer such as TaN is provided, it is possible to prevent a decrease in insulation of the interlayer insulating film due to diffusion or erosion of copper or impurities into the interlayer insulating film. And copper adhesion can be improved.

次いで、ＣＭＰにより、溝内以外に成膜された不要な銅及びバリアメタルを研磨して除去するとともに上部表面を可能な限り平坦化して、溝内にのみ金属膜を残して銅の配線・回路パターンを形成する。ＣＭＰは、一般的に回転機構を有する円形プラテン上に研磨パッドを搭載し、研磨パッドの中心上部から研磨材を滴下供給した状態で被研磨材を回転させ、加重を掛けながら研磨パッドに接触させることによって、共面の上部部分の銅及びバリアメタルを研磨して除去するものである。また、ＣＭＰで使用される研磨材は、通常、シリカ、アルミナ等の金属酸化物からなる平均粒子径が２００ｎｍ程度の球状の研磨用粒子と、配線・回路用金属の研磨速度を早めるための酸化剤、有機酸等の添加剤及び純水などの溶媒から構成されているが、より一層平坦な研磨面とすることが必要であり、この際に優れた研磨レートを示し、研磨面のスクラッチやエッチピットの発生も低い水準で抑えることのできる研磨用シリカゾルが求められていた。   Next, by CMP, unnecessary copper and barrier metal formed outside the trench are polished and removed, and the upper surface is flattened as much as possible, leaving a metal film only in the trench and copper wiring / circuits. Form a pattern. In CMP, a polishing pad is generally mounted on a circular platen having a rotation mechanism, and the material to be polished is rotated in a state where the polishing material is supplied dropwise from the center upper portion of the polishing pad, and brought into contact with the polishing pad while applying a load. Thus, the copper and barrier metal in the upper part of the coplanar surface are polished and removed. In addition, abrasives used in CMP are usually spherical polishing particles having an average particle diameter of about 200 nm made of a metal oxide such as silica and alumina, and oxidation for increasing the polishing rate of wiring / circuit metals. It is composed of an additive such as an agent, an organic acid, and a solvent such as pure water, but it is necessary to make the polishing surface even flatter. In this case, it exhibits an excellent polishing rate, There has been a demand for a polishing silica sol capable of suppressing the occurrence of etch pits at a low level.

アルミニウムで被覆した微細な酸化珪素微粒子を含むコロイドが、未被覆の酸化珪素微粒子を含む通常のコロイダルシリカよりも高アルカリ領域で安定であるという知見に基づき、研磨用組成物溶液として前記アルミニウムで被覆した微細な酸化珪素粒子を含むコロイドであって、ｐＨの緩衝作用を有し、導電率の高い溶液を研磨用組成物溶液とすることが公知である（例えば、特許文献１参照）。同特許文献１には、当該研磨用組成物は高ｐＨ領域でｐＨの変化が少なく、かつ研磨加工速度が高速で安定している旨の記載がある。   Based on the knowledge that colloids containing fine silicon oxide particles coated with aluminum are more stable in a high alkali region than ordinary colloidal silica containing uncoated silicon oxide particles, they are coated with the aluminum as a polishing composition solution. It is known that a colloid containing fine silicon oxide particles having a pH buffering action and a high conductivity is used as a polishing composition solution (see, for example, Patent Document 1). In the patent document 1, there is a description that the polishing composition has little change in pH in a high pH region and that the polishing processing speed is high and stable.

特開平１１−３０２６３５号公報JP-A-11-302635

本発明は、特に基体表面のスクラッチおよびエッチピットを抑制し、基体表面を平坦に研磨することのできる研磨用シリカゾルおよびその製造方法を提供することを課題とする。   An object of the present invention is to provide a polishing silica sol capable of suppressing scratches and etch pits on the surface of the substrate and polishing the surface of the substrate evenly, and a method for producing the same.

本発明に係る研磨用シリカゾルは、表面がシリカおよびアルミナで処理された球状シリカ微粒子が水系分散媒に分散してなる固形分濃度５〜５０重量％のシリカゾルであって、ａ）球状シリカ微粒子の平均粒子径が２０〜１１０ｎｍ、ｂ）粒子径が８００ｎｍ以上の粗大粒子の個数が該球状シリカ微粒子濃度１重量％当り３０００個／ｍｌ以下、ｃ）ｐHの範囲がｐH１〜４またはｐH８〜１１およびｄ）無機陰イオンの含有量が２０ｐｐｍ以下の各条件を満たすものであることを特徴とするものである。前記無機陰イオンとは、塩素イオン、硝酸イオン、硫酸イオンをいう。
前記表面がシリカおよびアルミナで処理された球状シリカ微粒子におけるアルミナとシリカのモル比ＭA/ＭSは２×１０-6〜１０００×１０-6であることが好ましい。ここで規定するアルミナとシリカのモル比ＭA/ＭSにおいて、シリカの量は球状シリカ微粒子に由来するシリカ量と酸性珪酸液または珪酸塩水溶液により被覆されたシリカ量が合計されたものが対象であり、アルミナ量はアルミン酸ナトリウム水溶液により被覆されたアルミナ量が対象となる。 The polishing silica sol according to the present invention is a silica sol having a solid concentration of 5 to 50% by weight in which spherical silica fine particles whose surfaces are treated with silica and alumina are dispersed in an aqueous dispersion medium. B) The number of coarse particles having an average particle size of 20 to 110 nm, the particle size of 800 nm or more is 3000 particles / ml or less per 1% by weight of the spherical silica fine particles, and c) the pH range is pH 1 to 4 or pH 8 to 11 and d) The inorganic anion content satisfies each condition of 20 ppm or less. The inorganic anion refers to chlorine ion, nitrate ion, and sulfate ion.
The molar ratio M A / M S of alumina and silica in the spherical silica fine particles whose surface is treated with silica and alumina is preferably 2 × 10 −6 to 1000 × 10 −6 . In the molar ratio M A / M S of alumina and silica specified here, the amount of silica is the sum of the amount of silica derived from spherical silica fine particles and the amount of silica coated with an acidic silicate solution or silicate aqueous solution. The amount of alumina is the amount of alumina coated with a sodium aluminate aqueous solution.

本発明に係る研磨用シリカゾルの製造方法は、次の（ａ）、（ｂ）および（ｃ）の工程を含むことを特徴とする。
（ａ）水性シリカゾルに、酸性珪酸液または珪酸塩水溶液と、アルミン酸ナトリウム水溶液とを同時に添加、混合してシリカ−アルミナ被覆シリカゾルを得る工程
（ｂ）前記工程（ａ）で得られたシリカ−アルミナ被覆シリカゾルに陽イオン交換処理及び／又は陰イオン交換処理を行った後、必要に応じてｐＨ調整剤を添加して、そのｐHを１〜４または８〜１１の範囲に調整する工程
（ｃ）前記工程（ｂ）で得られたシリカ−アルミナ被覆シリカゾルに遠心分離処理を行い、上澄み液を回収する工程 The method for producing a polishing silica sol according to the present invention comprises the following steps (a), (b) and (c).
(A) A step of obtaining an silica-alumina-coated silica sol by simultaneously adding and mixing an acidic silicic acid solution or an aqueous silicate solution and an aqueous sodium aluminate solution to the aqueous silica sol (b) The silica obtained in the step (a) A step of adjusting the pH to a range of 1 to 4 or 8 to 11 by adding a pH adjusting agent as necessary after performing cation exchange treatment and / or anion exchange treatment on the alumina-coated silica sol (c) ) A step of centrifuging the silica-alumina-coated silica sol obtained in the step (b) to recover the supernatant.

本発明に係る研磨用シリカゾルの製造方法では、前記工程（ａ）において、６０〜１５０℃で０．１〜２０時間、添加、混合を行うことが好ましい。
前記工程（ｂ）において、シリカ−アルミナ被覆シリカゾルに陽イオン交換樹脂を接触させて、シリカゾルのｐHを４以下とすることが好ましく、シリカ−アルミナ被覆シリカゾルに陰イオン交換樹脂を接触させて、シリカゾルのｐHを５以上とすることが好ましい。
また、前記工程（ｂ）における陰イオン交換処理を、シリカ−アルミナ被覆シリカゾル中の無機陰イオンの含有量が２０ｐｐｍ以下になるまで繰り返すことが好ましい。
前記工程（ｃ）では、上澄み液の６０〜９９．５％を回収することが好ましい。 In the method for producing a polishing silica sol according to the present invention, in the step (a), addition and mixing are preferably performed at 60 to 150 ° C. for 0.1 to 20 hours.
In the step (b), it is preferable that the cation exchange resin is brought into contact with the silica-alumina-coated silica sol so that the silica sol has a pH of 4 or less, and the silica-alumina-coated silica sol is brought into contact with the anion exchange resin to obtain a silica sol. It is preferable that the pH of is 5 or more.
Moreover, it is preferable to repeat the anion exchange treatment in the step (b) until the content of inorganic anions in the silica-alumina-coated silica sol is 20 ppm or less.
In the step (c), it is preferable to recover 60 to 99.5% of the supernatant.

本発明の研磨用シリカゾルは、基体表面を平坦に研磨する効果に優れ、かつ基体表面のスクラッチおよびエッチピットを抑制することが可能である。また、本発明の製造方法によりそのような研磨用シリカゾルを効率良く製造することが可能となった。   The polishing silica sol of the present invention is excellent in the effect of polishing the substrate surface flatly, and can suppress scratches and etch pits on the substrate surface. Moreover, it has become possible to efficiently produce such a polishing silica sol by the production method of the present invention.

研磨用シリカゾル
本発明の研磨用シリカゾルは、表面がシリカおよびアルミナで処理された球状シリカ微粒子が水系分散媒に分散してなる固形分濃度５〜５０重量％のシリカゾルであって、ａ）球状シリカ微粒子の平均粒子径が２０〜１１０ｎｍ、ｂ）粒子径が８００ｎｍ以上の粗大粒子の個数が該球状シリカ微粒子濃度１重量％当り３０００個／ｍｌ以下、ｃ）ｐHの範囲がｐH１〜４またはｐH８〜１１およびｄ）無機陰イオンの含有量が２０ｐｐｍ以下の各条件を満たすものであることを特徴とするものである。
本発明の研磨用シリカゾルは、研磨能率の上から固形分濃度が５〜５０重量％の範囲にあるものが使用される。固形分濃度が５重量％未満の場合は研磨能率が低く、５０重量％を超えるとシリカゾルが乾燥して、凝集異物が混入することがある。
本発明の研磨用シリカゾルに適用する分散媒としては、水系のものが使用されるが、好適には水が用いられる。 Polishing silica sol The polishing silica sol of the present invention is a silica sol having a solid content concentration of 5 to 50% by weight in which spherical silica fine particles whose surfaces are treated with silica and alumina are dispersed in an aqueous dispersion medium, and a) spherical silica The average particle diameter of the fine particles is 20 to 110 nm, b) the number of coarse particles having a particle diameter of 800 nm or more is 3000 particles / ml or less per 1% by weight of the spherical silica fine particle concentration, and c) the pH range is pH 1 to 4 or pH 8 to 11 and d) The inorganic anion content satisfies each condition of 20 ppm or less.
As the polishing silica sol of the present invention, those having a solid content concentration in the range of 5 to 50% by weight in terms of polishing efficiency are used. When the solid content concentration is less than 5% by weight, the polishing efficiency is low. When the solid content concentration exceeds 50% by weight, the silica sol is dried, and agglomerated foreign matter may be mixed.
As the dispersion medium applied to the polishing silica sol of the present invention, an aqueous medium is used, but water is preferably used.

研磨用シリカゾルを構成するシリカ微粒子には、スクラッチが発生し難いことから球状シリカ微粒子が用いられ、その平均粒子径は２０〜１１０ｎｍのものが使用される。この平均粒子径範囲のものであれば、優れた研磨性能が発揮されるが、２０ｎｍ未満の場合には研磨能率が低下する一方、１１０ｎｍを超える場合はスクラッチが増加する。
また、粒子径が８００ｎｍ以上の粗大粒子の個数が該球状シリカ微粒子濃度１重量％当り３０００個／ｍｌ以下であることが必要である。この個数が同じく３０００個／ｍｌを超える場合は、スクラッチやエッチピット等の問題が発生する。 As the silica fine particles constituting the polishing silica sol, spherical silica fine particles are used because scratches hardly occur, and those having an average particle diameter of 20 to 110 nm are used. When the average particle size is within the range, excellent polishing performance is exhibited. However, when the particle size is less than 20 nm, the polishing efficiency decreases, while when it exceeds 110 nm, the scratch increases.
Further, the number of coarse particles having a particle diameter of 800 nm or more needs to be 3000 particles / ml or less per 1% by weight of the spherical silica fine particle concentration. If this number similarly exceeds 3000 / ml, problems such as scratches and etch pits occur.

本発明の研磨用シリカゾルのｐH値については、ｐH１〜４またはｐH８〜１１であることが必要である。ｐHが１未満の場合は、研磨基体を構成する金属が溶出し易い。ｐHが４を超えて且つ８未満の範囲にあるものは、ゲル化し易くなる。ｐHが１１を超えると、シリカが溶出し易くなり好ましくない。
研磨用シリカゾルの無機陰イオンの含有量は、２０ｐｐｍ以下であることが必要である。２０ｐｐｍを超える場合、研磨基体を腐食する塩素イオン等の影響が強くなるため表面粗度が劣化し研磨用途に適さなくなる。
前記研磨用シリカゾルにおいて、前記表面がシリカおよびアルミナで処理された球状シリカ微粒子におけるアルミナとシリカのモル比ＭA/ＭSは、２×１０-6〜１０００×１０-6であることが好ましい。この範囲を外れると、研磨能率が低下するので好ましくない。 About pH value of the silica sol for polishing of this invention, it is required to be pH1-4 or pH8-11. When the pH is less than 1, the metal constituting the polishing substrate is likely to elute. Those having a pH in the range of more than 4 and less than 8 are easily gelled. If the pH exceeds 11, silica is likely to be eluted, which is not preferable.
The content of inorganic anions in the polishing silica sol needs to be 20 ppm or less. If it exceeds 20 ppm, the influence of chlorine ions or the like that corrode the polishing substrate becomes strong, so that the surface roughness is deteriorated and is not suitable for polishing applications.
In the polishing silica sol, the molar ratio M A / M S of alumina to silica in the spherical silica fine particles whose surface is treated with silica and alumina is preferably 2 × 10 −6 to 1000 × 10 −6 . Outside this range, the polishing efficiency decreases, which is not preferable.

本発明の研磨用シリカゾルの製造方法については、上記条件を満たすものが得られる限り限定されるものではない。代表的な製造方法としては、１）水系の球状シリカゾルを酸性珪酸液およびアルミン酸ナトリウム水溶液で処理し、イオン交換処理により無機陰イオンの除去とｐH調整を行い、遠心分離により粗大粒子を除去する方法、２）有機珪素化合物を加水分解する法あるいはオートクレーブを利用する法などにより粗大粒子が含まれない水性の球状シリカゾルを調製し、酸性珪酸液または珪酸塩水溶液とアルミン酸ナトリウム水溶液とで処理した後、イオン交換処理により無機陰イオンを除去し、ｐH調整を行う方法、等を例示することができる。   The method for producing the polishing silica sol of the present invention is not limited as long as a method satisfying the above conditions is obtained. As a typical production method, 1) an aqueous spherical silica sol is treated with an acidic silicic acid solution and an aqueous sodium aluminate solution, inorganic anions are removed and pH is adjusted by ion exchange treatment, and coarse particles are removed by centrifugation. Method 2) An aqueous spherical silica sol containing no coarse particles was prepared by a method of hydrolyzing an organosilicon compound or a method using an autoclave, and treated with an acidic silicic acid solution or an aqueous silicate solution and an aqueous sodium aluminate solution. Thereafter, a method of adjusting the pH by removing inorganic anions by ion exchange treatment can be exemplified.

研磨用シリカゾルの製造方法
本発明に係る研磨用シリカゾルの製造方法は、次の（ａ）、（ｂ）および（ｃ）の工程を含むことを特徴としている。
（ａ）水性シリカゾルに、酸性珪酸液または珪酸塩水溶液と、アルミン酸ナトリウム水溶液とを同時に添加、混合してシリカ−アルミナ被覆シリカゾルを得る工程
（ｂ）前記工程（ａ）で得られたシリカ−アルミナ被覆シリカゾルに陽イオン交換処理及び／又は陰イオン交換処理を行った後、必要に応じてｐＨ調整剤を添加して、そのｐHを１〜４または８〜１０の範囲に調整する工程
（ｃ）前記工程（ｂ）で得られたシリカ−アルミナ被覆シリカゾルに遠心分離処理を行い、上澄み液を回収する工程
以下、各工程を順次説明するが、初めに使用する原料について説明する。 Manufacturing Method of Polishing Silica Sol The manufacturing method of the polishing silica sol according to the present invention includes the following steps (a), (b) and (c).
(A) A step of obtaining an silica-alumina-coated silica sol by simultaneously adding and mixing an acidic silicic acid solution or an aqueous silicate solution and an aqueous sodium aluminate solution to the aqueous silica sol (b) The silica obtained in the step (a) A step of adjusting the pH to a range of 1 to 4 or 8 to 10 by adding a pH adjuster as necessary after performing a cation exchange treatment and / or an anion exchange treatment on the alumina-coated silica sol (c) ) Step of performing centrifugation treatment on the silica-alumina-coated silica sol obtained in the step (b) and recovering the supernatant liquid. Hereinafter, each step will be described in order, but the raw materials used first will be described.

［水性シリカゾル］
本発明に使用される水性シリカゾルは、球状のシリカ微粒子が水系溶媒に分散したものであれば、その製造方法に格別の限定はなく、例えば、珪酸塩の酸による中和法、解膠法、イオン交換樹脂法、金属アルコキシドをアルカリとアルコールの共存下で加水分解する方法等、公知の製造方法が挙げられる。
具体的には、例えば、特公平４−５６７５５号公報に開示されているように、シリカゾルに、ケイ酸ナトリウム溶液および純水を混合してシ−ド液を調製し、このシ−ド液を還流器、撹拌装置および加熱装置を備えたステンレス製容器に仕込み、これを所定温度に昇温し、その温度を保持しながら酸性ケイ酸液を一定の速度で添加してビルドアツプ工程を実施し、添加終了後、同一温度に約１時間保持したのち冷却し、限外濾過装置により、所定濃度まで濃縮することにより得られる。 [Aqueous silica sol]
The aqueous silica sol used in the present invention is not particularly limited in its production method as long as spherical silica fine particles are dispersed in an aqueous solvent. For example, a neutralization method using a silicate acid, a peptization method, Well-known manufacturing methods, such as an ion exchange resin method and the method of hydrolyzing a metal alkoxide in the coexistence of an alkali and alcohol, are mentioned.
Specifically, for example, as disclosed in Japanese Examined Patent Publication No. 4-56755, a silica sol is mixed with a sodium silicate solution and pure water to prepare a seed solution. Charge a stainless steel vessel equipped with a reflux device, a stirrer and a heating device, raise the temperature to a predetermined temperature, add an acidic silicic acid solution at a constant rate while maintaining the temperature, carry out a build-up process, After completion of the addition, the mixture is kept at the same temperature for about 1 hour, cooled, and concentrated to a predetermined concentration by an ultrafiltration device.

また、特開昭６３−４５１１４号公報に開示されているようにケイ酸ナトリウムなどのケイ酸水溶液および／またはアルカリ水溶液と、酸性ケイ酸液とを混合して、混合液のＳｉ０2／Ｍ2Ｏ（Ｍはアルカリ金属）を２．８〜１０に調整したのち、得られた混合液を６０℃以上の温度に加熱して熟成を行い、シ−ド液を調製し、次いで得られたシ−ド液に、酸性ケイ酸液を加熱下で添加して、シ−ド液中のシリカ粒子を成長させることによって所定の粒径を持つシリカ粒子が分散されてなるシリカゾルを得ることができる。
この水系シリカゾルとしては、平均粒子径が２０〜１１０ｎｍのものが好適である。平均粒子径が２０ｎｍ未満では研磨能率が低下する一方、平均粒子径が１１０ｎｍを超えるとスクラッチ発生し易くなるからである。 Further, as disclosed in JP-A-63-45114, an aqueous silicic acid solution such as sodium silicate and / or an alkaline aqueous solution and an acidic silicic acid solution are mixed, and a mixed solution of SiO 2 / M 2 is mixed. After adjusting O (M is an alkali metal) to 2.8 to 10, the obtained mixed solution is heated to a temperature of 60 ° C. or more to be aged to prepare a seed solution. -A silica sol in which silica particles having a predetermined particle diameter are dispersed can be obtained by adding an acidic silicic acid solution to a seed solution under heating to grow silica particles in the seed solution.
The aqueous silica sol preferably has an average particle size of 20 to 110 nm. This is because, if the average particle diameter is less than 20 nm, the polishing efficiency is lowered, whereas if the average particle diameter exceeds 110 nm, scratching is likely to occur.

［酸性珪酸液］
本発明に使用する酸性珪酸液としては、（１）アルカリ金属珪酸塩の水溶液をイオン交換樹脂等で脱アルカリして得られる酸性珪酸液、（２）有機ケイ素化合物を塩酸、硝酸、硫酸などの酸で加水分解して得られる酸性珪酸液、（３）アルカリ金属水酸化物水溶液および／または有機塩基水溶液に有機ケイ素化合物を加えた水溶液をイオン交換樹脂等で脱アルカリまたは脱有機塩基して得られる従来公知の酸性珪酸液等、を用いることができる。なお、前記アルカリ金属珪酸塩水溶液またはアルカリ金属水酸化物水溶液のアルカリとしては、ナトリウム、カリウム、リチウムが好ましい。
本発明の製造方法において使用される酸性珪酸液の濃度は、通常、1〜5％のものが使用される。 [Acid silicic acid solution]
The acidic silicic acid solution used in the present invention includes (1) an acidic silicic acid solution obtained by dealkalizing an aqueous solution of an alkali metal silicate with an ion exchange resin or the like, and (2) an organosilicon compound such as hydrochloric acid, nitric acid, sulfuric acid, etc. An acid silicic acid solution obtained by hydrolysis with an acid, and (3) an alkali metal hydroxide aqueous solution and / or an aqueous solution obtained by adding an organic silicon compound to an aqueous organic base solution by dealkali or deorganic base using an ion exchange resin or the like. A conventionally known acidic silicic acid solution or the like can be used. In addition, as an alkali of the said alkali metal silicate aqueous solution or alkali metal hydroxide aqueous solution, sodium, potassium, and lithium are preferable.
The concentration of the acidic silicic acid solution used in the production method of the present invention is usually 1 to 5%.

［珪酸塩水溶液］
本発明に使用される珪酸塩水溶液としては、珪酸ナトリウム（水ガラス）、珪酸カリウム（カリ水硝子）等のアルカリ金属珪酸塩の水溶液あるいは第４級アミンなど有機塩基にシリカを溶解した溶液を用いることができる。 [Silicate aqueous solution]
As the silicate aqueous solution used in the present invention, an aqueous solution of an alkali metal silicate such as sodium silicate (water glass) or potassium silicate (potassium water glass) or a solution in which silica is dissolved in an organic base such as a quaternary amine is used. be able to.

［アルミン酸ナトリウム］
本発明の製造方法では、アルミン酸ナトリウム水溶液の濃度は、0.001〜1.0％のものが好適に使用される。 [Sodium aluminate]
In the production method of the present invention, a sodium aluminate aqueous solution having a concentration of 0.001 to 1.0% is preferably used.

［工程（ａ）］
本発明の製造方法では、平均粒子径２０〜１１０ｎｍの水性シリカゾルを、例えば60〜150℃に加温し、これに酸性珪酸液または珪酸塩水溶液（固形分：１〜５重量％）と、アルミン酸ナトリウム水溶液（固形分：０．００１〜３０重量％）とを同時に添加し、60〜150℃で0.1〜20時間保持した後、冷却することによりシリカ−アルミナ被覆シリカゾルを得ることができる。前記加温時の温度が60℃未満の場合は被覆速度が遅く、他方、150℃を超える場合は経済的でない。
酸性珪酸液または珪酸塩水溶液に含まれる固形分が１重量％未満の場合は、成長に長時間かかり、一方、固形分が５重量％を超える場合は、凝集し易く十分な成長が見込めない。また、アルミン酸ナトリウム水溶液の固形分が０．００１重量％未満の場合は、析出速度が遅く粒子成長が不十分となり、固形分が３０重量％を超える場合は、部分的に凝集が発生する。
なお、上記水性シリカゾル：酸性ケイ酸液（珪酸塩水溶液）：アルミン酸ナトリウム水溶液の仕込量については、前記したモル比ＭA/ＭSの範囲内のシリカ−アルミナ被覆シリカゾルが得られる限りは格別に限定されるものではないが、例えば、固形分で１００：０．０１〜５：０．０００１〜５の範囲で投入される。 [Step (a)]
In the production method of the present invention, an aqueous silica sol having an average particle size of 20 to 110 nm is heated to, for example, 60 to 150 ° C., and an acidic silicate solution or an aqueous silicate solution (solid content: 1 to 5% by weight) and alumina. A sodium-acid aqueous solution (solid content: 0.001 to 30% by weight) is added at the same time, kept at 60 to 150 ° C. for 0.1 to 20 hours, and then cooled to obtain a silica-alumina-coated silica sol. When the heating temperature is less than 60 ° C, the coating speed is slow, while when it exceeds 150 ° C, it is not economical.
When the solid content contained in the acidic silicic acid solution or the silicate aqueous solution is less than 1% by weight, it takes a long time to grow. On the other hand, when the solid content exceeds 5% by weight, the solid content easily aggregates and sufficient growth cannot be expected. Further, when the solid content of the sodium aluminate aqueous solution is less than 0.001% by weight, the precipitation rate is slow and the particle growth is insufficient, and when the solid content exceeds 30% by weight, agglomeration occurs partially.
The above aqueous silica sol: acidic silicic acid solution (silicate solution): For the charged amount of sodium aluminate solution, silica within the range of the above-mentioned molar ratio M A / M S - particularly as long as the alumina-coated silica sol is obtained Although it is not limited to, for example, it is charged in a range of 100: 0.01 to 5: 0.0001 to 5 in terms of solid content.

前記添加後の水系シリカゾルの保持温度については、60℃未満では安定化が不十分であり、150℃を超える場合は不経済となる。また、保持時間については、粒子と可溶性シリカの平衡反応を充分行うために、通常、0.1〜20時間とする。
前記水性シリカゾルは、濃度調整のために適宜、希釈しても良い。希釈にあたっては純水または超純水等が好適であり、希釈後は通常、適宜攪拌する。
前記酸性珪酸液または珪酸塩水溶液およびアルミン酸ナトリウム水溶液の添加速度は、通常、それぞれ0.1〜10ｇ／ｍｉｎである。 As for the retention temperature of the aqueous silica sol after the addition, the stabilization is insufficient if it is less than 60 ° C, and it is uneconomical if it exceeds 150 ° C. The holding time is usually 0.1 to 20 hours in order to sufficiently perform the equilibrium reaction between the particles and the soluble silica.
The aqueous silica sol may be appropriately diluted for adjusting the concentration. For dilution, pure water, ultrapure water, or the like is suitable. After dilution, the mixture is usually stirred appropriately.
The addition rate of the acidic silicic acid solution or silicate aqueous solution and sodium aluminate aqueous solution is usually 0.1 to 10 g / min, respectively.

［工程（ｂ）］
工程（ｂ）では、前記工程（ａ）で得られたシリカ−アルミナ被覆シリカゾルに陽イオン交換処理及び／又は陰イオン交換処理を行った後、必要に応じてｐＨ調整剤を添加して、そのｐHを１〜４または８〜１１の範囲に調整する。
上記イオン交換処理には、イオン交換樹脂のほか、イオン交換膜やイオン交換機能を有するフィルターも使用することができるが、一般的には、市販の強酸性または弱酸性陽イオン交換樹脂、キレート樹脂が例示される。また、強塩基性または弱塩基性陰イオン交換樹脂、キレート樹脂が例示される。これらの陽イオン交換樹脂または陰イオン交換樹脂は、それぞれ単独または併用して用いられる。 [Step (b)]
In the step (b), the silica-alumina-coated silica sol obtained in the step (a) is subjected to a cation exchange treatment and / or an anion exchange treatment, and then a pH adjuster is added as necessary. The pH is adjusted to a range of 1 to 4 or 8 to 11.
In the ion exchange treatment, in addition to the ion exchange resin, an ion exchange membrane or a filter having an ion exchange function can be used. Generally, a commercially available strong acid or weak acid cation exchange resin or chelate resin is used. Is exemplified. Further, strong or weakly basic anion exchange resins and chelate resins are exemplified. These cation exchange resins or anion exchange resins are used alone or in combination.

シリカ−アルミナ被覆シリカゾルと陽イオン交換樹脂との接触では、シリカゾルのｐHを４以下、特に３以下となるように、ナトリウムイオン等の陽イオンを除去することが好ましい。また、シリカ−アルミナ被覆シリカゾルと陰イオン交換樹脂との接触では、シリカゾルのｐHが５以上となるように、塩素イオン、硝酸イオン、硫酸イオン等の無機陰イオン、特に塩素イオンを除去することが好ましい。
具体的には、陽イオン交換樹脂はシリカ−アルミナ被覆シリカゾル中のナトリウムイオン量１ｇに対して５〜５０ｍｌの範囲で、また、陰イオン交換樹脂は無機陰イオン量１ｇに対して５〜５０ｍｌの範囲で投入される。 In the contact between the silica-alumina-coated silica sol and the cation exchange resin, it is preferable to remove cations such as sodium ions so that the silica sol has a pH of 4 or less, particularly 3 or less. In addition, in the contact between the silica-alumina-coated silica sol and the anion exchange resin, inorganic anions such as chlorine ions, nitrate ions, sulfate ions, particularly chlorine ions can be removed so that the silica sol has a pH of 5 or more. preferable.
Specifically, the cation exchange resin is in the range of 5 to 50 ml with respect to 1 g of sodium ion in the silica-alumina-coated silica sol, and the anion exchange resin is in the range of 5 to 50 ml with respect to 1 g of inorganic anion. Thrown in range.

この陽イオン交換処理および陰イオン交換処理は、研磨用シリカゾルとして使用する際に、銅、アルミニウム、タングステン、タンタル、タンタルナイトライド等の研磨基体を腐食するおそれのある無機陰イオン、特には塩素イオンを除去することを主たる目的としている。従って、イオン交換処理はシリカ−アルミナ被覆シリカゾル中に含まれる無機陰イオン濃度が２０ｐｐｍ以下になるまで行うことが好ましく、無機陰イオン濃度がこのレベルになれば、研磨基体への影響は実用上問題とならない。
上記イオン交換処理の目的からして、陽イオン交換処理および陰イオン交換処理は、必要に応じて複数回繰返し行っても良い。また、シリカ−アルミナ被覆シリカゾル中に含まれる無機陰イオン濃度が２０ｐｐｍ以下であれば、陰イオン交換処理は不要となる。 This cation exchange treatment and anion exchange treatment are inorganic anions, particularly chlorine ions, that may corrode polishing substrates such as copper, aluminum, tungsten, tantalum, and tantalum nitride when used as a polishing silica sol. The main purpose is to remove the. Therefore, the ion exchange treatment is preferably performed until the inorganic anion concentration contained in the silica-alumina-coated silica sol is 20 ppm or less. If the inorganic anion concentration reaches this level, the influence on the polishing substrate is a practical problem. Not.
For the purpose of the ion exchange treatment, the cation exchange treatment and the anion exchange treatment may be repeated a plurality of times as necessary. Moreover, if the inorganic anion concentration contained in the silica-alumina-coated silica sol is 20 ppm or less, the anion exchange treatment is unnecessary.

イオン交換処理は、より具体的には例えば、前記工程（ａ）で得られたシリカ−アルミナ被覆シリカゾルを10〜50℃で攪拌し、陽イオン交換樹脂を接触させて、シリカゾルのｐHが４以下になるまで攪拌しながら保持し、その後、陽イオン交換樹脂を除去し、次にこのシリカ−アルミナ被覆シリカゾルを10〜50℃で攪拌し、陰イオン交換樹脂と接触させ、シリカゾルのｐHが５以上になるまで保持し、その後、陰イオン交換樹脂を除去することにより実施される。
一連のイオン交換処理を終えたシリカ−アルミナ被覆シリカゾルについては、濃度調整のために限外濾過膜等を使用してシリカ濃度を適宜調整してもよい。 More specifically, in the ion exchange treatment, for example, the silica-alumina-coated silica sol obtained in the step (a) is stirred at 10 to 50 ° C. and brought into contact with a cation exchange resin. The cation exchange resin is removed, and then the silica-alumina-coated silica sol is stirred at 10 to 50 ° C. and brought into contact with the anion exchange resin. The silica sol has a pH of 5 or more. Until it is, and then the anion exchange resin is removed.
For the silica-alumina-coated silica sol that has undergone a series of ion exchange treatments, the silica concentration may be adjusted as appropriate using an ultrafiltration membrane or the like for concentration adjustment.

上記イオン交換処理後、シリカ−アルミナ被覆シリカゾルには必要に応じてｐＨ調整剤を添加して、そのｐHを１〜４または８〜１１の範囲に調整する。ｐHが４を超えて８未満の範囲ではシリカゾルがゲル化し易くなり、好ましくない。ｐHが１未満では基板の腐食が起こり易く、また、ｐHが１１を超えるとシリカの溶出が起こり安定性が悪くなる。
ｐＨ調整剤としては、研磨用シリカゾルとして性能に影響を与えないもので、ｐH調整機能を有するものを使用することができる。酸性側に調整する場合は、クエン酸、シュウ酸、乳酸等が使用できる。また、アルカリ性側に調整する場合は、テトラメチルアンモニウムハイドライド等の第四級アミン類、トリエタノールアミン等の第三級アミン類あるいはＤＭＦ等の有機酸等が使用できる。これらのｐH調整剤は適宜希釈して使用される。 After the ion exchange treatment, a pH adjuster is added to the silica-alumina-coated silica sol as necessary to adjust its pH to a range of 1 to 4 or 8 to 11. When the pH is in the range of more than 4 and less than 8, the silica sol tends to gel, which is not preferable. If the pH is less than 1, the substrate is easily corroded, and if the pH exceeds 11, the silica is eluted and the stability is deteriorated.
As the pH adjusting agent, a silica sol for polishing that does not affect the performance and has a pH adjusting function can be used. When adjusting to the acidic side, citric acid, oxalic acid, lactic acid and the like can be used. When adjusting to the alkaline side, quaternary amines such as tetramethylammonium hydride, tertiary amines such as triethanolamine, or organic acids such as DMF can be used. These pH adjusting agents are used after appropriately diluted.

尚、本発明のシリカ−アルミナ被覆シリカゾルには、長期保存時の腐敗防止を目的として殺菌剤を添加しても構わない。この様な殺菌剤の例として、過酸化水素等の過酸化物、次亜塩素酸類等が挙げられる。   Note that a bactericidal agent may be added to the silica-alumina-coated silica sol of the present invention for the purpose of preventing decay during long-term storage. Examples of such bactericides include peroxides such as hydrogen peroxide, hypochlorous acid, and the like.

［工程（ｃ）］
前記工程（ｃ）では、工程（ｂ）で得られたシリカ-アルミナ被覆シリカゾルに遠心分離処理を行い、上澄み液を回収することにより、粗大粒子の除去された研磨用シリカゾルを得る。
粗大粒子は、研磨基体に対するスクラッチおよびエッチピット発生の原因となるため除去する必要がある。このためには、粒子径が８００ｎｍ以上の粗大粒子の個数が、シリカ微粒子濃度１重量％当り３０００個／ｍｌ以下であることが望ましい。このようなシリカ−アルミナ被覆シリカゾルを得るための遠心分離処理は、例えば、１９００Gで１０分以上行って、遠心分離処理後の上澄み液のうち６０〜９９．５％程度を回収することにより達成可能である。 [Step (c)]
In the step (c), the silica-alumina-coated silica sol obtained in the step (b) is subjected to a centrifugal separation treatment, and the supernatant liquid is recovered to obtain a polishing silica sol from which coarse particles are removed.
Coarse particles need to be removed because they cause scratches and etch pits on the polishing substrate. For this purpose, the number of coarse particles having a particle diameter of 800 nm or more is desirably 3000 particles / ml or less per 1% by weight of silica fine particle concentration. Centrifugation for obtaining such a silica-alumina-coated silica sol can be achieved, for example, by performing at 1900 G for 10 minutes or more and recovering about 60 to 99.5% of the supernatant after centrifugation. It is.

本発明の製造方法により製造されたシリカ−アルミナ被覆シリカゾルについては、適宜フィルタリング濾過等の処理を行っても良い。
この他、本発明のシリカ−アルミナ被覆シリカゾルに添加することができる添加剤としては、界面活性剤、アミン類、他の無機コロイド粒子、樹脂粒子、酸化剤、還元剤、水溶性ポリマー、無機塩類、有機塩類等が挙げられる。 The silica-alumina-coated silica sol produced by the production method of the present invention may be appropriately subjected to processing such as filtering filtration.
Other additives that can be added to the silica-alumina-coated silica sol of the present invention include surfactants, amines, other inorganic colloid particles, resin particles, oxidizing agents, reducing agents, water-soluble polymers, inorganic salts. And organic salts.

研磨用シリカゾルの製造
触媒化成工業（株）製シリカゾルSI-80P(シリカ濃度; 39.55%,平均粒子径;81nm) 21.49kgに超純水を21.01kg添加し、シリカ濃度20%に稀釈後30分間撹拌した。さらに稀釈したシリカゾルを攪拌しながら80℃に昇温して、3.0%酸性ケイ酸液0.5kgおよび0.01%アルミン酸ナトリウム液0.5kgを準備し、それぞれ2.8ｇ/minの添加速度で、同時に添加した(添加時間；3時間)。添加終了後、さらに同一温度で１時間保持したのち冷却してシリカアルミナ被覆処理をした。
前記のシリカアルミナ被覆処理を施したシリカゾルを23℃で撹拌をおこない、その中に陽イオン交換樹脂を6.40kg投入し、pH値が3以下になるまで撹拌しながら保持し、その後その陽イオン交換樹脂を除去した。次にこのシリカゾルを23℃で撹拌をおこない、その中に陰イオン交換樹脂を0.64kg投入し、pH値が5.2以上になるまで撹拌しながら保持し、その後その陰イオン交換樹脂を除去した。さらにこの前記シリカゾルを23℃で撹拌をおこない、その中に再度陽イオン交換樹脂を6.40kg投入し、投入後80℃に昇温して、その温度で3時間撹拌しながら保持した。その後冷却して陽イオン交換樹脂を除去した。さらにこのシリカゾルを23℃で撹拌をおこない、その中に再度陰イオン交換樹脂を0.64kg投入し、投入後40℃に昇温して、その温度で12時間撹拌しながら保持した。その後冷却して陰イオン交換樹脂を除去した。さらに前記のシリカゾルを23℃で撹拌をおこない、その中に陽イオン交換樹脂を6.40kg投入し、投入後シリカゾルのpH値が4以下になるまで撹拌しながら保持した。その後その陽イオン交換樹脂を除去した。前記の一連のイオン交換処理を施したシリカゾルに対して限外膜を使用し濃縮をおこない、この段階で固形分濃度を31％に調整した。
次に濃縮したシリカゾルを攪拌しながらpH調整のため5％テトラメチルアンモニウムハイドロオキサイド水溶液を添加しpH値が8.8となった。
pH調整したシリカゾルの粗大粒子数を低減するために、KOKUSAN社製H-38Fを使用し、遠心力1900Gで10分間遠心処理を施し、そのシリカゾルの上澄み液を約９０％回収した。
最後に前記の遠心処理を施したシリカゾルを窒素圧0.1kg/cm2の窒素で加圧し、日本ポール社製10μmフィルタ、1.2μｍフィルタさらに0.6μｍフィルタを順番に使用してフィルタリングろ過をした。最後に固形分濃度を30%に調整し研磨サンプルの調製を完了した。
このサンプルについて、ユアサアイオニクス（株）製の分析装置「マルチソーブ１２」を用いてその平均粒子径を測定したところ８１nmであった。なお、実施例２以降においても、同様に平均粒子径を測定し、その結果を表に示した。 Manufacture of silica sol for polishing Silica sol SI-80P manufactured by Catalyst Kasei Kogyo Co., Ltd. (silica concentration: 39.55%, average particle size: 81 nm) 21.01 kg of ultrapure water was added to 21.49 kg and diluted to 20% silica concentration for 30 minutes. Stir. Further, the diluted silica sol was heated to 80 ° C. with stirring to prepare 0.5 kg of 3.0% acidic silicic acid solution and 0.5 kg of 0.01% sodium aluminate solution, which were simultaneously added at an addition rate of 2.8 g / min. (Addition time; 3 hours). After completion of the addition, the mixture was further maintained at the same temperature for 1 hour and then cooled to perform silica alumina coating treatment.
The silica sol coated with the above silica-alumina coating is stirred at 23 ° C., and 6.40 kg of cation exchange resin is added to the silica sol, and the mixture is held with stirring until the pH value becomes 3 or less. The resin was removed. Next, this silica sol was stirred at 23 ° C., and 0.64 kg of an anion exchange resin was added therein, and the silica sol was held with stirring until the pH value became 5.2 or more, and then the anion exchange resin was removed. Further, the silica sol was stirred at 23 ° C., and 6.40 kg of the cation exchange resin was charged therein again. After the charging, the temperature was raised to 80 ° C. and held at that temperature for 3 hours with stirring. Thereafter, it was cooled to remove the cation exchange resin. Further, this silica sol was stirred at 23 ° C., and 0.64 kg of anion exchange resin was again charged therein. After the charging, the temperature was raised to 40 ° C. and held at that temperature for 12 hours with stirring. Thereafter, the anion exchange resin was removed by cooling. Further, the silica sol was stirred at 23 ° C., and 6.40 kg of a cation exchange resin was charged therein, and after the charging, the silica sol was held with stirring until the pH value of the silica sol became 4 or less. The cation exchange resin was then removed. The silica sol subjected to the above series of ion exchange treatments was concentrated using an ultra-membrane, and the solid content concentration was adjusted to 31% at this stage.
Next, 5% tetramethylammonium hydroxide aqueous solution was added to adjust the pH while stirring the concentrated silica sol, and the pH value became 8.8.
In order to reduce the number of coarse particles of the silica sol adjusted for pH, KOKUSAN H-38F was used and centrifuged at a centrifugal force of 1900 G for 10 minutes, and about 90% of the silica sol supernatant was recovered.
Finally, the silica sol subjected to the above centrifugal treatment was pressurized with nitrogen having a nitrogen pressure of 0.1 kg / cm 2 and filtered using a 10 μm filter, a 1.2 μm filter and a 0.6 μm filter manufactured by Nippon Pole Co., Ltd. in order. Finally, the solid content concentration was adjusted to 30% to complete the preparation of the polished sample.
With respect to this sample, the average particle diameter was measured using an analyzer “Multisorb 12” manufactured by Yuasa Ionics Co., Ltd. and found to be 81 nm. In Example 2 and later, the average particle size was measured in the same manner, and the results are shown in the table.

上記研磨サンプルの調製条件を表１に示す。なお、シリカゾルのpH測定は、測定用サンプル約50gをポリエチレン製のサンプル瓶に採取し、これを25℃の恒温槽に30分以上浸漬した後、pH4,7,9の標準液で更正が完了したHORIBA社製F22のガラス電極を挿入して実施した。
また、粗大粒子の測定については、アキュサイザー（型式：780APS）を使用し、測定試料を20%以下に希釈し、Loop：0.5ml, Syringe：2.5ml, DF2 200（装置内での２次希釈、希釈倍率２００倍）, 測定時間：120秒以下、の測定条件にて実施した。 Table 1 shows the conditions for preparing the polishing sample. For silica sol pH measurement, about 50 g of the sample for measurement is collected in a polyethylene sample bottle, immersed in a thermostatic bath at 25 ° C for 30 minutes or more, and then the calibration is completed with standard solutions of pH 4, 7, 9 This was carried out by inserting a glass electrode of F22 made by HORIBA.
For the measurement of coarse particles, use an Accusizer (model: 780APS), dilute the measurement sample to 20% or less, Loop: 0.5ml, Syringe: 2.5ml, DF2 200 (secondary dilution in the device) , Dilution ratio 200 times), measurement time: 120 seconds or less.

次に、上記研磨サンプルの性状とこれを使用した研磨テストの結果を表１に示す。
無機陰イオン濃度の測定は、ＤＩＯＮＥＸ社のイオンクロマトグラフ（型番；DX-AQ）を使用した。
研磨試験
29mm角の研磨テスト用基板（SiO2膜）を切出し、ナノファクタ社製NF300を使用して研磨テストを実施した。
研磨条件は、研磨荷重；350g/cm2、研磨時間；30sec、スラリ流量；70ml/min、研磨パッド；ロデールニッタ社製IC1000、研磨パッド回転速度；30rpm、である。研磨レートはSiO2膜の研磨レートである。
スクラッチの発生については、３０ｍｍ角基板（金属銅膜）を上記と同様に研磨処理した後、中心付近の１０ｍｍ角を金属顕微鏡で３０視野に分けて、倍率２００倍にて観察し、スクラッチ（線状痕）の個数を数えて合計した。また、エッチピットの発生についても、研磨処理後の３０ｍｍ角基板（金属銅膜）の中心付近の１０ｍｍ角を金属顕微鏡で１視野について、倍率２００倍にて観察し、エッチピット（斑状痕）の個数を数えた。エッチピット数の判定については、１視野について、「少ない：３０個以下」、「やや多い：３１個〜１００個」、「多い：１０１個以上」の３段階で評価した。
研磨サンプル微粒子におけるアルミナとシリカのモル比ＭA/ＭSは、アルミナについて、測定試料に硫酸とフッ酸を加えて蒸発乾固し、その乾燥品に塩酸と純水を加えて溶解させ、ニューロ結合プラズマ発光分光分析装置で測定し、シリカについて、試料に硫酸を加え、蒸発乾固し、1000℃にて焼成後、秤量し、また、硫酸とフッ化水素酸を加え、蒸発乾固し、1000℃にて焼成後残さを秤量し、重量差よりシリカ含有量を求め、これらの値から算出した。
最後に、研磨用シリカゾルを次の評価基準に従って判定した。
○：実用性に優れる
△：実用性が劣る
×：実用性が著しく劣る Next, Table 1 shows the properties of the polishing sample and the results of a polishing test using the sample.
The inorganic anion concentration was measured using an ion chromatograph (model number; DX-AQ) manufactured by DIONEX.
Polishing test
A 29 mm square polishing test substrate (SiO 2 film) was cut out and a polishing test was performed using NF300 manufactured by Nano Factor.
Polishing conditions are polishing load: 350 g / cm 2 , polishing time: 30 sec, slurry flow rate: 70 ml / min, polishing pad: Rodel Nitta IC1000, polishing pad rotation speed: 30 rpm. The polishing rate is the polishing rate of the SiO 2 film.
Regarding the generation of scratches, after polishing a 30 mm square substrate (metal copper film) in the same manner as above, the 10 mm square near the center was divided into 30 fields of view with a metal microscope and observed at a magnification of 200 times. The number of traces) was counted and totaled. In addition, regarding the occurrence of etch pits, a 10 mm square near the center of the 30 mm square substrate (metal copper film) after the polishing treatment was observed with a metal microscope for one field of view at a magnification of 200 times. Counted the number. Regarding the determination of the number of etch pits, one visual field was evaluated in three stages: “less: 30 or less”, “slightly more: 31 to 100”, and “more: 101 or more”.
The molar ratio M A / M S of alumina and silica in the polished sample fine particles was determined by adding sulfuric acid and hydrofluoric acid to the measurement sample, evaporating to dryness, adding hydrochloric acid and pure water to the dried product, and dissolving it. Measured with a coupled plasma optical emission spectrometer, sulfuric acid was added to the sample for silica, evaporated to dryness, calcined at 1000 ° C., weighed, and sulfuric acid and hydrofluoric acid were added to evaporate to dryness. After firing at 1000 ° C., the residue was weighed, and the silica content was determined from the weight difference and calculated from these values.
Finally, the polishing silica sol was determined according to the following evaluation criteria.
○: Excellent in practicality △: Inferior in practicality ×: Extremely inferior in practicality

触媒化成工業（株）製シリカゾルSI-80P(シリカ濃度; 39.55%,平均粒子径;81nm) 21.49kgに超純水を21.01kg添加し、シリカ濃度20%に稀釈後30分間撹拌した。さらに稀釈したシリカゾルを攪拌しながら80℃に昇温して、3.0%酸性ケイ酸液0.5kgおよび0.56%アルミン酸ナトリウム液0.5kgを準備し、それぞれ2.8ｇ/minの添加速度で、同時に添加した(添加時間；3時間)。添加終了後、さらに同一温度で１時間保持したのち冷却してシリカアルミナ被覆処理をした。
前記のシリカアルミナ被覆処理を施したシリカゾルを23℃で撹拌をおこない、その中に陽イオン交換樹脂を6.40kg投入し、pH値が3以下になるまで撹拌しながら保持し、その後その陽イオン交換樹脂を除去した。次にこのシリカゾルを23℃で撹拌をおこない、その中に陰イオン交換樹脂を0.64kg投入し、pH値が5.2以上になるまで撹拌しながら保持し、その後その陰イオン交換樹脂を除去した。さらにこの前記シリカゾルを23℃で撹拌をおこない、その中に再度陽イオン交換樹脂を6.40kg投入し、投入後80℃に昇温して、その温度で3時間撹拌しながら保持した。その後冷却して陽イオン交換樹脂を除去した。さらにこのシリカゾルを23℃で撹拌をおこない、その中に再度陰イオン交換樹脂を0.64kg投入し、投入後40℃に昇温して、その温度で12時間撹拌しながら保持した。その後冷却して陰イオン交換樹脂を除去した。さらに前記のシリカゾルを23℃で撹拌をおこない、その中に陽イオン交換樹脂を6.40kg投入し、投入後シリカゾルのpH値が4以下になるまで撹拌しながら保持した。その後その陽イオン交換樹脂を除去した。前記の一連のイオン交換処理を施したシリカゾルに対して限外膜を使用し濃縮をおこない、この段階で固形分濃度を31％に調整した。
次に濃縮したシリカゾルを攪拌しながらpH調整のため5％テトラメチルアンモニウムハイドロオキサイド水溶液を添加しpH値が9.2となった。
さらに殺菌を目的として、前記のシリカゾルを80℃へ昇温し、その温度で1時間撹拌しながら保持した。その後、60℃へ冷却し、3.1％に希釈した過酸化水素水を16.9gを撹拌しながら添加し、1時間撹拌した。なお、過酸化水素水は、全量の50ppmになるように調整した。
殺菌処理をした前記のシリカゾルの粗大粒子数を低減するために、遠心力1900Gで10分間遠心処理を施し、そのシリカゾルの上澄み液を約９０％回収した。
最後に前記の遠心処理を施したシリカゾルを窒素圧0.1kg/cm2の窒素で加圧し、日本ポール社製10μmフィルタ、1.2μｍフィルタさらに0.6μｍフィルタを順番に使用してフィルタリングろ過をした。最後に固形分濃度を30%に調整し研磨サンプルの調製を完了した。 Silica sol SI-80P (Silica concentration: 39.55%, average particle size: 81 nm) 21.01 kg of ultrapure water was added to 21.49 kg and diluted to a silica concentration of 20%, followed by stirring for 30 minutes. Further, the diluted silica sol was heated to 80 ° C. while stirring to prepare 0.5 kg of a 3.0% acidic silicic acid solution and 0.5 kg of a 0.56% sodium aluminate solution, which were simultaneously added at an addition rate of 2.8 g / min. (Addition time; 3 hours). After completion of the addition, the mixture was further maintained at the same temperature for 1 hour and then cooled to perform silica alumina coating treatment.
The silica sol coated with the above silica-alumina coating is stirred at 23 ° C., and 6.40 kg of cation exchange resin is added to the silica sol, and the mixture is held with stirring until the pH value becomes 3 or less. The resin was removed. Next, this silica sol was stirred at 23 ° C., and 0.64 kg of an anion exchange resin was added therein, and the silica sol was held with stirring until the pH value became 5.2 or more, and then the anion exchange resin was removed. Further, the silica sol was stirred at 23 ° C., and 6.40 kg of the cation exchange resin was charged therein again. After the charging, the temperature was raised to 80 ° C. and held at that temperature for 3 hours with stirring. Thereafter, it was cooled to remove the cation exchange resin. Further, this silica sol was stirred at 23 ° C., and 0.64 kg of anion exchange resin was again charged therein. After the charging, the temperature was raised to 40 ° C. and held at that temperature for 12 hours with stirring. Thereafter, the anion exchange resin was removed by cooling. Further, the silica sol was stirred at 23 ° C., and 6.40 kg of a cation exchange resin was charged therein, and after the charging, the silica sol was held with stirring until the pH value of the silica sol became 4 or less. The cation exchange resin was then removed. The silica sol subjected to the above series of ion exchange treatments was concentrated using an ultra-membrane, and the solid content concentration was adjusted to 31% at this stage.
Next, 5% tetramethylammonium hydroxide aqueous solution was added to adjust the pH while stirring the concentrated silica sol, and the pH value became 9.2.
Further, for the purpose of sterilization, the silica sol was heated to 80 ° C. and held at that temperature with stirring for 1 hour. Thereafter, the mixture was cooled to 60 ° C., 16.9 g of hydrogen peroxide diluted to 3.1% was added with stirring, and the mixture was stirred for 1 hour. The hydrogen peroxide solution was adjusted to 50 ppm of the total amount.
In order to reduce the number of coarse particles of the sterilized silica sol, centrifugation was performed at a centrifugal force of 1900 G for 10 minutes, and about 90% of the silica sol supernatant was recovered.
Finally, the silica sol subjected to the above centrifugal treatment was pressurized with nitrogen having a nitrogen pressure of 0.1 kg / cm 2 and filtered using a 10 μm filter, a 1.2 μm filter and a 0.6 μm filter manufactured by Nippon Pole Co., Ltd. in order. Finally, the solid content concentration was adjusted to 30% to complete the preparation of the polished sample.

触媒化成工業（株）製シリカゾルSI-80P(シリカ濃度;39.55%,平均粒子径;81nm) 21.49kgに超純水を21.01kg添加し、シリカ濃度20%に稀釈後30分間撹拌した。さらに稀釈したシリカゾルを攪拌しながら80℃に昇温して、3.0%酸性ケイ酸液0.5kgおよび2.22%アルミン酸ナトリウム液0.5kgを準備し、それぞれ2.8ｇ/minの添加速度で、同時に添加した(添加時間；3時間)。添加終了後、さらに同一温度で１時間保持したのち冷却してシリカアルミナ被覆処理をした。
前記のシリカアルミナ被覆処理を施したシリカゾルを23℃で撹拌をおこない、その中に陽イオン交換樹脂を6.40kg投入し、pH値が3以下になるまで撹拌しながら保持し、その後その陽イオン交換樹脂を除去した。次にこのシリカゾルを23℃で撹拌をおこない、その中に陰イオン交換樹脂を0.64kg投入し、pH値が5.2以上になるまで撹拌しながら保持し、その後その陰イオン交換樹脂を除去した。さらにこの前記シリカゾルを23℃で撹拌をおこない、その中に再度陽イオン交換樹脂を6.40kg投入し、投入後80℃に昇温して、その温度で3時間撹拌しながら保持した。その後冷却して陽イオン交換樹脂を除去した。さらにこのシリカゾルを23℃で撹拌をおこない、その中に再度陰イオン交換樹脂を0.64kg投入し、投入後40℃に昇温して、その温度で12時間撹拌しながら保持した。その後冷却して陰イオン交換樹脂を除去した。さらに前記のシリカゾルを23℃で撹拌をおこない、その中に陽イオン交換樹脂を6.40kg投入し、投入後シリカゾルのpH値が4以下になるまで撹拌しながら保持した。その後その陽イオン交換樹脂を除去した。前記の一連のイオン交換処理を施したシリカゾルに対して限外膜を使用し濃縮をおこない、この段階で固形分濃度を31％に調整した。
次に濃縮したシリカゾルを攪拌しながらpH調整のため5％テトラメチルアンモニウムハイドロオキサイド水溶液を添加しpH値が9.4となった。
さらに殺菌を目的として、前記のシリカゾルを80℃へ昇温し、その温度で1時間撹拌しながら保持した。その後、60℃へ冷却し、3.1％に希釈した過酸化水素水を16.9gを撹拌しながら添加し、1時間撹拌した。なお、過酸化水素水は、全量の50ppmになるように調整した。
殺菌処理をした前記のシリカゾルの粗大粒子数を低減するために、遠心力1900Gで10分間遠心処理を施し、そのシリカゾルの上澄み液を約９０％回収した。
最後に前記の遠心処理を施したシリカゾルを窒素圧0.1kg/cm2の窒素で加圧し、日本ポール社製10μmフィルタ、1.2μｍフィルタさらに0.6μｍフィルタを順番に使用してフィルタリングろ過をした。最後に固形分濃度を30%に調整し研磨サンプルの調製を完了した。 Silica sol SI-80P (silica concentration: 39.55%, average particle size: 81 nm) manufactured by Catalytic Chemical Industry Co., Ltd. 21.01 kg of ultrapure water was added to 21.49 kg, diluted to a silica concentration of 20%, and stirred for 30 minutes. Further, the diluted silica sol was heated to 80 ° C. while stirring to prepare 0.5 kg of a 3.0% acidic silicic acid solution and 0.5 kg of a 2.22% sodium aluminate solution, which were simultaneously added at an addition rate of 2.8 g / min. (Addition time; 3 hours). After completion of the addition, the mixture was further maintained at the same temperature for 1 hour and then cooled to perform silica alumina coating treatment.
The silica sol coated with the above silica-alumina coating is stirred at 23 ° C., and 6.40 kg of cation exchange resin is added to the silica sol, and the mixture is held with stirring until the pH value becomes 3 or less. The resin was removed. Next, this silica sol was stirred at 23 ° C., and 0.64 kg of an anion exchange resin was added therein, and the silica sol was held with stirring until the pH value became 5.2 or more, and then the anion exchange resin was removed. Further, the silica sol was stirred at 23 ° C., and 6.40 kg of the cation exchange resin was charged therein again. After the charging, the temperature was raised to 80 ° C. and held at that temperature for 3 hours with stirring. Thereafter, it was cooled to remove the cation exchange resin. Further, this silica sol was stirred at 23 ° C., and 0.64 kg of anion exchange resin was again charged therein. After the charging, the temperature was raised to 40 ° C. and held at that temperature for 12 hours with stirring. Thereafter, the anion exchange resin was removed by cooling. Further, the silica sol was stirred at 23 ° C., and 6.40 kg of a cation exchange resin was charged therein, and after the charging, the silica sol was held with stirring until the pH value of the silica sol became 4 or less. The cation exchange resin was then removed. The silica sol subjected to the above series of ion exchange treatments was concentrated using an ultra-membrane, and the solid content concentration was adjusted to 31% at this stage.
Next, 5% tetramethylammonium hydroxide aqueous solution was added to adjust the pH while stirring the concentrated silica sol, and the pH value became 9.4.
Further, for the purpose of sterilization, the silica sol was heated to 80 ° C. and held at that temperature with stirring for 1 hour. Thereafter, the mixture was cooled to 60 ° C., 16.9 g of hydrogen peroxide diluted to 3.1% was added with stirring, and the mixture was stirred for 1 hour. The hydrogen peroxide solution was adjusted to 50 ppm of the total amount.
In order to reduce the number of coarse particles of the sterilized silica sol, centrifugation was performed at a centrifugal force of 1900 G for 10 minutes, and about 90% of the silica sol supernatant was recovered.
Finally, the silica sol subjected to the above centrifugal treatment was pressurized with nitrogen having a nitrogen pressure of 0.1 kg / cm 2 and filtered using a 10 μm filter, a 1.2 μm filter and a 0.6 μm filter manufactured by Nippon Pole Co., Ltd. in order. Finally, the solid content concentration was adjusted to 30% to complete the preparation of the polished sample.

触媒化成工業（株）製シリカゾルSI-80P(シリカ濃度;40.40%,平均粒子径;81nm) 21.04kgに超純水を21.46kg添加し、シリカ濃度20%に稀釈後30分間撹拌した。さらに稀釈したシリカゾルを攪拌しながら80℃に昇温して、3.0%酸性ケイ酸液0.5kgおよび0.56%アルミン酸ナトリウム液0.5kgを準備し、それぞれ2.8ｇ/minの添加速度で、同時に添加した(添加時間；3時間)。添加終了後、さらに同一温度で１時間保持したのち冷却してシリカアルミナ被覆処理をした。
前記のシリカアルミナ被覆処理を施したシリカゾルを23℃で撹拌をおこない、その中に陽イオン交換樹脂を6.40kg投入し、pH値が3以下になるまで撹拌しながら保持し、その後その陽イオン交換樹脂を除去した。次にこのシリカゾルを23℃で撹拌をおこない、その中に陰イオン交換樹脂を0.64kg投入し、pH値が5.2以上になるまで撹拌しながら保持し、その後その陰イオン交換樹脂を除去した。さらにこの前記シリカゾルを23℃で撹拌をおこない、その中に再度陽イオン交換樹脂を6.40kg投入し、投入後80℃に昇温して、その温度で3時間撹拌しながら保持した。その後冷却して陽イオン交換樹脂を除去した。さらにこのシリカゾルを23℃で撹拌をおこない、その中に再度陰イオン交換樹脂を0.64kg投入し、投入後40℃に昇温して、その温度で12時間撹拌しながら保持した。その後冷却して陰イオン交換樹脂を除去した。さらに前記のシリカゾルを23℃で撹拌をおこない、その中に陽イオン交換樹脂を6.40kg投入し、投入後シリカゾルのpH値が4以下になるまで撹拌しながら保持した。その後その陽イオン交換樹脂を除去した。前記の一連のイオン交換処理を施したシリカゾルに対して限外膜を使用し濃縮をおこない、この段階で固形分濃度を31％に調整した。
次に濃縮したシリカゾルを攪拌しながらpH調整のため5％クエン酸水溶液を添加しpH値が2.9となった。
さらに殺菌を目的として、前記のシリカゾルを80℃へ昇温し、その温度で1時間撹拌しながら保持した。その後、60℃へ冷却し、3.1％に希釈した過酸化水素水を16.9gを撹拌しながら添加し、1時間撹拌した。なお、過酸化水素水は、全量の50ppmになるように調整した。
殺菌処理をした前記のシリカゾルの粗大粒子数を低減するために、遠心力1900Gで10分間遠心処理を施し、そのシリカゾルの上澄み液を約９０％回収した。
最後に前記の遠心処理を施したシリカゾルを窒素圧0.1kg/cm2の窒素で加圧し、日本ポール社製10μmフィルタ、1.2μｍフィルタさらに0.6μｍフィルタを順番に使用してフィルタリングろ過をした。最後に固形分濃度を30%に調整し研磨サンプルの調製を完了した。 Silica sol SI-80P (Silica concentration: 40.40%, average particle size: 81 nm) 21.04 kg of ultrapure water was added to 21.04 kg, diluted to 20% silica concentration, and stirred for 30 minutes. Further, the diluted silica sol was heated to 80 ° C. while stirring to prepare 0.5 kg of a 3.0% acidic silicic acid solution and 0.5 kg of a 0.56% sodium aluminate solution, which were simultaneously added at an addition rate of 2.8 g / min. (Addition time; 3 hours). After completion of the addition, the mixture was further maintained at the same temperature for 1 hour and then cooled to perform silica alumina coating treatment.
The silica sol coated with the above silica-alumina coating is stirred at 23 ° C., and 6.40 kg of cation exchange resin is added to the silica sol, and the mixture is held with stirring until the pH value becomes 3 or less. The resin was removed. Next, this silica sol was stirred at 23 ° C., and 0.64 kg of an anion exchange resin was added therein, and the silica sol was held with stirring until the pH value became 5.2 or more, and then the anion exchange resin was removed. Further, the silica sol was stirred at 23 ° C., and 6.40 kg of the cation exchange resin was again charged therein. After the charging, the temperature was raised to 80 ° C. and held at that temperature for 3 hours with stirring. Thereafter, it was cooled to remove the cation exchange resin. Further, this silica sol was stirred at 23 ° C., and 0.64 kg of anion exchange resin was again charged therein. After the charging, the temperature was raised to 40 ° C. and held at that temperature for 12 hours with stirring. Thereafter, the anion exchange resin was removed by cooling. Further, the silica sol was stirred at 23 ° C., and 6.40 kg of a cation exchange resin was added thereto, and after the addition, the silica sol was held with stirring until the pH value of the silica sol became 4 or less. The cation exchange resin was then removed. The silica sol subjected to the above-described series of ion exchange treatments was concentrated using an ultra-membrane, and the solid content concentration was adjusted to 31% at this stage.
Next, 5% citric acid aqueous solution was added to adjust the pH while stirring the concentrated silica sol, and the pH value became 2.9.
Further, for the purpose of sterilization, the silica sol was heated to 80 ° C. and held at that temperature with stirring for 1 hour. Thereafter, the mixture was cooled to 60 ° C., 16.9 g of hydrogen peroxide diluted to 3.1% was added with stirring, and the mixture was stirred for 1 hour. The hydrogen peroxide solution was adjusted to 50 ppm of the total amount.
In order to reduce the number of coarse particles of the sterilized silica sol, centrifugation was performed at a centrifugal force of 1900 G for 10 minutes, and about 90% of the supernatant of the silica sol was recovered.
Finally, the silica sol subjected to the above centrifugal treatment was pressurized with nitrogen having a nitrogen pressure of 0.1 kg / cm 2 , and filtered using a 10 μm filter, a 1.2 μm filter, and a 0.6 μm filter made by Nippon Pole in order. Finally, the solid content concentration was adjusted to 30% to complete the preparation of the polished sample.

触媒化成工業（株）製シリカゾルSI-80P(シリカ濃度;40.40%,平均粒子径;81nm) 21.04kgに超純水を21.46kg添加し、シリカ濃度20%に稀釈後30分間撹拌した。さらに稀釈したシリカゾルを攪拌しながら80℃に昇温して、3.0%酸性ケイ酸液0.5kgおよび0.56%アルミン酸ナトリウム液0.5kgを準備し、それぞれ2.8ｇ/minの添加速度で、同時に添加した(添加時間；3時間)。添加終了後、さらに同一温度で１時間保持したのち冷却してシリカアルミナ被覆処理をした。
前記のシリカアルミナ被覆処理を施したシリカゾルを23℃で撹拌をおこない、その中に陽イオン交換樹脂を6.40kg投入し、pH値が3以下になるまで撹拌しながら保持し、その後その陽イオン交換樹脂を除去した。次にこのシリカゾルを23℃で撹拌をおこない、その中に陰イオン交換樹脂を0.64kg投入し、pH値が5.2以上になるまで撹拌しながら保持し、その後その陰イオン交換樹脂を除去した。さらにこの前記シリカゾルを23℃で撹拌をおこない、その中に再度陽イオン交換樹脂を6.40kg投入し、投入後80℃に昇温して、その温度で3時間撹拌しながら保持した。その後冷却して陽イオン交換樹脂を除去した。さらにこのシリカゾルを23℃で撹拌をおこない、その中に再度陰イオン交換樹脂を0.64kg投入し、投入後40℃に昇温して、その温度で12時間撹拌しながら保持した。その後冷却して陰イオン交換樹脂を除去した。さらに前記のシリカゾルを23℃で撹拌をおこない、その中に陽イオン交換樹脂を6.40kg投入し、投入後シリカゾルのpH値が4以下になるまで撹拌しながら保持した。その後その陽イオン交換樹脂を除去した。前記の一連のイオン交換処理を施したシリカゾルに対して限外膜を使用し濃縮をおこない、この段階で固形分濃度を31％に調整した。
次に濃縮したシリカゾルを攪拌しながらpH調整のため5％クエン酸水溶液を添加しpH値が3.1となった。
さらに殺菌を目的として、前記のシリカゾルを80℃へ昇温し、その温度で1時間撹拌しながら保持した。その後、60℃へ冷却し、0.5％に希釈した次亜塩素酸ナトリウム水溶液を16.9gを撹拌しながら添加し、1時間撹拌した。なお、次亜塩素酸ナトリウム水溶液は、全量の2ppmになるように調整した。
殺菌処理をした前記のシリカゾルの粗大粒子数を低減するために、遠心力1900Gで10分間遠心処理を施し、そのシリカゾルの上澄み液を約９０％回収した。
最後に前記の遠心処理を施したシリカゾルを窒素圧0.1kg/cm2の窒素で加圧し、日本ポール社製10μmフィルタ、1.2μｍフィルタさらに0.6μｍフィルタを順番に使用してフィルタリングろ過をした。最後に固形分濃度を30%に調整し研磨サンプルの調製を完了した。 Silica sol SI-80P (Silica concentration: 40.40%, average particle size: 81 nm) 21.04 kg of ultrapure water was added to 21.04 kg, diluted to 20% silica concentration, and stirred for 30 minutes. Further, the diluted silica sol was heated to 80 ° C. while stirring to prepare 0.5 kg of a 3.0% acidic silicic acid solution and 0.5 kg of a 0.56% sodium aluminate solution, which were simultaneously added at an addition rate of 2.8 g / min. (Addition time; 3 hours). After completion of the addition, the mixture was further maintained at the same temperature for 1 hour and then cooled to perform silica alumina coating treatment.
The silica sol coated with the above silica-alumina coating is stirred at 23 ° C., and 6.40 kg of cation exchange resin is added to the silica sol, and the mixture is held with stirring until the pH value becomes 3 or less. The resin was removed. Next, this silica sol was stirred at 23 ° C., and 0.64 kg of an anion exchange resin was added therein, and the silica sol was held with stirring until the pH value became 5.2 or more, and then the anion exchange resin was removed. Further, the silica sol was stirred at 23 ° C., and 6.40 kg of the cation exchange resin was charged therein again. After the charging, the temperature was raised to 80 ° C. and held at that temperature for 3 hours with stirring. Thereafter, it was cooled to remove the cation exchange resin. Further, this silica sol was stirred at 23 ° C., and 0.64 kg of anion exchange resin was again charged therein. After the charging, the temperature was raised to 40 ° C. and held at that temperature for 12 hours with stirring. Thereafter, the anion exchange resin was removed by cooling. Further, the silica sol was stirred at 23 ° C., and 6.40 kg of a cation exchange resin was charged therein, and after the charging, the silica sol was held with stirring until the pH value of the silica sol became 4 or less. The cation exchange resin was then removed. The silica sol subjected to the above series of ion exchange treatments was concentrated using an ultra-membrane, and the solid content concentration was adjusted to 31% at this stage.
Next, 5% citric acid aqueous solution was added to adjust the pH while stirring the concentrated silica sol, and the pH value became 3.1.
Further, for the purpose of sterilization, the silica sol was heated to 80 ° C. and held at that temperature with stirring for 1 hour. Thereafter, the mixture was cooled to 60 ° C., 16.9 g of a sodium hypochlorite aqueous solution diluted to 0.5% was added with stirring, and the mixture was stirred for 1 hour. The aqueous sodium hypochlorite solution was adjusted to 2 ppm based on the total amount.
In order to reduce the number of coarse particles of the sterilized silica sol, centrifugation was performed at a centrifugal force of 1900 G for 10 minutes, and about 90% of the silica sol supernatant was recovered.
Finally, the silica sol subjected to the above centrifugal treatment was pressurized with nitrogen having a nitrogen pressure of 0.1 kg / cm 2 and filtered using a 10 μm filter, a 1.2 μm filter and a 0.6 μm filter manufactured by Nippon Pole Co., Ltd. in order. Finally, the solid content concentration was adjusted to 30% to complete the preparation of the polished sample.

触媒化成工業（株）製シリカゾルSI-80P(シリカ濃度;40.40%,平均粒子径;81nm) 21.04kgに超純水を21.46kg添加し、シリカ濃度20%に稀釈後30分間撹拌した。さらに稀釈したシリカゾルを攪拌しながら80℃に昇温して、3.0%酸性ケイ酸液0.5kgおよび2.22%アルミン酸ナトリウム液0.5kgを準備し、それぞれ2.8ｇ/minの添加速度で、同時に添加した(添加時間；3時間)。添加終了後、さらに同一温度で１時間保持したのち冷却してシリカアルミナ被覆処理をした。
前記のシリカアルミナ被覆処理を施したシリカゾルを23℃で撹拌をおこない、その中に陽イオン交換樹脂を6.40kg投入し、pH値が3以下になるまで撹拌しながら保持し、その後その陽イオン交換樹脂を除去した。次にこのシリカゾルを23℃で撹拌をおこない、その中に陰イオン交換樹脂を0.64kg投入し、pH値が5.2以上になるまで撹拌しながら保持し、その後その陰イオン交換樹脂を除去した。さらにこの前記シリカゾルを23℃で撹拌をおこない、その中に再度陽イオン交換樹脂を6.40kg投入し、投入後80℃に昇温して、その温度で3時間撹拌しながら保持した。その後冷却して陽イオン交換樹脂を除去した。さらにこのシリカゾルを23℃で撹拌をおこない、その中に再度陰イオン交換樹脂を0.64kg投入し、投入後40℃に昇温して、その温度で12時間撹拌しながら保持した。その後冷却して陰イオン交換樹脂を除去した。さらに前記のシリカゾルを23℃で撹拌をおこない、その中に陽イオン交換樹脂を6.40kg投入し、投入後シリカゾルのpH値が4以下になるまで撹拌しながら保持した。その後その陽イオン交換樹脂を除去した。前記の一連のイオン交換処理を施したシリカゾルに対して限外膜を使用し濃縮をおこない、この段階で固形分濃度を31％に調整した。
次に濃縮したシリカゾルを攪拌しながらpH調整のため5％クエン酸水溶液を添加しpH値が3.1となった。
さらに殺菌を目的として、前記のシリカゾルを80℃へ昇温し、その温度で1時間撹拌しながら保持した。その後、60℃へ冷却し、0.5％に希釈した次亜塩素酸ナトリウム水溶液を16.9gを撹拌しながら添加し、1時間撹拌した。なお、過酸化水素水は、全量の2ppmになるように調整した。
殺菌処理をした前記のシリカゾルの粗大粒子数を低減するために、遠心力1900Gで10分間遠心処理を施し、そのシリカゾルの上澄み液を約９０％回収した。
最後に前記の遠心処理を施したシリカゾルを窒素圧0.1kg/cm2の窒素で加圧し、日本ポール社製10μmフィルタ、1.2μｍフィルタさらに0.6μｍフィルタを順番に使用してフィルタリングろ過をした。最後に固形分濃度を30%に調整し研磨サンプルの調製を完了した。 Silica sol SI-80P (Silica concentration: 40.40%, average particle size: 81 nm) 21.04 kg of ultrapure water was added to 21.04 kg, diluted to 20% silica concentration, and stirred for 30 minutes. Further, the diluted silica sol was heated to 80 ° C. while stirring to prepare 0.5 kg of a 3.0% acidic silicic acid solution and 0.5 kg of a 2.22% sodium aluminate solution, which were simultaneously added at an addition rate of 2.8 g / min. (Addition time; 3 hours). After completion of the addition, the mixture was further maintained at the same temperature for 1 hour and then cooled to perform silica alumina coating treatment.
The silica sol coated with the above silica-alumina coating is stirred at 23 ° C., and 6.40 kg of cation exchange resin is added to the silica sol, and the mixture is held with stirring until the pH value becomes 3 or less. The resin was removed. Next, this silica sol was stirred at 23 ° C., and 0.64 kg of an anion exchange resin was added therein, and the silica sol was held with stirring until the pH value became 5.2 or more, and then the anion exchange resin was removed. Further, the silica sol was stirred at 23 ° C., and 6.40 kg of the cation exchange resin was charged therein again. After the charging, the temperature was raised to 80 ° C. and held at that temperature for 3 hours with stirring. Thereafter, it was cooled to remove the cation exchange resin. Further, this silica sol was stirred at 23 ° C., and 0.64 kg of anion exchange resin was again charged therein. After the charging, the temperature was raised to 40 ° C. and held at that temperature for 12 hours with stirring. Thereafter, the anion exchange resin was removed by cooling. Further, the silica sol was stirred at 23 ° C., and 6.40 kg of a cation exchange resin was charged therein, and after the charging, the silica sol was held with stirring until the pH value of the silica sol became 4 or less. The cation exchange resin was then removed. The silica sol subjected to the above series of ion exchange treatments was concentrated using an ultra-membrane, and the solid content concentration was adjusted to 31% at this stage.
Next, 5% citric acid aqueous solution was added to adjust the pH while stirring the concentrated silica sol, and the pH value became 3.1.
Further, for the purpose of sterilization, the silica sol was heated to 80 ° C. and held at that temperature with stirring for 1 hour. Thereafter, the mixture was cooled to 60 ° C., 16.9 g of a sodium hypochlorite aqueous solution diluted to 0.5% was added with stirring, and the mixture was stirred for 1 hour. The hydrogen peroxide solution was adjusted to 2 ppm of the total amount.
In order to reduce the number of coarse particles of the sterilized silica sol, centrifugation was performed at a centrifugal force of 1900 G for 10 minutes, and about 90% of the silica sol supernatant was recovered.
Finally, the silica sol subjected to the above centrifugal treatment was pressurized with nitrogen having a nitrogen pressure of 0.1 kg / cm 2 and filtered using a 10 μm filter, a 1.2 μm filter and a 0.6 μm filter manufactured by Nippon Pole Co., Ltd. in order. Finally, the solid content concentration was adjusted to 30% to complete the preparation of the polished sample.

触媒化成工業（株）製シリカゾルSI-80P(シリカ濃度; 39.55%,平均粒子径;81nm) 21.49kgに超純水を21.01kg添加し、シリカ濃度20%に稀釈後30分間撹拌した。さらに稀釈したシリカゾルを攪拌しながら80℃に昇温して、シリカ濃度を3.0%に希釈した3号水硝子水溶液0.5kgおよび0.56%アルミン酸ナトリウム液0.5kgを準備し、それぞれ2.8ｇ/minの添加速度で、同時に添加した(添加時間；3時間)。添加終了後、さらに同一温度で１時間保持したのち冷却してシリカアルミナ被覆処理をした。
前記のシリカアルミナ被覆処理を施したシリカゾルを23℃で撹拌をおこない、その中に陽イオン交換樹脂を7.50kg投入し、pH値が3以下になるまで撹拌しながら保持し、その後その陽イオン交換樹脂を除去した。次にこのシリカゾルを23℃で撹拌をおこない、その中に陰イオン交換樹脂を0.64kg投入し、pH値が5.2以上になるまで撹拌しながら保持し、その後その陰イオン交換樹脂を除去した。さらにこの前記シリカゾルを23℃で撹拌をおこない、その中に再度陽イオン交換樹脂を7.50kg投入し、投入後80℃に昇温して、その温度で3時間撹拌しながら保持した。その後冷却して陽イオン交換樹脂を除去した。さらにこのシリカゾルを23℃で撹拌をおこない、その中に再度陰イオン交換樹脂を0.64kg投入し、投入後40℃に昇温して、その温度で12時間撹拌しながら保持した。その後冷却して陰イオン交換樹脂を除去した。さらに前記のシリカゾルを23℃で撹拌をおこない、その中に陽イオン交換樹脂を7.50kg投入し、投入後シリカゾルのpH値が4以下になるまで撹拌しながら保持した。その後その陽イオン交換樹脂を除去した。前記の一連のイオン交換処理を施したシリカゾルに対して限外膜を使用し濃縮をおこない、この段階で固形分濃度を31％に調整した。
次に濃縮したシリカゾルを攪拌しながらpH調整のため5％テトラメチルアンモニウムハイドロオキサイド水溶液を添加しpH値が9.1となった。
さらに殺菌を目的として、前記のシリカゾルを80℃へ昇温し、その温度で1時間撹拌しながら保持した。その後、60℃へ冷却し、3.1％に希釈した過酸化水素水を16.9gを撹拌しながら添加し、1時間撹拌した。なお、過酸化水素水は、全量の50ppmになるように調整した。
殺菌処理をした前記のシリカゾルの粗大粒子数を低減するために、遠心力1900Gで10分間遠心処理を施し、そのシリカゾルの上澄み液を約９０％回収した。
最後に前記の遠心処理を施したシリカゾルを窒素圧0.1kg/cm2の窒素で加圧し、日本ポール社製10μmフィルタ、1.2μｍフィルタさらに0.6μｍフィルタを順番に使用してフィルタリングろ過をした。最後に固形分濃度を30%に調整し研磨サンプルの調製を完了した。 Silica sol SI-80P (Silica concentration: 39.55%, average particle size: 81 nm) 21.01 kg of ultrapure water was added to 21.49 kg and diluted to a silica concentration of 20%, followed by stirring for 30 minutes. Further, the diluted silica sol was heated to 80 ° C. while stirring to prepare 0.5 kg of No. 3 water glass aqueous solution and 0.5 kg of 0.56% sodium aluminate solution, each diluted to 3.0%, and each containing 2.8 g / min. The addition was carried out simultaneously at the addition rate (addition time; 3 hours). After completion of the addition, the mixture was further maintained at the same temperature for 1 hour and then cooled to perform silica alumina coating treatment.
The silica sol coated with the silica-alumina coating is stirred at 23 ° C., and 7.50 kg of cation exchange resin is added to the silica sol, and the mixture is held with stirring until the pH value becomes 3 or less. The resin was removed. Next, this silica sol was stirred at 23 ° C., and 0.64 kg of an anion exchange resin was added therein, and the silica sol was held with stirring until the pH value became 5.2 or more, and then the anion exchange resin was removed. Further, the silica sol was stirred at 23 ° C., and 7.50 kg of the cation exchange resin was again charged therein. After the charging, the temperature was raised to 80 ° C. and held at that temperature for 3 hours with stirring. Thereafter, it was cooled to remove the cation exchange resin. Further, this silica sol was stirred at 23 ° C., and 0.64 kg of anion exchange resin was again charged therein. After the charging, the temperature was raised to 40 ° C. and held at that temperature for 12 hours with stirring. Thereafter, the anion exchange resin was removed by cooling. Further, the silica sol was stirred at 23 ° C., and 7.50 kg of a cation exchange resin was added thereto, and after the addition, the silica sol was held with stirring until the pH value of the silica sol became 4 or less. The cation exchange resin was then removed. The silica sol subjected to the above series of ion exchange treatments was concentrated using an ultra-membrane, and the solid content concentration was adjusted to 31% at this stage.
Next, a 5% tetramethylammonium hydroxide aqueous solution was added to adjust the pH while stirring the concentrated silica sol, and the pH value became 9.1.
Further, for the purpose of sterilization, the silica sol was heated to 80 ° C. and held at that temperature with stirring for 1 hour. Thereafter, the mixture was cooled to 60 ° C., 16.9 g of hydrogen peroxide diluted to 3.1% was added with stirring, and the mixture was stirred for 1 hour. The hydrogen peroxide solution was adjusted to 50 ppm of the total amount.
In order to reduce the number of coarse particles of the sterilized silica sol, centrifugation was performed at a centrifugal force of 1900 G for 10 minutes, and about 90% of the silica sol supernatant was recovered.
Finally, the silica sol subjected to the above centrifugal treatment was pressurized with nitrogen having a nitrogen pressure of 0.1 kg / cm 2 and filtered using a 10 μm filter, a 1.2 μm filter and a 0.6 μm filter manufactured by Nippon Pole Co., Ltd. in order. Finally, the solid content concentration was adjusted to 30% to complete the preparation of the polished sample.

比較例１Comparative Example 1

触媒化成工業（株）製シリカゾルSI-80P(シリカ濃度; 39.55%,平均粒子径;81nm) 21.49kgに超純水を21.01kg添加し、シリカ濃度20%に稀釈後30分間撹拌した。
前記の希釈を施したシリカゾルを23℃で撹拌をおこない、その中に陽イオン交換樹脂を6.40kg投入し、pH値が3以下になるまで撹拌しながら保持し、その後その陽イオン交換樹脂を除去した。次にこのシリカゾルを23℃で撹拌をおこない、その中に陰イオン交換樹脂を0.64kg投入し、pH値が5.2以上になるまで撹拌しながら保持し、その後その陰イオン交換樹脂を除去した。さらにこの前記シリカゾルを23℃で撹拌をおこない、その中に再度陽イオン交換樹脂を6.40kg投入し、投入後80℃に昇温して、その温度で3時間撹拌しながら保持した。その後冷却して陽イオン交換樹脂を除去した。さらにこのシリカゾルを23℃で撹拌をおこない、その中に再度陰イオン交換樹脂を0.64kg投入し、投入後40℃に昇温して、その温度で12時間撹拌しながら保持した。その後冷却して陰イオン交換樹脂を除去した。さらに前記のシリカゾルを23℃で撹拌をおこない、その中に陽イオン交換樹脂を6.40kg投入し、投入後シリカゾルのpH値が4以下になるまで撹拌しながら保持した。その後その陽イオン交換樹脂を除去した。前記の一連のイオン交換処理を施したシリカゾルに対して限外膜を使用し濃縮をおこない、この段階で固形分濃度を31％に調整した。
次に濃縮したシリカゾルを攪拌しながらpH調整のため5％テトラメチルアンモニウムハイドロオキサイド水溶液を添加しpH値が8.6となった。
さらに殺菌を目的として、前記のシリカゾルを80℃へ昇温し、その温度で1時間撹拌しながら保持した。その後、60℃へ冷却し、3.1％に希釈した過酸化水素水を16.9gを撹拌しながら添加し、1時間撹拌した。なお、過酸化水素水は、全量の50ppmになるように調整した。
殺菌処理をした前記のシリカゾルの粗大粒子数を低減するために、遠心力1900Gで10分間遠心処理を施し、そのシリカゾルの上澄み液を約９０％回収した。
最後に前記の遠心処理を施したシリカゾルを窒素圧0.1kg/cm2の窒素で加圧し、日本ポール社製10μmフィルタ、1.2μｍフィルタさらに0.6μｍフィルタを順番に使用してフィルタリングろ過をした。最後に固形分濃度を30%に調整し研磨サンプルの調製を完了した。 Silica sol SI-80P (Silica concentration: 39.55%, average particle size: 81 nm) 21.01 kg of ultrapure water was added to 21.49 kg and diluted to a silica concentration of 20%, followed by stirring for 30 minutes.
The silica sol diluted as described above is stirred at 23 ° C., and 6.40 kg of cation exchange resin is added to it and held while stirring until the pH value becomes 3 or less, and then the cation exchange resin is removed. did. Next, this silica sol was stirred at 23 ° C., and 0.64 kg of an anion exchange resin was added therein, and the silica sol was held with stirring until the pH value became 5.2 or more, and then the anion exchange resin was removed. Further, the silica sol was stirred at 23 ° C., and 6.40 kg of the cation exchange resin was charged therein again. After the charging, the temperature was raised to 80 ° C. and held at that temperature for 3 hours with stirring. Thereafter, it was cooled to remove the cation exchange resin. Further, this silica sol was stirred at 23 ° C., and 0.64 kg of anion exchange resin was again charged therein. After the charging, the temperature was raised to 40 ° C. and held at that temperature for 12 hours with stirring. Thereafter, the anion exchange resin was removed by cooling. Further, the silica sol was stirred at 23 ° C., and 6.40 kg of a cation exchange resin was charged therein, and after the charging, the silica sol was held with stirring until the pH value of the silica sol became 4 or less. The cation exchange resin was then removed. The silica sol subjected to the above series of ion exchange treatments was concentrated using an ultra-membrane, and the solid content concentration was adjusted to 31% at this stage.
Next, 5% tetramethylammonium hydroxide aqueous solution was added to adjust the pH while stirring the concentrated silica sol, and the pH value became 8.6.
Further, for the purpose of sterilization, the silica sol was heated to 80 ° C. and held at that temperature with stirring for 1 hour. Thereafter, the mixture was cooled to 60 ° C., 16.9 g of hydrogen peroxide diluted to 3.1% was added with stirring, and the mixture was stirred for 1 hour. The hydrogen peroxide solution was adjusted to 50 ppm of the total amount.
In order to reduce the number of coarse particles of the sterilized silica sol, centrifugation was performed at a centrifugal force of 1900 G for 10 minutes, and about 90% of the silica sol supernatant was recovered.
Finally, the silica sol subjected to the above centrifugal treatment was pressurized with nitrogen having a nitrogen pressure of 0.1 kg / cm 2 and filtered using a 10 μm filter, a 1.2 μm filter and a 0.6 μm filter manufactured by Nippon Pole Co., Ltd. in order. Finally, the solid content concentration was adjusted to 30% to complete the preparation of the polished sample.

比較例２Comparative Example 2

触媒化成工業（株）製シリカゾルSI-80P(シリカ濃度; 39.55%,平均粒子径;81nm) 21.49kgに超純水を21.01kg添加し、シリカ濃度20%に稀釈後30分間撹拌した。さらに稀釈したシリカゾルを攪拌しながら80℃に昇温して、3.0%酸性ケイ酸液0.5kgおよび0.56%アルミン酸ナトリウム液0.5kgを準備し、それぞれ2.8ｇ/minの添加速度で、同時に添加した(添加時間；3時間)。添加終了後、さらに同一温度で１時間保持したのち冷却してシリカアルミナ被覆処理をした。
前記のシリカアルミナ被覆処理を施したシリカゾルを23℃で撹拌をおこない、その中に陽イオン交換樹脂を6.40kg投入し、pH値が3以下になるまで撹拌しながら保持し、その後その陽イオン交換樹脂を除去した。次にこのシリカゾルを23℃で撹拌をおこない、その中に陰イオン交換樹脂を0.64kg投入し、pH値が5.2以上になるまで撹拌しながら保持し、その後その陰イオン交換樹脂を除去した。さらにこの前記シリカゾルを23℃で撹拌をおこない、その中に再度陽イオン交換樹脂を6.40kg投入し、投入後80℃に昇温して、その温度で3時間撹拌しながら保持した。その後冷却して陽イオン交換樹脂を除去した。前記の一連のイオン交換処理を施したシリカゾルに対して限外膜を使用し濃縮をおこない、この段階で固形分濃度を31％に調整した。
次に濃縮したシリカゾルを攪拌しながらpH調整のため5％テトラメチルアンモニウムハイドロオキサイド水溶液を添加しpH値が8.6となった。
さらに殺菌を目的として、前記のシリカゾルを80℃へ昇温し、その温度で1時間撹拌しながら保持した。その後、60℃へ冷却し、3.1％に希釈した過酸化水素水を16.9gを撹拌しながら添加し、1時間撹拌した。なお、過酸化水素水は、全量の50ppmになるように調整した。
殺菌処理をした前記のシリカゾルの粗大粒子数を低減するために、遠心力1900Gで10分間遠心処理を施し、そのシリカゾルの上澄み液を約９０％回収した。
最後に前記の遠心処理を施したシリカゾルを窒素圧0.1kg/cm2の窒素で加圧し、日本ポール社製10μmフィルタ、1.2μｍフィルタさらに0.6μｍフィルタを順番に使用してフィルタリングろ過をした。最後に固形分濃度を30%に調整し研磨サンプルの調製を完了した。 Silica sol SI-80P (Silica concentration: 39.55%, average particle size: 81 nm) 21.01 kg of ultrapure water was added to 21.49 kg and diluted to a silica concentration of 20%, followed by stirring for 30 minutes. Further, the diluted silica sol was heated to 80 ° C. while stirring to prepare 0.5 kg of a 3.0% acidic silicic acid solution and 0.5 kg of a 0.56% sodium aluminate solution, which were simultaneously added at an addition rate of 2.8 g / min. (Addition time; 3 hours). After completion of the addition, the mixture was further maintained at the same temperature for 1 hour and then cooled to perform silica alumina coating treatment.
The silica sol coated with the above silica-alumina coating is stirred at 23 ° C., and 6.40 kg of cation exchange resin is added to the silica sol, and the mixture is held with stirring until the pH value becomes 3 or less. The resin was removed. Next, this silica sol was stirred at 23 ° C., and 0.64 kg of an anion exchange resin was added therein, and the silica sol was held with stirring until the pH value became 5.2 or more, and then the anion exchange resin was removed. Further, the silica sol was stirred at 23 ° C., and 6.40 kg of the cation exchange resin was charged therein again. After the charging, the temperature was raised to 80 ° C. and held at that temperature for 3 hours with stirring. Thereafter, it was cooled to remove the cation exchange resin. The silica sol subjected to the above series of ion exchange treatments was concentrated using an ultra-membrane, and the solid content concentration was adjusted to 31% at this stage.
Next, 5% tetramethylammonium hydroxide aqueous solution was added to adjust the pH while stirring the concentrated silica sol, and the pH value became 8.6.
Further, for the purpose of sterilization, the silica sol was heated to 80 ° C. and held at that temperature with stirring for 1 hour. Thereafter, the mixture was cooled to 60 ° C., 16.9 g of hydrogen peroxide diluted to 3.1% was added with stirring, and the mixture was stirred for 1 hour. The hydrogen peroxide solution was adjusted to 50 ppm of the total amount.
In order to reduce the number of coarse particles of the sterilized silica sol, centrifugation was performed at a centrifugal force of 1900 G for 10 minutes, and about 90% of the silica sol supernatant was recovered.
Finally, the silica sol subjected to the above centrifugal treatment was pressurized with nitrogen having a nitrogen pressure of 0.1 kg / cm 2 and filtered using a 10 μm filter, a 1.2 μm filter and a 0.6 μm filter manufactured by Nippon Pole Co., Ltd. in order. Finally, the solid content concentration was adjusted to 30% to complete the preparation of the polished sample.

比較例３Comparative Example 3

触媒化成工業（株）製シリカゾルSI-80P(シリカ濃度; 39.55%,平均粒子径;81nm) 21.49kgに超純水を21.01kg添加し、シリカ濃度20%に稀釈後30分間撹拌した。さらに稀釈したシリカゾルを攪拌しながら80℃に昇温して、1.6%酸性ケイ酸液0.93kgおよび3%アルミン酸ナトリウム液0.93kgを準備し、それぞれ2.8ｇ/minの添加速度で、同時に添加した(添加時間；5.5時間)。添加終了後、さらに同一温度で１時間保持したのち冷却してシリカアルミナ被覆処理をした。
前記のシリカアルミナ被覆処理を施したシリカゾルを23℃で撹拌をおこない、その中に陽イオン交換樹脂を6.40kg投入し、pH値が3以下になるまで撹拌しながら保持し、その後その陽イオン交換樹脂を除去した。さらにシリカゾルに対して限外膜を使用し濃縮をおこない、この段階で固形分濃度を31％に調整した。
次に濃縮したシリカゾルを攪拌しながらpH調整のため5％テトラメチルアンモニウムハイドロオキサイド水溶液を添加しpH値が9.1となった。
さらに殺菌を目的として、前記のシリカゾルを80℃へ昇温し、その温度で1時間撹拌しながら保持した。その後、60℃へ冷却し、3.1％に希釈した過酸化水素水を16.9gを撹拌しながら添加し、1時間撹拌した。なお、過酸化水素水は、全量の50ppmになるように調整した。
殺菌処理をした前記のシリカゾルの粗大粒子数を低減するために、遠心力1900Gで10分間遠心処理を施し、そのシリカゾルの上澄み液を約９０％回収した。
最後に前記の遠心処理を施したシリカゾルを窒素圧0.1kg/cm2の窒素で加圧し、日本ポール社製10μmフィルタ、1.2μｍフィルタさらに0.6μｍフィルタを順番に使用してフィルタリングろ過をした。最後に固形分濃度を30%に調整し研磨サンプルの調製を完了した。 Silica sol SI-80P (Silica concentration: 39.55%, average particle size: 81 nm) 21.01 kg of ultrapure water was added to 21.49 kg and diluted to a silica concentration of 20%, followed by stirring for 30 minutes. Further, the diluted silica sol was heated to 80 ° C. while stirring to prepare 0.93 kg of 1.6% acidic silicic acid solution and 0.93 kg of 3% sodium aluminate solution, which were added simultaneously at an addition rate of 2.8 g / min. (Addition time; 5.5 hours). After completion of the addition, the mixture was further maintained at the same temperature for 1 hour and then cooled to perform silica alumina coating treatment.
The silica sol coated with the above silica-alumina coating is stirred at 23 ° C., and 6.40 kg of cation exchange resin is added to the silica sol, and the mixture is held with stirring until the pH value becomes 3 or less. The resin was removed. Further, the silica sol was concentrated using an ultra-thin film, and the solid concentration was adjusted to 31% at this stage.
Next, a 5% tetramethylammonium hydroxide aqueous solution was added to adjust the pH while stirring the concentrated silica sol, and the pH value became 9.1.
Further, for the purpose of sterilization, the silica sol was heated to 80 ° C. and held at that temperature with stirring for 1 hour. Thereafter, the mixture was cooled to 60 ° C., 16.9 g of hydrogen peroxide diluted to 3.1% was added with stirring, and the mixture was stirred for 1 hour. The hydrogen peroxide solution was adjusted to 50 ppm of the total amount.
In order to reduce the number of coarse particles of the sterilized silica sol, centrifugation was performed at a centrifugal force of 1900 G for 10 minutes, and about 90% of the silica sol supernatant was recovered.
Finally, the silica sol subjected to the above centrifugal treatment was pressurized with nitrogen having a nitrogen pressure of 0.1 kg / cm 2 and filtered using a 10 μm filter, a 1.2 μm filter and a 0.6 μm filter manufactured by Nippon Pole Co., Ltd. in order. Finally, the solid content concentration was adjusted to 30% to complete the preparation of the polished sample.

比較例４Comparative Example 4

触媒化成工業（株）製シリカゾルSI-80P(シリカ濃度; 39.55%,平均粒子径;81nm) 21.49kgに超純水を21.01kg添加し、シリカ濃度20%に稀釈後30分間撹拌した。さらに稀釈したシリカゾルを攪拌しながら80℃に昇温して、1.6%酸性ケイ酸液0.93kgおよび3%アルミン酸ナトリウム液0.93kgを準備し、それぞれ2.8ｇ/minの添加速度で、同時に添加した(添加時間；5.5時間)。添加終了後、さらに同一温度で１時間保持したのち冷却してシリカアルミナ被覆処理をした。
前記のシリカアルミナ被覆処理を施したシリカゾルを23℃で撹拌をおこない、その中に陽イオン交換樹脂を6.40kg投入し、pH値が3以下になるまで撹拌しながら保持し、その後その陽イオン交換樹脂を除去した。さらにシリカゾルに対して限外膜を使用し濃縮をおこない、この段階で固形分濃度を31％に調整した。
次に濃縮したシリカゾルを攪拌しながらpH調整のため5％テトラメチルアンモニウムハイドロオキサイド水溶液を添加しpH値が9.0となった。
さらに殺菌を目的として、前記のシリカゾルを80℃へ昇温し、その温度で1時間撹拌しながら保持した。その後、60℃へ冷却し、3.1％に希釈した過酸化水素水を16.9gを撹拌しながら添加し、1時間撹拌した。なお、過酸化水素水は、全量の50ppmになるように調整した。
最後に殺菌処理を施したシリカゾルを窒素圧0.1kg/cm2の窒素で加圧し、日本ポール社製10μmフィルタ、1.2μｍフィルタを順番に使用してフィルタリングろ過をした。最後に固形分濃度を30%に調整し研磨サンプルの調製を完了した。 Silica sol SI-80P (Silica concentration: 39.55%, average particle size: 81 nm) 21.01 kg of ultrapure water was added to 21.49 kg and diluted to a silica concentration of 20%, followed by stirring for 30 minutes. Further, the diluted silica sol was heated to 80 ° C. while stirring to prepare 0.93 kg of 1.6% acidic silicic acid solution and 0.93 kg of 3% sodium aluminate solution, which were added simultaneously at an addition rate of 2.8 g / min. (Addition time; 5.5 hours). After completion of the addition, the mixture was further maintained at the same temperature for 1 hour and then cooled to perform silica alumina coating treatment.
The silica sol coated with the above silica-alumina coating is stirred at 23 ° C., and 6.40 kg of cation exchange resin is added to the silica sol, and the mixture is held with stirring until the pH value becomes 3 or less. The resin was removed. Further, the silica sol was concentrated using an ultra-thin film, and the solid concentration was adjusted to 31% at this stage.
Next, 5% tetramethylammonium hydroxide aqueous solution was added to adjust the pH while stirring the concentrated silica sol, and the pH value became 9.0.
Further, for the purpose of sterilization, the silica sol was heated to 80 ° C. and held at that temperature with stirring for 1 hour. Thereafter, the mixture was cooled to 60 ° C., 16.9 g of hydrogen peroxide diluted to 3.1% was added with stirring, and the mixture was stirred for 1 hour. The hydrogen peroxide solution was adjusted to 50 ppm of the total amount.
Finally, the sterilized silica sol was pressurized with nitrogen having a nitrogen pressure of 0.1 kg / cm 2 , and filtered using a 10 μm filter and a 1.2 μm filter made by Nippon Pole in order. Finally, the solid content concentration was adjusted to 30% to complete the preparation of the polished sample.

比較例５Comparative Example 5

触媒化成工業（株）製シリカゾルSI-80P(シリカ濃度;40.40%,平均粒子径;81nm) 21.04kgに超純水を21.46kg添加し、シリカ濃度20%に稀釈後30分間撹拌した。
前記の希釈を施したシリカゾルを23℃で撹拌をおこない、その中に陽イオン交換樹脂を6.40kg投入し、pH値が3以下になるまで撹拌しながら保持し、その後その陽イオン交換樹脂を除去した。次にこのシリカゾルを23℃で撹拌をおこない、その中に陰イオン交換樹脂を0.64kg投入し、pH値が5.2以上になるまで撹拌しながら保持し、その後その陰イオン交換樹脂を除去した。さらにこの前記シリカゾルを23℃で撹拌をおこない、その中に再度陽イオン交換樹脂を6.40kg投入し、投入後80℃に昇温して、その温度で3時間撹拌しながら保持した。その後冷却して陽イオン交換樹脂を除去した。さらにこのシリカゾルを23℃で撹拌をおこない、その中に再度陰イオン交換樹脂を0.64kg投入し、投入後40℃に昇温して、その温度で12時間撹拌しながら保持した。その後冷却して陰イオン交換樹脂を除去した。さらに前記のシリカゾルを23℃で撹拌をおこない、その中に陽イオン交換樹脂を6.40kg投入し、投入後シリカゾルのpH値が4以下になるまで撹拌しながら保持した。その後その陽イオン交換樹脂を除去した。前記の一連のイオン交換処理を施したシリカゾルに対して限外膜を使用し濃縮をおこない、この段階で固形分濃度を31％に調整した。
次に濃縮したシリカゾルを攪拌しながらpH調整のため5％クエン酸水溶液を添加しpH値が2.9となった。
さらに殺菌を目的として、前記のシリカゾルを80℃へ昇温し、その温度で1時間撹拌しながら保持した。その後、60℃へ冷却し、3.1％に希釈した過酸化水素水を16.9gを撹拌しながら添加し、1時間撹拌した。なお、過酸化水素水は、全量の50ppmになるように調整した。
殺菌処理をした前記のシリカゾルの粗大粒子数を低減するために、遠心力1900Gで10分間遠心処理を施し、そのシリカゾルの上澄み液を約９０％回収した。
最後に前記の遠心処理を施したシリカゾルを窒素圧0.1kg/cm2の窒素で加圧し、日本ポール社製10μmフィルタ、1.2μｍフィルタさらに0.6μｍフィルタを順番に使用してフィルタリングろ過をした。最後に固形分濃度を30%に調整し研磨サンプルの調製を完了した。 Silica sol SI-80P (Silica concentration: 40.40%, average particle size: 81 nm) 21.04 kg of ultrapure water was added to 21.04 kg, diluted to 20% silica concentration, and stirred for 30 minutes.
The silica sol diluted as described above is stirred at 23 ° C., and 6.40 kg of cation exchange resin is added to it and held while stirring until the pH value becomes 3 or less, and then the cation exchange resin is removed. did. Next, this silica sol was stirred at 23 ° C., and 0.64 kg of an anion exchange resin was added therein, and the silica sol was held with stirring until the pH value became 5.2 or more, and then the anion exchange resin was removed. Further, the silica sol was stirred at 23 ° C., and 6.40 kg of the cation exchange resin was charged therein again. After the charging, the temperature was raised to 80 ° C. and held at that temperature for 3 hours with stirring. Thereafter, it was cooled to remove the cation exchange resin. Further, this silica sol was stirred at 23 ° C., and 0.64 kg of anion exchange resin was again charged therein. After the charging, the temperature was raised to 40 ° C. and held at that temperature for 12 hours with stirring. Thereafter, the anion exchange resin was removed by cooling. Further, the silica sol was stirred at 23 ° C., and 6.40 kg of a cation exchange resin was charged therein, and after the charging, the silica sol was held with stirring until the pH value of the silica sol became 4 or less. The cation exchange resin was then removed. The silica sol subjected to the above series of ion exchange treatments was concentrated using an ultra-membrane, and the solid content concentration was adjusted to 31% at this stage.
Next, a 5% aqueous citric acid solution was added to adjust the pH while stirring the concentrated silica sol, and the pH value became 2.9.
Further, for the purpose of sterilization, the silica sol was heated to 80 ° C. and held at that temperature with stirring for 1 hour. Thereafter, the mixture was cooled to 60 ° C., 16.9 g of hydrogen peroxide diluted to 3.1% was added with stirring, and the mixture was stirred for 1 hour. The hydrogen peroxide solution was adjusted to 50 ppm of the total amount.
In order to reduce the number of coarse particles of the sterilized silica sol, centrifugation was performed at a centrifugal force of 1900 G for 10 minutes, and about 90% of the silica sol supernatant was recovered.
Finally, the silica sol subjected to the above centrifugal treatment was pressurized with nitrogen having a nitrogen pressure of 0.1 kg / cm 2 and filtered using a 10 μm filter, a 1.2 μm filter and a 0.6 μm filter manufactured by Nippon Pole Co., Ltd. in order. Finally, the solid content concentration was adjusted to 30% to complete the preparation of the polished sample.

比較例６Comparative Example 6

触媒化成工業（株）製シリカゾルSI-80P(シリカ濃度;40.40%,平均粒子径;81nm) 21.04kgに超純水を21.46kg添加し、シリカ濃度20%に稀釈後30分間撹拌した。さらに稀釈したシリカゾルを攪拌しながら80℃に昇温して、3.0%酸性ケイ酸液0.5kgおよび2.22%アルミン酸ナトリウム液0.5kgを準備し、それぞれ2.8ｇ/minの添加速度で、同時に添加した(添加時間；3時間)。添加終了後、さらに同一温度で１時間保持したのち冷却してシリカアルミナ被覆処理をした。
前記のシリカアルミナ被覆処理を施したシリカゾルを23℃で撹拌をおこない、その中に陽イオン交換樹脂を6.40kg投入し、pH値が3以下になるまで撹拌しながら保持し、その後その陽イオン交換樹脂を除去した。次にこのシリカゾルを23℃で撹拌をおこない、その中に陰イオン交換樹脂を0.64kg投入し、pH値が5.2以上になるまで撹拌しながら保持し、その後その陰イオン交換樹脂を除去した。さらにこの前記シリカゾルを23℃で撹拌をおこない、その中に再度陽イオン交換樹脂を6.40kg投入し、投入後80℃に昇温して、その温度で3時間撹拌しながら保持した。その後冷却して陽イオン交換樹脂を除去した。前記の一連のイオン交換処理を施したシリカゾルに対して限外膜を使用し濃縮をおこない、この段階で固形分濃度を31％に調整した。
次に濃縮したシリカゾルを攪拌しながらpH調整のため5％クエン酸水溶液を添加しpH値が2.7となった。
さらに殺菌を目的として、前記のシリカゾルを80℃へ昇温し、その温度で1時間撹拌しながら保持した。その後、60℃へ冷却し、0.5％に希釈した次亜塩素酸ナトリウム水溶液を16.9gを撹拌しながら添加し、1時間撹拌した。なお、過酸化水素水は、全量の2ppmになるように調整した。
殺菌処理をした前記のシリカゾルの粗大粒子数を低減するために、遠心力1900Gで10分間遠心処理を施し、そのシリカゾルの上澄み液を約９０％回収した。
最後に前記の遠心処理を施したシリカゾルを窒素圧0.1kg/cm2の窒素で加圧し、日本ポール社製10μmフィルタ、1.2μｍフィルタさらに0.6μｍフィルタを順番に使用してフィルタリングろ過をした。最後に固形分濃度を30%に調整し研磨サンプルの調製を完了した。 Silica sol SI-80P (Silica concentration: 40.40%, average particle size: 81 nm) 21.04 kg of ultrapure water was added to 21.04 kg, diluted to 20% silica concentration, and stirred for 30 minutes. Further, the diluted silica sol was heated to 80 ° C. while stirring to prepare 0.5 kg of a 3.0% acidic silicic acid solution and 0.5 kg of a 2.22% sodium aluminate solution, which were simultaneously added at an addition rate of 2.8 g / min. (Addition time; 3 hours). After completion of the addition, the mixture was further maintained at the same temperature for 1 hour and then cooled to perform silica alumina coating treatment.
The silica sol coated with the above silica-alumina coating is stirred at 23 ° C., and 6.40 kg of cation exchange resin is added to the silica sol, and the mixture is held with stirring until the pH value becomes 3 or less. The resin was removed. Next, this silica sol was stirred at 23 ° C., and 0.64 kg of an anion exchange resin was added therein, and the silica sol was held with stirring until the pH value became 5.2 or more, and then the anion exchange resin was removed. Further, the silica sol was stirred at 23 ° C., and 6.40 kg of the cation exchange resin was charged therein again. After the charging, the temperature was raised to 80 ° C. and held at that temperature for 3 hours with stirring. Thereafter, it was cooled to remove the cation exchange resin. The silica sol subjected to the above series of ion exchange treatments was concentrated using an ultra-membrane, and the solid content concentration was adjusted to 31% at this stage.
Next, 5% citric acid aqueous solution was added to adjust the pH while stirring the concentrated silica sol, and the pH value became 2.7.
Further, for the purpose of sterilization, the silica sol was heated to 80 ° C. and held at that temperature with stirring for 1 hour. Thereafter, the mixture was cooled to 60 ° C., 16.9 g of a sodium hypochlorite aqueous solution diluted to 0.5% was added with stirring, and the mixture was stirred for 1 hour. The hydrogen peroxide solution was adjusted to 2 ppm of the total amount.
In order to reduce the number of coarse particles of the sterilized silica sol, centrifugation was performed at a centrifugal force of 1900 G for 10 minutes, and about 90% of the silica sol supernatant was recovered.
Finally, the silica sol subjected to the above centrifugal treatment was pressurized with nitrogen having a nitrogen pressure of 0.1 kg / cm 2 and filtered using a 10 μm filter, a 1.2 μm filter and a 0.6 μm filter manufactured by Nippon Pole Co., Ltd. in order. Finally, the solid content concentration was adjusted to 30% to complete the preparation of the polished sample.

比較例７Comparative Example 7

触媒化成工業（株）製シリカゾルSI-80P(シリカ濃度;40.40%,平均粒子径;81nm) 21.04kgに超純水を21.46kg添加し、シリカ濃度20%に稀釈後30分間撹拌した。さらに稀釈したシリカゾルを攪拌しながら80℃に昇温して、3.0%酸性ケイ酸液0.5kgおよび0.56%アルミン酸ナトリウム液0.5kgを準備し、それぞれ2.8ｇ/minの添加速度で、同時に添加した(添加時間；3時間)。添加終了後、さらに同一温度で１時間保持したのち冷却してシリカアルミナ被覆処理をした。
前記のシリカアルミナ被覆処理を施したシリカゾルを23℃で撹拌をおこない、その中に陽イオン交換樹脂を6.40kg投入し、pH値が3以下になるまで撹拌しながら保持し、その後その陽イオン交換樹脂を除去した。さらにシリカゾルに対して限外膜を使用し濃縮をおこない、この段階で固形分濃度を31％に調整した。
次に濃縮したシリカゾルを攪拌しながらpH調整のため5％クエン酸水溶液を添加しpH値が2.7となった。
さらに殺菌を目的として、前記のシリカゾルを80℃へ昇温し、その温度で1時間撹拌しながら保持した。その後、60℃へ冷却し、0.5％に希釈した次亜塩素酸ナトリウム水溶液を16.9gを撹拌しながら添加し、1時間撹拌した。なお、過酸化水素水は、全量の2ppmになるように調整した。
殺菌処理をした前記のシリカゾルの粗大粒子数を低減するために、遠心力1900Gで10分間遠心処理を施し、そのシリカゾルの上澄み液を約９０％回収した。
最後に前記の遠心処理を施したシリカゾルを窒素圧0.1kg/cm2の窒素で加圧し、日本ポール社製10μmフィルタ、1.2μｍフィルタさらに0.6μｍフィルタを順番に使用してフィルタリングろ過をした。最後に固形分濃度を30%に調整し研磨サンプルの調製を完了した。 Silica sol SI-80P (Silica concentration: 40.40%, average particle size: 81 nm) 21.04 kg of ultrapure water was added to 21.04 kg, diluted to 20% silica concentration, and stirred for 30 minutes. Further, the diluted silica sol was heated to 80 ° C. while stirring to prepare 0.5 kg of a 3.0% acidic silicic acid solution and 0.5 kg of a 0.56% sodium aluminate solution, which were simultaneously added at an addition rate of 2.8 g / min. (Addition time; 3 hours). After completion of the addition, the mixture was further maintained at the same temperature for 1 hour and then cooled to perform silica alumina coating treatment.
The silica sol coated with the above silica-alumina coating is stirred at 23 ° C., and 6.40 kg of cation exchange resin is added to the silica sol, and the mixture is held with stirring until the pH value becomes 3 or less. The resin was removed. Further, the silica sol was concentrated using an ultra-thin film, and the solid concentration was adjusted to 31% at this stage.
Next, 5% citric acid aqueous solution was added to adjust the pH while stirring the concentrated silica sol, and the pH value became 2.7.
Further, for the purpose of sterilization, the silica sol was heated to 80 ° C. and held at that temperature with stirring for 1 hour. Thereafter, the mixture was cooled to 60 ° C., 16.9 g of a sodium hypochlorite aqueous solution diluted to 0.5% was added with stirring, and the mixture was stirred for 1 hour. The hydrogen peroxide solution was adjusted to 2 ppm of the total amount.
In order to reduce the number of coarse particles of the sterilized silica sol, centrifugation was performed at a centrifugal force of 1900 G for 10 minutes, and about 90% of the silica sol supernatant was recovered.
Finally, the silica sol subjected to the above centrifugal treatment was pressurized with nitrogen having a nitrogen pressure of 0.1 kg / cm 2 and filtered using a 10 μm filter, a 1.2 μm filter and a 0.6 μm filter manufactured by Nippon Pole Co., Ltd. in order. Finally, the solid content concentration was adjusted to 30% to complete the preparation of the polished sample.

比較例８Comparative Example 8

触媒化成工業（株）製シリカゾルSI-80P(シリカ濃度;40.40%,平均粒子径;81nm) 21.04kgに超純水を21.46kg添加し、シリカ濃度20%に稀釈後30分間撹拌した。さらに稀釈したシリカゾルを攪拌しながら80℃に昇温して、3.0%酸性ケイ酸液0.5kgおよび2.22%アルミン酸ナトリウム液0.5kgを準備し、それぞれ2.8ｇ/minの添加速度で、同時に添加した(添加時間；3時間)。添加終了後、さらに同一温度で１時間保持したのち冷却してシリカアルミナ被覆処理をした。
前記のシリカアルミナ被覆処理を施したシリカゾルを23℃で撹拌をおこない、その中に陽イオン交換樹脂を6.40kg投入し、pH値が3以下になるまで撹拌しながら保持し、さらにシリカゾルに対して限外膜を使用し濃縮をおこない、この段階で固形分濃度を31％に調整した。
次に濃縮したシリカゾルを攪拌しながらpH調整のため5％クエン酸水溶液を添加しpH値が2.9となった。
さらに殺菌を目的として、前記のシリカゾルを80℃へ昇温し、その温度で1時間撹拌しながら保持した。その後、60℃へ冷却し、0.5％に希釈した次亜塩素酸ナトリウム水溶液を16.9gを撹拌しながら添加し、1時間撹拌した。なお、過酸化水素水は、全量の2ppmになるように調整した。
最後に殺菌処理を施したシリカゾルを窒素圧0.1kg/cm2の窒素で加圧し、日本ポール社製10μmフィルタ、1.2μｍフィルタを順番に使用してフィルタリングろ過をした。最後に固形分濃度を30%に調整し研磨サンプルの調製を完了した。 Silica sol SI-80P (Silica concentration: 40.40%, average particle size: 81 nm) 21.04 kg of ultrapure water was added to 21.04 kg, diluted to 20% silica concentration, and stirred for 30 minutes. Further, the diluted silica sol was heated to 80 ° C. while stirring to prepare 0.5 kg of a 3.0% acidic silicic acid solution and 0.5 kg of a 2.22% sodium aluminate solution, which were simultaneously added at an addition rate of 2.8 g / min. (Addition time; 3 hours). After completion of the addition, the mixture was further maintained at the same temperature for 1 hour and then cooled to perform silica alumina coating treatment.
The silica sol subjected to the above-mentioned silica-alumina coating treatment is stirred at 23 ° C., and 6.40 kg of cation exchange resin is added to the silica sol, and the mixture is held with stirring until the pH value becomes 3 or less. Concentration was performed using an ultra-membrane, and the solid content concentration was adjusted to 31% at this stage.
Next, a 5% aqueous citric acid solution was added to adjust the pH while stirring the concentrated silica sol, and the pH value became 2.9.
Further, for the purpose of sterilization, the silica sol was heated to 80 ° C. and held at that temperature with stirring for 1 hour. Thereafter, the mixture was cooled to 60 ° C., 16.9 g of a sodium hypochlorite aqueous solution diluted to 0.5% was added with stirring, and the mixture was stirred for 1 hour. The hydrogen peroxide solution was adjusted to 2 ppm of the total amount.
Finally, the sterilized silica sol was pressurized with nitrogen having a nitrogen pressure of 0.1 kg / cm 2 , and filtered using a 10 μm filter and a 1.2 μm filter made by Nippon Pole in order. Finally, the solid content concentration was adjusted to 30% to complete the preparation of the polished sample.

Figure 2006012969
Figure 2006012969

Claims (8)

表面がシリカおよびアルミナで処理された球状シリカ微粒子が水系分散媒に分散してなる固形分濃度５〜５０重量％のシリカゾルであって、ａ）球状シリカ微粒子の平均粒子径が２０〜１１０ｎｍ、ｂ）粒子径が８００ｎｍ以上の粗大粒子の個数が該球状シリカ微粒子濃度１重量％当り３０００個／ｍｌ以下、ｃ）ｐHの範囲がｐH１〜４またはｐH８〜１１およびｄ）無機陰イオンの含有量が２０ｐｐｍ以下の各条件を満たすものであることを特徴とする研磨用シリカゾル。
A silica sol having a solid content concentration of 5 to 50% by weight in which spherical silica fine particles whose surfaces are treated with silica and alumina are dispersed in an aqueous dispersion medium, and a) the average particle size of the spherical silica fine particles is 20 to 110 nm, b ) The number of coarse particles having a particle diameter of 800 nm or more is 3000 particles / ml or less per 1% by weight of the spherical silica fine particle concentration, c) the pH range is pH 1-4 or pH 8-11, and d) the content of inorganic anions. A polishing silica sol characterized by satisfying each condition of 20 ppm or less.
前記表面がシリカおよびアルミナで処理された球状シリカ微粒子におけるアルミナとシリカのモル比ＭA/ＭSが２×１０-6〜１０００×１０-6であることを特徴とする請求項１の研磨用シリカゾル。
2. The polishing according to claim 1, wherein the molar ratio M A / M S of alumina and silica in the spherical silica fine particles whose surface is treated with silica and alumina is 2 × 10 −6 to 1000 × 10 −6 . Silica sol.
次の（ａ）、（ｂ）および（ｃ）の工程を含むことを特徴とする請求項１または２の研磨用シリカゾルの製造方法。
（ａ）水性シリカゾルに、酸性珪酸液または珪酸塩水溶液と、アルミン酸ナトリウム水溶液とを同時に添加、混合してシリカ−アルミナ被覆シリカゾルを得る工程
（ｂ）前記工程（ａ）で得られたシリカ−アルミナ被覆シリカゾルに陽イオン交換処理及び／又は陰イオン交換処理を行った後、必要に応じてｐＨ調整剤を添加して、そのｐHを１〜４または８〜１１の範囲に調整する工程
（ｃ）前記工程（ｂ）で得られたシリカ−アルミナ被覆シリカゾルに遠心分離処理を行い、上澄み液を回収する工程
The method for producing a polishing silica sol according to claim 1 or 2, comprising the following steps (a), (b) and (c).
(A) A step of obtaining an silica-alumina-coated silica sol by simultaneously adding and mixing an acidic silicic acid solution or an aqueous silicate solution and an aqueous sodium aluminate solution to the aqueous silica sol (b) The silica obtained in the step (a) A step of adjusting the pH to a range of 1 to 4 or 8 to 11 by adding a pH adjusting agent as necessary after performing cation exchange treatment and / or anion exchange treatment on the alumina-coated silica sol (c) ) A step of centrifuging the silica-alumina-coated silica sol obtained in the step (b) to recover the supernatant.
前記工程（ａ）において、６０〜１５０℃で０．１〜２０時間、添加、混合を行う請求項３の研磨用シリカゾルの製造方法。
The method for producing a polishing silica sol according to claim 3, wherein the addition and mixing are performed at 60 to 150 ° C for 0.1 to 20 hours in the step (a).
前記工程（ｂ）において、シリカ−アルミナ被覆シリカゾルに陽イオン交換樹脂を接触させて、シリカゾルのｐHを４以下とすることを含む請求項３の研磨用シリカゾルの製造方法。
The method for producing a silica sol for polishing according to claim 3, wherein in the step (b), a cation exchange resin is brought into contact with the silica-alumina-coated silica sol so that the pH of the silica sol is 4 or less.
前記工程（ｂ）において、シリカ−アルミナ被覆シリカゾルに陰イオン交換樹脂を接触させて、シリカゾルのｐHを５以上とすることを含む請求項３の研磨用シリカゾルの製造方法。
4. The method for producing a silica sol for polishing according to claim 3, wherein in the step (b), an anion exchange resin is brought into contact with the silica-alumina-coated silica sol so that the pH of the silica sol is 5 or more.
前記工程（ｂ）における陰イオン交換処理を、シリカ−アルミナ被覆シリカゾル中の無機陰イオンの含有量が２０ｐｐｍ以下になるまで繰り返すことを含む請求項３の研磨用シリカゾルの製造方法。
The method for producing a polishing silica sol according to claim 3, comprising repeating the anion exchange treatment in the step (b) until the content of inorganic anions in the silica-alumina-coated silica sol is 20 ppm or less.
前記工程（ｃ）において、上澄み液の６０〜９９．５％を回収する請求項３の研磨用シリカゾルの製造方法。
The method for producing a polishing silica sol according to claim 3, wherein 60 to 99.5% of the supernatant liquid is recovered in the step (c).
JP2004184947A 2004-06-23 2004-06-23 Silica sol for polish, and its manufacturing method Pending JP2006012969A (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007088461A1 (en) * 2006-02-02 2007-08-09 Element Six (Production) (Proprietary) Limited Glass coated hard and ultra-hard abrasive particles and a method of making them
JP2008181955A (en) * 2007-01-23 2008-08-07 Fujifilm Corp Polishing liquid for metal and polishing method using the same
JP2009155180A (en) * 2007-12-27 2009-07-16 Jgc Catalysts & Chemicals Ltd Particle-linked alumina-silica composite sol and method for manufacturing the same
JP2010095568A (en) * 2008-10-14 2010-04-30 Jgc Catalysts & Chemicals Ltd Silica sol for polishing, composition for polishing, and method for producing silica sol for polishing
CN106661426A (en) * 2014-07-01 2017-05-10 戴蒙得创新股份有限公司 Glass coated cbn abrasives and method of making them
CN110240866A (en) * 2018-03-07 2019-09-17 福吉米株式会社 Composition for polishing
JP2020109053A (en) * 2015-03-31 2020-07-16 日揮触媒化成株式会社 Silica-based composite fine particle dispersion, method for producing the same and polishing slurry containing silica-based composite fine particle dispersion
CN113480942A (en) * 2021-08-06 2021-10-08 大连理工大学 Polycrystalline YAG ceramic chemical mechanical polishing solution

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007088461A1 (en) * 2006-02-02 2007-08-09 Element Six (Production) (Proprietary) Limited Glass coated hard and ultra-hard abrasive particles and a method of making them
JP2008181955A (en) * 2007-01-23 2008-08-07 Fujifilm Corp Polishing liquid for metal and polishing method using the same
JP2009155180A (en) * 2007-12-27 2009-07-16 Jgc Catalysts & Chemicals Ltd Particle-linked alumina-silica composite sol and method for manufacturing the same
JP2010095568A (en) * 2008-10-14 2010-04-30 Jgc Catalysts & Chemicals Ltd Silica sol for polishing, composition for polishing, and method for producing silica sol for polishing
CN106661426A (en) * 2014-07-01 2017-05-10 戴蒙得创新股份有限公司 Glass coated cbn abrasives and method of making them
JP2020109053A (en) * 2015-03-31 2020-07-16 日揮触媒化成株式会社 Silica-based composite fine particle dispersion, method for producing the same and polishing slurry containing silica-based composite fine particle dispersion
CN110240866A (en) * 2018-03-07 2019-09-17 福吉米株式会社 Composition for polishing
US10851267B2 (en) 2018-03-07 2020-12-01 Fujimi Incorporated Polishing composition
TWI798345B (en) * 2018-03-07 2023-04-11 日商福吉米股份有限公司 Polishing composition
CN113480942A (en) * 2021-08-06 2021-10-08 大连理工大学 Polycrystalline YAG ceramic chemical mechanical polishing solution

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