TWI811415B

TWI811415B - Method of polishing magnetic disk substrate, and polishing composition formagnetic disk substrate

Info

Publication number: TWI811415B
Application number: TW108127248A
Authority: TW
Inventors: 安藤順一郎
Original assignee: 日商山口精研工業股份有限公司
Priority date: 2018-08-03
Filing date: 2019-07-31
Publication date: 2023-08-11
Also published as: JP2020021528A; MY195012A; JP7128685B2; TW202007738A

Abstract

一種磁碟基板之研磨方法，其可維持生產性，並實現減少多段研磨方式中粗研磨步驟後基板表面的起伏與滾降；以及其中所使用的研磨劑組成物。 A method for polishing magnetic disk substrates, which can maintain productivity and reduce the fluctuation and roll-off of the substrate surface after the coarse polishing step in a multi-stage polishing method; and an abrasive composition used therein.

本發明的磁碟基板之研磨方法包含多段研磨方式的磁碟基板之研磨方法中的粗研磨步驟中的研磨方法。其包含：(1)使用含有氧化鋁粒子、有機硫酸酯鹽化合物及水之研磨劑組成物A的前段粗研磨的步驟；(2)前段粗研磨後的沖洗處理的步驟；(3)沖洗處理後使用含有膠質氧化矽及水之研磨劑組成物B的後段粗研磨的步驟；其中，使研磨劑組成物A及/或研磨劑組成物B中含有特定的水溶性高分子化合物。 The polishing method of the magnetic disk substrate of the present invention includes the polishing method in the rough polishing step of the multi-stage polishing method of the magnetic disk substrate. It includes: (1) the step of rough grinding in the front stage using the abrasive composition A containing alumina particles, organic sulfate ester salt compounds and water; (2) the step of rinsing after the rough grinding in the front stage; (3) rinsing. Then, the abrasive composition B containing colloidal silica and water is used for the subsequent coarse grinding step; wherein, the abrasive composition A and/or the abrasive composition B is made to contain a specific water-soluble polymer compound.

Description

磁碟基板之研磨方法及磁碟基板用研磨劑組成物 Polishing method for magnetic disk substrate and abrasive composition for magnetic disk substrate

本發明係關於一種廣泛用作磁碟驅動器之磁碟基板的鋁製硬碟基板之研磨方法。其中係關於一種於鋁合金基板的表面形成有鎳-磷鍍覆皮膜之磁記錄媒體用磁碟基板的研磨方法。特別是關於一種在以多段研磨方式進行於鋁合金基板的表面形成有鎳-磷鍍覆皮膜之磁記錄媒體用磁碟基板的研磨時，在最終研磨步驟之前的研磨步驟中進行的研磨方法。 The present invention relates to a method for grinding aluminum hard disk substrates, which are widely used as disk substrates for disk drives. The invention relates to a method for polishing a disk substrate for a magnetic recording medium in which a nickel-phosphorus plating film is formed on the surface of an aluminum alloy substrate. In particular, it relates to a polishing method performed in a polishing step before a final polishing step when polishing a magnetic disk substrate for a magnetic recording medium with a nickel-phosphorus plating film formed on the surface of an aluminum alloy substrate using a multi-stage polishing method.

近年來，磁碟驅動器邁向小型化、大容量化，而尋求高記錄密度化。於是，必須提升高記錄密度磁信號的檢測感度，而正在開發進一步降低磁頭之浮起高度、縮小單位記錄面積的技術。對於磁碟基板，為了應對磁頭之低浮起化與確保記錄面積，嚴格要求提升平滑性及平坦性(減少表面粗糙度、起伏、滾降)及減少表面缺陷(減少殘留研磨粒、刮痕、突起、凹處等)。 In recent years, magnetic disk drives have become smaller and larger in capacity, and higher recording densities have been sought. Therefore, it is necessary to improve the detection sensitivity of high recording density magnetic signals, and technology is being developed to further reduce the flying height of the magnetic head and reduce the unit recording area. For magnetic disk substrates, in order to reduce head lift and ensure recording area, there are strict requirements to improve smoothness and flatness (reduce surface roughness, undulations, roll-off) and reduce surface defects (reduce residual abrasive grains, scratches, protrusions, recesses, etc.).

對於這種要求，從兼顧起伏小且滾降小等表面品質提升與生產性提升的觀點來看，在磁碟基板之研磨方法中，大多採用具有兩階段以上之研磨步驟的多段研磨方式(專利文獻1)。一般而言，多段研磨方式的最終研磨步驟、亦即精研磨步驟中，從減少表面粗糙度、減少刮痕、突起、凹處等缺陷的觀點來看，係使用包含二氧化矽粒子的研磨劑組成物。另一方面，其之前的研磨步驟(亦稱為粗研磨步驟)中，從提升生產性的觀點來看，大多使用包含氧化鋁粒子的研磨劑組成物。 In response to such requirements, from the viewpoint of improving surface quality such as small undulations and small roll-off, and improving productivity, most magnetic disk substrate polishing methods use a multi-stage polishing method with two or more polishing steps (patented Document 1). Generally speaking, in the final polishing step of the multi-stage polishing method, that is, the fine polishing step, an abrasive containing silica particles is used from the perspective of reducing surface roughness and defects such as scratches, protrusions, and recesses. composition. On the other hand, in the previous polishing step (also called a rough polishing step), from the viewpoint of improving productivity, a polishing composition containing alumina particles is often used.

然而，進行鋁製硬碟基板的研磨時，相較於鋁合金基板，氧化鋁粒子的硬度相當高，因此，由於將氧化鋁研磨粒固定於基板而起伏加劇，此情況對精研磨造成不良影響而成為問題。 However, when polishing an aluminum hard disk substrate, the hardness of the alumina particles is much higher than that of the aluminum alloy substrate. Therefore, the alumina abrasive grains are fixed to the substrate and the fluctuations are aggravated. This situation has a negative impact on fine polishing. and become a problem.

作為這種問題的解決對策，有人揭示了一種研磨方法，係在粗研磨步驟中以同一研磨機進行使用含有氧化鋁之研磨劑組成物的研磨及使用含有膠質氧化矽之研磨劑組成物的研磨(專利文獻2)。再者，亦有人揭示了一種在使用含有氧化鋁之研磨劑組成物的研磨與使用含有膠質氧化矽之研磨劑組成物的研磨之間供給不含研磨粒之清洗液的研磨方法(專利文獻3)。 As a solution to this problem, a polishing method has been disclosed in which polishing using an abrasive composition containing alumina and polishing using a polishing composition containing colloidal silica are performed in the same polishing machine in the rough polishing step. (Patent document 2). Furthermore, someone has also disclosed a polishing method in which a cleaning solution containing no abrasive particles is supplied between polishing using an abrasive composition containing alumina and polishing using an abrasive composition containing colloidal silica (Patent Document 3) ).

又，亦有人提出了在使用包含研磨材料、研磨助劑及水的研磨材料組成物來研磨磁記錄媒體基板時，氧化鋁研磨粒為研磨材料的情況下，研磨助劑為脂肪族系有機硫酸鹽，藉此實現研磨速度提升與表面粗糙度降低(專利文獻4)。 In addition, it has also been proposed that when a magnetic recording medium substrate is polished using an abrasive composition containing a polishing material, a polishing aid and water, when alumina abrasive grains are used as the polishing material, the polishing aid is an aliphatic organic sulfuric acid. Salt, thereby increasing the polishing speed and reducing surface roughness (Patent Document 4).

[先前技術文獻] [Prior technical literature]

專利文獻 patent documents

專利文獻1：日本特開昭62-208869號公報 Patent Document 1: Japanese Patent Application Publication No. Sho 62-208869

專利文獻2：日本特開2012-25873號公報 Patent Document 2: Japanese Patent Application Publication No. 2012-25873

專利文獻3：日本特開2012-43493號公報 Patent Document 3: Japanese Patent Application Publication No. 2012-43493

專利文獻4：國際公開第1998/021289號 Patent Document 4: International Publication No. 1998/021289

隨著磁碟驅動器的大容量化，對基板之表面品質所要求的特性變得更加嚴格，在磁碟基板的研磨步驟中，尋求維持生產性，並且進一步減少基板表面上的起伏與滾降。 As the capacity of disk drives increases, the characteristics required for the surface quality of the substrate have become more stringent. In the polishing step of the disk substrate, it is sought to maintain productivity and further reduce the undulation and roll-off on the substrate surface.

於是，本發明提供一種磁碟基板之研磨方法，其可實現維持生產性，並且減少多段研磨方式中的粗研磨步驟後基板表面的起伏與滾降；以及其中所使用的磁碟基板用研磨劑組成物。 Therefore, the present invention provides a method for polishing a magnetic disk substrate, which can maintain productivity and reduce the fluctuation and roll-off of the substrate surface after the rough grinding step in a multi-stage polishing method; and the abrasive for magnetic disk substrates used therein. composition.

為了解決上述課題，根據本發明，可提供以下的磁碟基板之研磨方法及磁碟基板用研磨劑組成物。 In order to solve the above problems, according to the present invention, the following polishing method for a magnetic disk substrate and a polishing composition for a magnetic disk substrate can be provided.

[1]一種磁碟基板之研磨方法，其具有下述(1)~(3)的步驟，且以同一研磨機進行各步驟(1)~(3)。 [1] A method of polishing a magnetic disk substrate, which has the following steps (1) to (3), and uses the same polishing machine to perform each step (1) to (3).

(1)將含有氧化鋁粒子、水溶性高分子化合物、有機硫酸酯鹽化合物及水的研磨劑組成物A供給至研磨機，進行磁碟基板之前段研磨的步驟 (1) The step of supplying the abrasive composition A containing alumina particles, a water-soluble polymer compound, an organic sulfate ester salt compound, and water to a grinder to perform polishing of the disk substrate in the previous stage

(2)將步驟(1)所得到的該磁碟基板進行沖洗處理的步驟 (2) The step of rinsing the disk substrate obtained in step (1)

(3)將含有膠質氧化矽、水溶性高分子化合物及水的研磨劑組成物B供給至研磨機，進行該磁碟基板之後段研磨的步驟。 (3) The abrasive composition B containing colloidal silica, a water-soluble polymer compound and water is supplied to the grinder, and the subsequent step of grinding the disk substrate is performed.

[4]如該[1]至[3]中任一項之磁碟基板之研磨方法，其中，該水溶性高分子化合物係以具有羧酸基之單體及具有磺酸基之單體為必要單體的共聚物，且其重量平均分子量為1,000~1,000,000。 [4] The method for polishing a magnetic disk substrate according to any one of [1] to [3], wherein the water-soluble polymer compound is a monomer having a carboxylic acid group and a monomer having a sulfonic acid group. A copolymer of essential monomers with a weight average molecular weight of 1,000~1,000,000.

[5]如該[4]之磁碟基板之研磨方法，其中，該水溶性高分子化合物，即以具有羧酸基之單體及具有磺酸基之單體為必要單體的共聚物，係以具有羧酸基之單體與具有磺酸基之單體及具有醯胺基之單體為必要單體的共聚物，且其重量平均分子量為1,000~1,000,000。 [5] The method for polishing a disk substrate according to [4], wherein the water-soluble polymer compound is a copolymer using a monomer having a carboxylic acid group and a monomer having a sulfonic acid group as essential monomers, It is a copolymer with a monomer having a carboxylic acid group, a monomer having a sulfonic acid group and a monomer having an amide group as essential monomers, and its weight average molecular weight is 1,000~1,000,000.

[6]如該[4]或[5]之磁碟基板之研磨方法，其中，該具有羧酸基之單體係選自丙烯酸或其鹽、甲基丙烯酸或其鹽的單體，該水溶性高分子化合物中源自具有羧酸基之單體的構成單元的比例為5~95mol%。 [6] The method for polishing a magnetic disk substrate according to [4] or [5], wherein the monomer having a carboxylic acid group is selected from the group consisting of acrylic acid or its salts, methacrylic acid or its salts, and the water-soluble monomer The proportion of structural units derived from monomers having carboxylic acid groups in the polymer compound is 5 to 95 mol%.

[7]如該[4]或[5]之磁碟基板之研磨方法，其中，該具有磺酸基之單體係選自異戊二烯磺酸、2-丙烯醯胺-2-甲基丙磺酸、2-甲基丙烯醯胺-2-甲基丙磺酸、苯乙烯磺酸、乙烯磺酸、烯丙基磺酸、異戊烯磺酸、乙烯萘磺酸及該等之鹽的單體，該水溶性高分子化合物中源自具有磺酸基之單體的構成單元的比例為5~95mol%。 [7] The method for polishing a disk substrate according to [4] or [5], wherein the monosystem having a sulfonic acid group is selected from the group consisting of isoprene sulfonic acid and 2-acrylamide-2-methyl. Propanesulfonic acid, 2-methacrylamide-2-methylpropanesulfonic acid, styrenesulfonic acid, ethylenesulfonic acid, allylsulfonic acid, isopentenesulfonic acid, vinyl naphthalenesulfonic acid and their salts The proportion of structural units derived from the monomer having a sulfonic acid group in the water-soluble polymer compound is 5 to 95 mol%.

[8]如該[5]之磁碟基板之研磨方法，其中，該具有醯胺基之單體係選自丙烯醯胺、甲基丙烯醯胺、N-烷基丙烯醯胺、N-烷基甲基丙烯醯胺的單體。 [8] The method for polishing a disk substrate according to [5], wherein the monosystem having an amide group is selected from the group consisting of acrylamide, methacrylamide, N-alkyl acrylamide, and N-alkyl Monomer of methacrylamide.

[9]如該[1]至[3]中任一項之磁碟基板之研磨方法，其中，該水溶性高分子化合物係包含以具有羧酸基之單體為必要單體的聚合物與以具有磺酸基之單體為必要單體的聚合物的混合物，該以具有羧酸基之單體為必要單體的聚合物及該以具有磺酸基之單體為必要單體的聚合物的重量平均分子量分別為1,000~1,000,000，以具有羧酸基之單體為必要單體的聚合物的比例為5~95質量%，且以具有磺酸基之單體為必要單體的聚合物的比例為5~95質量%。 [9] The method for polishing a disk substrate according to any one of [1] to [3], wherein the water-soluble polymer compound contains a polymer containing a monomer having a carboxylic acid group as an essential monomer and A mixture of polymers using a monomer having a sulfonic acid group as an essential monomer, a polymer using a monomer having a carboxylic acid group as an essential monomer, and a polymerization of a monomer having a sulfonic acid group as an essential monomer The weight average molecular weight of the polymer is 1,000 to 1,000,000, the proportion of the polymer using a monomer with a carboxylic acid group as an essential monomer is 5 to 95% by mass, and the polymerization uses a monomer with a sulfonic acid group as an essential monomer. The proportion of substances is 5~95% by mass.

[10]如該[1]至[9]中任一項之磁碟基板之研磨方法，其中，該有機硫酸酯鹽化合物係以下列通式(1)表示：R-O-SO₃M (1) [10] The method for polishing a disk substrate according to any one of [1] to [9], wherein the organic sulfate ester salt compound is represented by the following general formula (1): RO-SO ₃ M (1)

式中，R表示碳數5~21的直鏈或分支之烷基、烯基、芳基或烷基芳基，M表示鹼金屬、鹼土金屬、銨離子或有機陽離子。 In the formula, R represents a linear or branched alkyl, alkenyl, aryl or alkylaryl group having 5 to 21 carbon atoms, and M represents an alkali metal, alkaline earth metal, ammonium ion or organic cation.

[11]如該[1]至[9]中任一項之磁碟基板之研磨方法，其中，該有機硫酸酯鹽化合物係以下列通式(2)表示：R-O-(AO)_n-SO₃M (2) [11] The method for polishing a disk substrate according to any one of [1] to [9], wherein the organic sulfate ester salt compound is represented by the following general formula (2): RO-(AO) _n -SO _3M (2)

式中，R表示碳數5~21的直鏈或分支之烷基、烯基、芳基或烷基芳基，AO表示碳數2或3之氧伸烷基，n表示1~30之整數，M表示鹼金屬、鹼土金屬、銨離子或有機陽離子。 In the formula, R represents a linear or branched alkyl, alkenyl, aryl or alkylaryl group with 5 to 21 carbon atoms, AO represents an oxyalkylene group with 2 or 3 carbon atoms, and n represents an integer from 1 to 30. , M represents alkali metal, alkaline earth metal, ammonium ion or organic cation.

[12]如該[1]至[11]中任一項之磁碟基板之研磨方法，其中，該研磨劑組成物A及該研磨劑組成物B進一步含有酸及/或其鹽，且pH值(25℃)在0.1~4.0的範圍。 [12] The method for polishing a magnetic disk substrate according to any one of [1] to [11], wherein the abrasive composition A and the abrasive composition B further contain an acid and/or a salt thereof, and the pH The value (25℃) is in the range of 0.1~4.0.

[13]如該[1]至[12]中任一項之磁碟基板之研磨方法，其中，該研磨劑組成物A及該研磨劑組成物B進一步含有氧化劑。 [13] The method for polishing a magnetic disk substrate according to any one of [1] to [12], wherein the abrasive composition A and the abrasive composition B further contain an oxidizing agent.

[14]如該[1]至[13]中任一項之磁碟基板之研磨方法，其中，針對在鋁合金基板的表面形成有鎳-磷鍍覆皮膜的磁記錄媒體用磁碟基板，在以多段研磨方式進行研磨時，係在最終研磨步驟之前的研磨步驟中進行。 [14] The method for polishing a magnetic disk substrate according to any one of [1] to [13], wherein the magnetic disk substrate for a magnetic recording medium has a nickel-phosphorus plating film formed on the surface of an aluminum alloy substrate, When grinding is performed in a multi-stage grinding method, it is performed in the grinding step before the final grinding step.

[15]一種磁碟基板用研磨劑組成物，係在如該[2]或[3]之磁碟基板之研磨方法中，步驟(3)所使用的研磨劑組成物B，其含有膠質氧化矽、水溶性高分子化合物及水。 [15] An abrasive composition for magnetic disk substrates, which is the abrasive composition B used in step (3) of the magnetic disk substrate polishing method of [2] or [3], which contains colloidal oxide Silicon, water-soluble polymer compounds and water.

[16]如該[15]之磁碟基板用研磨劑組成物，其中，該水溶性高分子化合物係以具有羧酸基之單體及具有磺酸基之單體為必要單體的共聚物，且其重量平均分子量為1,000~1,000,000。 [16] The abrasive composition for magnetic disk substrates of [15], wherein the water-soluble polymer compound is a copolymer using a monomer having a carboxylic acid group and a monomer having a sulfonic acid group as essential monomers. , and its weight average molecular weight is 1,000~1,000,000.

[17]如該[16]之磁碟基板用研磨劑組成物，其中，該水溶性高分子化合物，即以具有羧酸基之單體及具有磺酸基之單體為必要單體的共聚物，係以具有羧酸基之單體與具有磺酸基之單體及具有醯胺基之單體為必要單體的共聚物，且其重量平均分子量為1,000~1,000,000。 [17] The abrasive composition for magnetic disk substrates of [16], wherein the water-soluble polymer compound is a copolymer of a monomer having a carboxylic acid group and a monomer having a sulfonic acid group as essential monomers It is a copolymer with a monomer having a carboxylic acid group, a monomer having a sulfonic acid group and a monomer having an amide group as essential monomers, and its weight average molecular weight is 1,000~1,000,000.

[18]如該[16]或[17]之磁碟基板用研磨劑組成物，其中，該具有羧酸基之單體係選自丙烯酸或其鹽、甲基丙烯酸或其鹽的單體，該水溶性高分子化合物中源自具有羧酸基之單體的構成單元的比例為5~95mol%。 [18] The abrasive composition for magnetic disk substrates of [16] or [17], wherein the monomer having a carboxylic acid group is selected from the group consisting of acrylic acid or its salts, methacrylic acid or its salts, The proportion of structural units derived from a monomer having a carboxylic acid group in the water-soluble polymer compound is 5 to 95 mol%.

[19]如該[16]或[17]之磁碟基板用研磨劑組成物，其中，該具有磺酸基之單體係選自異戊二烯磺酸、2-丙烯醯胺-2-甲基丙磺酸、2-甲基丙烯醯胺-2-甲基丙磺酸、苯乙烯磺酸、乙烯磺酸、烯丙基磺酸、異戊烯磺酸、乙烯萘磺酸及該等之鹽的單體，該水溶性高分子化合物中源自具有磺酸基之單體的構成單元的比例為5~95mol%。 [19] The abrasive composition for magnetic disk substrates of [16] or [17], wherein the monosystem having a sulfonic acid group is selected from the group consisting of isoprene sulfonic acid and 2-acrylamide-2- Methylpropanesulfonic acid, 2-methacrylamide-2-methylpropanesulfonic acid, styrenesulfonic acid, ethylenesulfonic acid, allylsulfonic acid, isopentenesulfonic acid, vinyl naphthalenesulfonic acid and the like The proportion of structural units derived from the monomer having a sulfonic acid group in the water-soluble polymer compound is 5 to 95 mol%.

[20]如該[17]之磁碟基板用研磨劑組成物，其中，該具有醯胺基之單體係選自丙烯醯胺、甲基丙烯醯胺、N-烷基丙烯醯胺、N-烷基甲基丙烯醯胺的單體。 [20] The abrasive composition for magnetic disk substrates of [17], wherein the monosystem having an amide group is selected from the group consisting of acrylamide, methacrylamide, N-alkyl acrylamide, N -Monomer of alkyl methacrylamide.

[21]如該[15]之磁碟基板用研磨劑組成物，其中，該水溶性高分子化合物係包含以具有羧酸基之單體為必要單體的聚合物與以具有磺酸基之單體為必要單體的聚合物的混合物，該以具有羧酸基之單體為必要單體的聚合物及該以具有磺酸基之單體為必要單體的聚合物的重量平均分子量分別為1,000~1,000,000，以具有羧酸基之單體為必要單體的聚合物的比例為5~95質量%，且以具有磺酸基之單體為必要單體的聚合物的比例為5~95質量%。 [21] The abrasive composition for magnetic disk substrates of [15], wherein the water-soluble polymer compound contains a polymer containing a monomer having a carboxylic acid group as an essential monomer and a polymer containing a sulfonic acid group. The weight average molecular weights of the mixture of polymers in which the monomer is an essential monomer, the polymer in which the monomer with a carboxylic acid group is the essential monomer, and the polymer in which the monomer with a sulfonic acid group is the essential monomer are respectively is 1,000~1,000,000, the proportion of the polymer using the monomer having a carboxylic acid group as the essential monomer is 5~95% by mass, and the proportion of the polymer using the monomer having the sulfonic acid group as the essential monomer is 5~ 95% by mass.

根據本發明，可得到以下效果：能夠高生產性地製造多段研磨方式中的粗研磨步驟後基板表面上的起伏與滾降減少的基板。 According to the present invention, it is possible to produce a substrate with reduced undulations and roll-off on the surface of the substrate after the rough polishing step in the multi-stage polishing system with high productivity.

A、B、C、D‧‧‧點 Point A, B, C, D‧‧‧

h‧‧‧垂線 h‧‧‧vertical line

j、k、m、t‧‧‧線 j, k, m, t‧‧‧ line

圖1係基板之剖面圖，用以對研磨基板表面時滾降的測量進行說明。 Figure 1 is a cross-sectional view of a substrate used to illustrate the measurement of roll-off when grinding the substrate surface.

以下，對本發明之實施形態進行說明。本發明並不限定於以下實施形態，只要不脫離發明的範圍，可加以變更、修正、改良。 Hereinafter, embodiments of the present invention will be described. The present invention is not limited to the following embodiments, and changes, corrections, and improvements can be made without departing from the scope of the invention.

本發明係關於包含多段研磨方式中的粗研磨步驟與精研磨步驟的磁碟基板之研磨方法中的粗研磨步驟，其係將粗研磨步驟在同一研磨機中進行研磨的方法。在進行(1)使用含有氧化鋁粒子、有機硫酸酯鹽化合物及水的研磨劑組成物A的前段粗研磨、(2)前段粗研磨後的沖洗處理、(3)沖洗處理後使用含有膠質氧化矽及水之研磨劑組成物B的後段粗研磨時，使研磨劑組成物A及/或研磨劑組成物B中含有特定的水溶性高分子化合物。藉此，可維持研磨速度，並且減少粗研磨步驟後基板表面上的起伏與滾降，本發明係基於此見解。 The present invention relates to a rough polishing step in a magnetic disk substrate polishing method that includes a rough polishing step and a fine polishing step in a multi-stage polishing method. The invention is a method of polishing the rough polishing step in the same polishing machine. (1) rough grinding in the first stage using the abrasive composition A containing alumina particles, an organic sulfate ester salt compound and water, (2) rinsing treatment after the rough grinding in the first stage, and (3) after the rinsing treatment, using the abrasive composition A containing alumina particles, an organic sulfate ester salt compound and water. During the subsequent rough grinding of silicon and water abrasive composition B, a specific water-soluble polymer compound is included in abrasive composition A and/or abrasive composition B. Thereby, the polishing speed can be maintained and the undulations and roll-off on the substrate surface after the rough polishing step can be reduced. The present invention is based on this insight.

以下，對本發明的磁碟基板之研磨方法進行說明。本發明之研磨方法中的被研磨基板為磁碟基板，較佳為鍍鎳-磷之鋁製磁碟基板。 Hereinafter, the polishing method of the magnetic disk substrate of the present invention will be described. The substrate to be polished in the polishing method of the present invention is a magnetic disk substrate, preferably a nickel-phosphorus plated aluminum magnetic disk substrate.

步驟(1)：前段的研磨 Step (1): Preliminary grinding

本發明的磁碟基板之研磨方法具有步驟(1)，其係多段研磨方式中的粗研磨步驟，將含有氧化鋁粒子、有機硫酸酯鹽化合物及水的研磨劑組成物A供給至被研磨基板的研磨對象面，使研磨墊與研磨對象面接觸，移動研磨墊及/或被研磨對象基板來將研磨對象面進行研磨。步驟(1)所使用的研磨機並無特別限定，可使用磁碟基板研磨用的習知研磨機。 The polishing method of the magnetic disk substrate of the present invention has step (1), which is a rough polishing step in a multi-stage polishing method. The polishing agent composition A containing alumina particles, organic sulfate ester salt compounds and water is supplied to the substrate to be polished. The polishing target surface is brought into contact with the polishing pad, and the polishing pad and/or the substrate to be polished is moved to polish the polishing target surface. The grinder used in step (1) is not particularly limited, and a conventional grinder used for grinding disk substrates can be used.

步驟(2)：沖洗處理 Step (2): Rinse

從多段研磨方式中的粗研磨步驟後基板表面上的起伏減少的觀點來看，本發明之基板研磨方法在步驟(1)之後具有在同一研磨機中將步驟(1)所得到之基板進行沖洗處理的步驟(步驟(2))。用於沖洗處理的沖洗液並無特別限制，從經濟性的觀點來看，可使用蒸餾水、離子交換水、純水及超純水等的水。又，從生產性的觀點來看，步驟(2)係不將被研磨基板從步驟(1)所使用之研磨機取出，而在相同研磨機內進行。此外，在本發明中，沖洗處理係指以排出殘留於基板表面之研磨粒、研磨屑為目的的處理。 From the viewpoint of reducing the undulations on the substrate surface after the rough grinding step in the multi-stage grinding method, the substrate grinding method of the present invention includes rinsing the substrate obtained in step (1) in the same grinder after step (1). Processing steps (step (2)). The rinse liquid used for the rinse treatment is not particularly limited. From an economical point of view, water such as distilled water, ion exchange water, pure water, ultrapure water, etc. can be used. Furthermore, from the viewpoint of productivity, step (2) is performed in the same grinder without removing the substrate to be polished from the grinder used in step (1). In addition, in the present invention, the flushing process refers to a process for the purpose of discharging the abrasive grains and abrasive dust remaining on the surface of the substrate.

步驟(3)：後段的研磨 Step (3): Later grinding

從減少多段研磨方式中的粗研磨步驟後基板表面上之起伏的觀點來看，本發明的磁碟基板之研磨方法具有步驟(3)，將含有膠質氧化矽及水的研磨劑組成物B供給至沖洗處理步驟(2)所得到之基板的研磨對象面，使研磨墊與研磨對象面接觸，移動研磨墊及/或該被研磨基板來將研磨對象面進行研磨。從生產性提升的觀點及粗研磨步驟後基板表面上之起伏減少的觀點來看，步驟(1)~(3)係在同一研磨機中進行。 From the viewpoint of reducing the undulations on the substrate surface after the rough grinding step in the multi-stage grinding method, the grinding method of the magnetic disk substrate of the present invention has step (3) of supplying the abrasive composition B containing colloidal silica and water. To the polishing target surface of the substrate obtained in the rinsing process step (2), the polishing pad is brought into contact with the polishing target surface, and the polishing pad and/or the substrate to be polished is moved to polish the polishing target surface. From the viewpoint of productivity improvement and the reduction of undulations on the substrate surface after the rough grinding step, steps (1) to (3) are performed in the same grinding machine.

本發明之基板研磨方法係在上述多段研磨方式中的前段粗研磨步驟(1)、沖洗處理步驟(2)、後段粗研磨步驟(3)中，使前段粗研磨步驟(1)及/或後段粗研磨步驟(3)所使用的研磨劑組成物含有特定的水溶性高分子化合物，藉此有效率地製造粗研磨步驟後基板表面上之起伏與滾降有效地減少的基板。 The substrate polishing method of the present invention includes the front rough grinding step (1), the rinse treatment step (2), and the rear rough grinding step (3) in the above-mentioned multi-stage polishing method. The abrasive composition used in the rough grinding step (3) contains a specific water-soluble polymer compound, thereby efficiently producing a substrate in which undulations and roll-off on the surface of the substrate after the rough grinding step are effectively reduced.

具體而言，本發明的磁碟基板之研磨方法具有以下第1至第3的研磨方法。第1至第3的研磨方法分別具有(1)~(3)步驟，並以同一研磨機進行各步驟(1)~(3)。 Specifically, the polishing method of the magnetic disk substrate of the present invention includes the following first to third polishing methods. The first to third grinding methods respectively have steps (1) to (3), and the same grinder is used to perform each step (1) to (3).

[第1研磨方法] [First grinding method]

(2)將步驟(1)所得到之磁碟基板進行沖洗處理的步驟 (2) The step of rinsing the disk substrate obtained in step (1)

(3)將含有膠質氧化矽及水的研磨劑組成物B供給至研磨機，進行磁碟基板之後段研磨的步驟 (3) Supply the abrasive composition B containing colloidal silica and water to the grinder, and perform the subsequent step of grinding the disk substrate

[第2研磨方法] [Second grinding method]

(1)將含有氧化鋁粒子、有機硫酸酯鹽化合物及水的研磨劑組成物A供給至研磨機，進行磁碟基板之前段研磨的步驟 (1) The step of supplying the abrasive composition A containing alumina particles, an organic sulfate ester salt compound, and water to a polishing machine to perform polishing of the disk substrate in the previous stage

(3)將含有膠質氧化矽、水溶性高分子化合物及水的研磨劑組成物B供給至研磨機，進行磁碟基板之後段研磨的步驟 (3) Supply the abrasive composition B containing colloidal silica, a water-soluble polymer compound and water to the grinder, and perform the subsequent step of grinding the disk substrate

[第3研磨方法] [Third grinding method]

以下，對本發明之基板研磨方法所使用的研磨劑組成物進行說明。 Next, the abrasive composition used in the substrate polishing method of the present invention will be described.

(A)研磨劑組成物A (A) Abrasive composition A

本發明的磁碟基板之研磨方法的步驟(1)所使用之研磨劑組成物A為含有氧化鋁粒子的水系組成物，其含有水溶性高分子化合物作為必要成分或任意成分。此處，水溶性高分子化合物較佳為包含以具有羧酸基之單體為必要單體的聚合物與以具有磺酸基之單體為必要單體的聚合物的混合物及/或以具有羧酸基之單體及具有磺酸基之單體為必要單體的共聚物。此外，研磨劑組成物A係含有有機硫酸酯鹽化合物的組成物。亦可進一步含有酸及/或其鹽用於調整pH或作為任意成分。又，亦可含有氧化劑作為研磨促進劑。 The abrasive composition A used in step (1) of the magnetic disk substrate polishing method of the present invention is an aqueous composition containing alumina particles, and contains a water-soluble polymer compound as an essential or optional component. Here, the water-soluble polymer compound is preferably a mixture containing a polymer containing a monomer having a carboxylic acid group as an essential monomer and a polymer containing a monomer having a sulfonic acid group as an essential monomer and/or a mixture having The monomer with a carboxylic acid group and the monomer with a sulfonic acid group are copolymers of essential monomers. Furthermore, the polishing composition A is a composition containing an organic sulfate ester salt compound. An acid and/or its salt may be further contained for pH adjustment or as an optional component. Furthermore, an oxidizing agent may be contained as a polishing accelerator.

(A-1)氧化鋁粒子 (A-1) Aluminum oxide particles

氧化鋁粒子較佳為包含α-氧化鋁及/或中間氧化鋁。作為中間氧化鋁，可列舉：γ-氧化鋁、δ-氧化鋁、θ-氧化鋁等。又，包含α-氧化鋁與中間氧化鋁兩者時的混合比(中間氧化鋁/α-氧化鋁，質量比)較佳為0.1~2.0，再佳為0.5~1.0。 The alumina particles preferably contain α-alumina and/or intermediate alumina. Examples of intermediate alumina include γ-alumina, δ-alumina, θ-alumina, and the like. Moreover, when both α-alumina and intermediate alumina are included, the mixing ratio (intermediate alumina/α-alumina, mass ratio) is preferably 0.1 to 2.0, more preferably 0.5 to 1.0.

作為製造氧化鋁時的原料，可列舉：三水鋁石：Al₂O₃．3H₂O、水鋁石：Al₂O₃．H₂O、擬水鋁石：Al₂O₃．nH₂O(n=1~2)等。該等氧化鋁原料例如係用以下方法製備。 Examples of raw materials for producing alumina include: gibbsite: Al ₂ O ₃ . 3H ₂ O, diaspore: Al ₂ O ₃ ． H ₂ O, pseudodiaspore: Al ₂ O ₃ . nH ₂ O(n=1~2) etc. These alumina raw materials are prepared by the following method, for example.

三水鋁石：Al₂O₃．3H₂O Gibbsite: Al ₂ O ₃ . 3H ₂ O

藉由使鋁礬土在氫氧化鈉的熱溶液中溶解，將利用過濾去除不溶成分而得的溶液進行冷卻，並將結果所得之沉澱物進行乾燥而得。 It is obtained by dissolving bauxite in a hot solution of sodium hydroxide, cooling the solution obtained by removing insoluble components by filtration, and drying the resulting precipitate.

水鋁石：Al₂O₃．H₂O Diaspore: Al ₂ O ₃ . H ₂ O

藉由將由金屬鋁與醇的反應而得的烷氧化鋁：Al(OR)₃進行水解而得。 It is obtained by hydrolyzing aluminum alkoxide: Al(OR) ₃ , which is obtained by the reaction of metallic aluminum and alcohol.

擬水鋁石：Al₂O₃．nH₂O(n=1~2) Pseudodiaspore: Al ₂ O ₃ . nH ₂ O(n=1~2)

將三水鋁石在鹼性氣體環境下、水蒸氣下進行處理而得。 It is obtained by treating gibbsite in an alkaline gas environment and water vapor.

藉由將該等氧化鋁原料進行燒製，而得到α-氧化鋁、γ-氧化鋁、δ-氧化鋁、θ-氧化鋁等。 By firing these alumina raw materials, α-alumina, γ-alumina, δ-alumina, θ-alumina, etc. are obtained.

氧化鋁粒子的平均粒徑(D50)較佳為0.1~2.0μm，更佳為0.2~1.0μm。藉由使氧化鋁粒子的平均粒徑為0.1μm以上，可抑制研磨速度降低。藉由使氧化鋁粒子的平均粒徑為2.0μm以下，可抑制研磨後的起伏加劇。 The average particle diameter (D50) of the alumina particles is preferably 0.1 to 2.0 μm, more preferably 0.2 to 1.0 μm. By setting the average particle diameter of the alumina particles to 0.1 μm or more, a decrease in the polishing rate can be suppressed. By setting the average particle diameter of the alumina particles to 2.0 μm or less, it is possible to suppress the increase in fluctuations after polishing.

氧化鋁粒子在研磨劑組成物A中的濃度較佳為1~50質量%，更佳為2~40質量%。藉由使氧化鋁粒子的濃度為1質量%以上，可抑制研磨速度降低。藉由使氧化鋁粒子的濃度為50質量%以下，可避免使用不需要的氧化鋁粒子，而經濟上有利地進行研磨。 The concentration of alumina particles in the abrasive composition A is preferably 1 to 50 mass%, more preferably 2 to 40 mass%. By setting the concentration of alumina particles to 1% by mass or more, a decrease in the polishing speed can be suppressed. By setting the concentration of alumina particles to 50% by mass or less, unnecessary use of alumina particles can be avoided, and grinding can be performed economically.

(A-2)水溶性高分子化合物 (A-2) Water-soluble polymer compound

研磨劑組成物A所含有的水溶性高分子化合物較佳為包含以具有羧酸基之單體為必要單體的聚合物與以具有磺酸基之單體為必要單體的聚合物的混合物及/或以具有羧酸基之單體及具有磺酸基之單體為必要單體的共聚物。又，亦可使用該等以外的單體。作為具有羧酸基之單體及具有磺酸基之單體以外的單體，可舉例如具有醯胺基之單體。 The water-soluble polymer compound contained in the abrasive composition A is preferably a mixture containing a polymer containing a monomer having a carboxylic acid group as an essential monomer and a polymer containing a monomer having a sulfonic acid group as an essential monomer. And/or a copolymer using a monomer having a carboxylic acid group and a monomer having a sulfonic acid group as essential monomers. In addition, monomers other than these may also be used. Examples of the monomer other than the monomer having a carboxylic acid group and the monomer having a sulfonic acid group include a monomer having a amide group.

(A-2-1)具有羧酸基之單體 (A-2-1) Monomer having carboxylic acid group

作為具有羧酸基之單體，較佳為使用不飽和脂肪族羧酸及其鹽。具體而言，可列舉：丙烯酸、甲基丙烯酸、馬來酸、衣康酸及該等之鹽。作為鹽，可列舉：鈉鹽、鉀鹽、鎂鹽、銨鹽、胺鹽、烷基銨鹽等。 As the monomer having a carboxylic acid group, unsaturated aliphatic carboxylic acid and its salt are preferably used. Specific examples include acrylic acid, methacrylic acid, maleic acid, itaconic acid and salts thereof. Examples of salts include sodium salts, potassium salts, magnesium salts, ammonium salts, amine salts, alkylammonium salts, and the like.

水溶性化合物中，具有羧酸基之單體係以酸的狀態存在的比例較多或是以鹽的狀態存在的比例較多，能夠以水溶性高分子化合物的pH值進行評價。作為酸存在的比例越多則pH值越低，作為鹽存在的比例越多則pH值越高。在本發明中，例如，可使用濃度10質量%之水溶性高分子化合物水溶液中的pH值(25℃)在0.1~13之範圍的水溶性高分子化合物。 Among water-soluble compounds, a large proportion of monosystems having a carboxylic acid group exist in an acid state or a large proportion exist in a salt state, and the pH value of the water-soluble polymer compound can be evaluated. The greater the proportion of acid present, the lower the pH value, and the greater the proportion of salt present, the higher the pH value. In the present invention, for example, a water-soluble polymer compound having a pH value (25°C) in the range of 0.1 to 13 in a water-soluble polymer compound aqueous solution with a concentration of 10% by mass can be used.

(A-2-2)具有磺酸基之單體 (A-2-2) Monomer with sulfonic acid group

作為具有磺酸基之單體的具體例，可列舉：異戊二烯磺酸、2-丙烯醯胺-2-甲基丙磺酸、2-甲基丙烯醯胺-2-甲基丙磺酸、苯乙烯磺酸、乙烯磺酸、烯丙基磺酸、異戊烯磺酸、乙烯萘磺酸及該等之鹽等。較佳可列舉：2-丙烯醯胺-2-甲基丙磺酸、2-甲基丙烯醯胺-2-甲基丙磺酸及該等之鹽等。 Specific examples of the monomer having a sulfonic acid group include isoprene sulfonic acid, 2-acrylamide-2-methylpropanesulfonic acid, and 2-methacrylamide-2-methylpropanesulfonic acid. Acid, styrene sulfonic acid, vinyl sulfonic acid, allyl sulfonic acid, isopentenesulfonic acid, vinyl naphthalene sulfonic acid and their salts, etc. Preferred examples include: 2-acrylamide-2-methylpropanesulfonic acid, 2-methacrylamide-2-methylpropanesulfonic acid, and salts thereof.

(A-2-3)其他單體 (A-2-3) Other monomers

研磨劑組成物A含有水溶性高分子化合物作為必要成分或任意成分。研磨劑組成物A所含有的水溶性高分子化合物中，具有羧酸基之單體及具有磺酸基之單體為必要單體，但亦可使用該等以外的單體。例如，亦可使用具有醯胺基之單體。具體而言，可使用丙烯醯胺、甲基丙烯醯胺、N-烷基丙烯醯胺、N-烷基甲基丙烯醯胺等。 The abrasive composition A contains a water-soluble polymer compound as an essential component or an optional component. Among the water-soluble polymer compounds contained in the polishing composition A, monomers having a carboxylic acid group and a monomer having a sulfonic acid group are essential monomers, but monomers other than these may also be used. For example, a monomer having a amide group can also be used. Specifically, acrylamide, methacrylamide, N-alkyl acrylamide, N-alkyl methacrylamide, etc. can be used.

作為N-烷基丙烯醯胺、N-烷基甲基丙烯醯胺的具體例，可列舉：N-甲基丙烯醯胺、N-乙基丙烯醯胺、N-正丙基丙烯醯胺、N-異丙基丙烯醯胺、N-正丁基丙烯醯胺、N-異丁基丙烯醯胺、N-第二丁基丙烯醯胺、N-第三丁基丙烯醯胺、N-甲基甲基丙烯醯胺、N-乙基甲基丙烯醯胺、N-正丙基甲基丙烯醯胺、N-異丙基甲基丙烯醯胺、N-正丁基甲基丙烯醯胺、N-異丁基甲基丙烯醯胺、N-第二丁基甲基丙烯醯胺、N-第三丁基甲基丙烯醯胺等。 Specific examples of N-alkyl acrylamide and N-alkyl methacrylamide include: N-methacrylamide, N-ethylacrylamide, N-n-propylacrylamide, N-isopropylacrylamide, N-n-butylacrylamide, N-isobutylacrylamide, N-second butylacrylamide, N-tert-butylacrylamide, N-methyl Methylmethacrylamide, N-ethylmethacrylamide, N-n-propylmethacrylamide, N-isopropylmethacrylamide, N-n-butylmethacrylamide, N- Isobutyl methacrylamide, N-second butyl methacrylamide, N-third butyl methacrylamide, etc.

(A-2-4)聚合物的混合物 (A-2-4) Polymer mixture

本發明中，研磨劑組成物A所含有的水溶性高分子化合物亦可為包含以具有羧酸基之單體為必要單體的聚合物與以具有磺酸基之單體為必要單體的聚合物的混合物。此情況下，作為構成混合物的聚合物，作為以具有羧酸基之單體為必要單體的聚合物，可列舉：使具有羧酸基之單體進行聚合而得的聚合物、具有羧酸基之單體與具有磺酸基之單體的共聚物、具有羧酸基之單體與其他單體的共聚物、具有羧酸基之單體與具有磺酸基之單體與其他單體的共聚物等。 In the present invention, the water-soluble polymer compound contained in the polishing agent composition A may also be a polymer containing a monomer having a carboxylic acid group as an essential monomer and a monomer having a sulfonic acid group as an essential monomer. Mixture of polymers. In this case, the polymer constituting the mixture includes a polymer obtained by polymerizing a monomer having a carboxylic acid group, a polymer having a carboxylic acid group as an essential monomer, and a polymer having a carboxylic acid group as an essential monomer. Copolymers of monomers with carboxylic acid groups and monomers with sulfonic acid groups, copolymers of monomers with carboxylic acid groups and other monomers, copolymers of monomers with carboxylic acid groups, monomers with sulfonic acid groups and other monomers copolymers, etc.

又，作為以具有磺酸基之單體為必要單體的聚合物，可列舉：使具有磺酸基之單體進行聚合而得的聚合物、具有羧酸基之單體與具有磺酸基之單體的共聚物、具有磺酸基之單體與其他單體的共聚物、具有羧酸基之單體與具有磺酸基之單體與其他單體的共聚物等。 Examples of polymers containing a monomer having a sulfonic acid group as an essential monomer include a polymer obtained by polymerizing a monomer having a sulfonic acid group, a monomer having a carboxylic acid group, and a monomer having a sulfonic acid group. Copolymers of monomers, copolymers of monomers with sulfonic acid groups and other monomers, copolymers of monomers with carboxylic acid groups, copolymers of monomers with sulfonic acid groups and other monomers, etc.

包含以具有羧酸基之單體為必要單體的聚合物與以具有磺酸基之單體為必要單體的聚合物的混合物，亦可為來自該等以具有羧酸基之單體為必要單體的聚合物及以具有磺酸基之單體為必要單體的聚合物各一種以上之聚合物的混合物。混合物中以具有羧酸基之單體為必要單體的聚合物的比例較佳為5~95質量%，更佳為8~92質量%，再佳為10~90質量%。混合物中以具有磺酸基之單體為必要單體的聚合物的比例較佳為5~95質量%，更佳為8~92質量%，再佳為10~90質量%。 A mixture containing a polymer containing a monomer having a carboxylic acid group as an essential monomer and a polymer containing a monomer having a sulfonic acid group as an essential monomer may also be derived from the monomer containing a carboxylic acid group. A mixture of polymers containing one or more essential monomers and polymers containing one or more polymers each containing a monomer having a sulfonic acid group as an essential monomer. The proportion of the polymer containing a monomer having a carboxylic acid group as an essential monomer in the mixture is preferably 5 to 95 mass %, more preferably 8 to 92 mass %, and still more preferably 10 to 90 mass %. The proportion of the polymer containing a monomer having a sulfonic acid group as an essential monomer in the mixture is preferably 5 to 95 mass %, more preferably 8 to 92 mass %, and still more preferably 10 to 90 mass %.

(A-2-5)共聚物 (A-2-5) Copolymer

本發明中，研磨劑組成物A所含有的水溶性高分子化合物亦可為以具有羧酸基之單體及具有磺酸基之單體為必要單體的共聚物。水溶性高分子化合物中，源自具有羧酸基之單體的構成單元的比例較佳為5~95mol%，更佳為8~92mol%，再佳為10~90mol%。源自具有磺酸基之單體的構成單元的比例較佳為5~95mol%，更佳為8~92mol%，再佳為10~90mol%。 In the present invention, the water-soluble polymer compound contained in the abrasive composition A may be a copolymer containing a monomer having a carboxylic acid group and a monomer having a sulfonic acid group as essential monomers. In the water-soluble polymer compound, the proportion of structural units derived from the monomer having a carboxylic acid group is preferably 5 to 95 mol%, more preferably 8 to 92 mol%, and still more preferably 10 to 90 mol%. The proportion of structural units derived from the monomer having a sulfonic acid group is preferably 5 to 95 mol%, more preferably 8 to 92 mol%, and still more preferably 10 to 90 mol%.

(A-2-6)水溶性高分子化合物的製造方法 (A-2-6) Method for producing water-soluble polymer compounds

水溶性高分子化合物的製造方法並無特別限制，較佳為水溶液聚合法。根據水溶液聚合法，可得到形成均勻溶液的水溶性高分子化合物。作為上述水溶液聚合的聚合溶劑，較佳為水性溶劑，特佳為水。又，為了提升上述單體成分對於溶劑的溶解性，在不會造成不良影響的範圍內，亦可於各單體的聚合中適當加入有機溶劑。作為上述有機溶劑，可列舉：異丙醇等的醇類、丙酮等的酮類。該等可單獨使用1種或是組合2種以上使用。 The method for producing the water-soluble polymer compound is not particularly limited, but an aqueous solution polymerization method is preferred. According to the aqueous solution polymerization method, a water-soluble polymer compound forming a uniform solution can be obtained. As the polymerization solvent for the above-mentioned aqueous solution polymerization, an aqueous solvent is preferred, and water is particularly preferred. In addition, in order to improve the solubility of the above-mentioned monomer components in the solvent, an organic solvent may be appropriately added during the polymerization of each monomer within a range that does not cause adverse effects. Examples of the organic solvent include alcohols such as isopropyl alcohol and ketones such as acetone. These can be used individually by 1 type or in combination of 2 or more types.

以下說明使用上述水性溶劑之水溶性高分子化合物的製造方法。聚合反應中可使用習知的聚合起始劑，但特佳為使用自由基聚合起始劑。作為自由基聚合起始劑，可舉例如：過硫酸鈉、過硫酸鉀及過硫酸銨等的過硫酸鹽、氫過氧化第三丁基等的氫過氧化物類、過氧化氫等的水溶性過氧化物、過氧化丁酮、過氧化環己酮等的過氧化酮類、過氧化二(第三丁基)、過氧化第三丁基異丙苯基等的過氧化二烷基類等的油溶性過氧化物、偶氮雙異丁腈、二氫氧化2,2-偶氮雙(2-甲基丙脒)等的偶氮化合物。該等過氧化物系自由基聚合起始劑可僅使用1種或併用2種以上。上述過氧化物系自由基聚合起始劑之中，從容易控制生成之水溶性高分子化合物的分子量的觀點來看，較佳為過硫酸鹽或偶氮化合物，特佳為偶氮雙異丁腈。 The following describes a method for producing a water-soluble polymer compound using the above-mentioned aqueous solvent. Conventional polymerization initiators can be used in the polymerization reaction, but it is particularly preferred to use a radical polymerization initiator. Examples of the radical polymerization initiator include persulfates such as sodium persulfate, potassium persulfate, and ammonium persulfate, hydroperoxides such as tert-butyl hydroperoxide, and water-soluble hydrogen peroxide. Peroxides, ketone peroxides such as butanone peroxide, cyclohexanone peroxide, etc., dialkyl peroxides such as di(tert-butyl)peroxide, tert-butylcumyl peroxide, etc. Azo compounds such as oil-soluble peroxides, azobisisobutyronitrile, and 2,2-azobis(2-methylpropionamidine) dihydroxide. Only one type of these peroxide-based radical polymerization initiators may be used or two or more types may be used in combination. Among the above-mentioned peroxide-based radical polymerization initiators, from the viewpoint of easy control of the molecular weight of the produced water-soluble polymer compound, persulfate or azo compound is preferred, and azobisisobutyl is particularly preferred. Nitrile.

上述自由基聚合起始劑的使用量並無特別限制，基於水溶性高分子化合物的全部單體總質量，較佳係以0.1~15質量%、特別是0.5~10質量%的比例使用。藉由使該比例為0.1質量%以上，可提升共聚合率，藉由使其為15質量%以下，可提升水溶性高分子化合物的穩定性。 The usage amount of the above-mentioned radical polymerization initiator is not particularly limited. Based on the total mass of all monomers of the water-soluble polymer compound, it is preferably used in a proportion of 0.1 to 15 mass %, especially 0.5 to 10 mass %. By setting the ratio to 0.1% by mass or more, the copolymerization rate can be increased, and by setting the ratio to 15% by mass or less, the stability of the water-soluble polymer compound can be improved.

又，視情況，水溶性高分子化合物亦可使用水溶性氧化還原系聚合起始劑進行製造。作為氧化還原系聚合起始劑，可列舉：氧化劑(例如上述過氧化物)與重亞硫酸鈉、重亞硫酸銨、亞硫酸銨、低亞硫酸鈉(sodium hydrosulfite)等的還原劑或鐵明礬、鉀明礬等的組合。 In addition, if necessary, the water-soluble polymer compound may be produced using a water-soluble redox polymerization initiator. Examples of the redox polymerization initiator include an oxidizing agent (for example, the above-mentioned peroxide) and a reducing agent such as sodium bisulfite, ammonium bisulfite, ammonium sulfite, sodium hydrosulfite, or iron alum, potassium alum, etc. combination.

在製造水溶性高分子化合物中，亦可將鏈轉移劑適當添加至聚合系中，用於調整分子量。作為鏈轉移劑，可舉例如：亞磷酸鈉、次磷酸鈉、次磷酸鉀、亞硫酸鈉、亞硫酸氫鈉、巰乙酸、巰丙酸、硫乙醇酸、2-丙硫醇、2-巰基乙醇及硫酚等。 In the production of water-soluble polymer compounds, a chain transfer agent can also be appropriately added to the polymerization system to adjust the molecular weight. Examples of the chain transfer agent include sodium phosphite, sodium hypophosphite, potassium hypophosphite, sodium sulfite, sodium bisulfite, thioglycolic acid, mercaptopropionic acid, thioglycolic acid, 2-propanethiol, 2-mercaptoethanol, and thiophenol etc.

製造水溶性高分子化合物時的聚合溫度並無特別限制，但聚合溫度較佳係以60~100℃進行。藉由使聚合溫度為60℃以上，聚合反應順利地進行，且生產性優異，藉由使其為100℃以下，可抑制著色。 The polymerization temperature when producing the water-soluble polymer compound is not particularly limited, but the polymerization temperature is preferably 60 to 100°C. By setting the polymerization temperature to 60° C. or higher, the polymerization reaction proceeds smoothly and the productivity is excellent, and by setting the polymerization temperature to 100° C. or lower, coloring can be suppressed.

又，聚合反應亦可在加壓或減壓下進行，但設置加壓或減壓反應用設備需要成本，因此較佳在常壓下進行。聚合時間較佳為進行2~20小時，特別是3~10小時。 In addition, the polymerization reaction may be performed under increased pressure or reduced pressure. However, it is costly to install equipment for the pressure increased or reduced pressure reaction, so it is preferably performed under normal pressure. The polymerization time is preferably 2 to 20 hours, especially 3 to 10 hours.

聚合反應後，因應需求以鹼性化合物進行中和。作為用於中和的鹼性化合物，可列舉：氫氧化鈉、氫氧化鉀等的鹼金屬氫氧化物、氫氧化鈣、氫氧化鎂等的鹼土金屬之氫氧化物、氨水、單乙醇胺、二乙醇胺、三乙醇胺等的有機胺類等。 After the polymerization reaction, neutralize with an alkaline compound if necessary. Examples of alkaline compounds used for neutralization include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide, ammonia, monoethanolamine, diamine, etc. Organic amines such as ethanolamine and triethanolamine, etc.

水溶性高分子化合物濃度為10質量%之水溶液的情況下，中和後的pH值(25℃)較佳為2~9，再佳為3~8。 In the case of an aqueous solution with a water-soluble polymer compound concentration of 10% by mass, the pH value (25°C) after neutralization is preferably 2 to 9, and more preferably 3 to 8.

(A-2-7)重量平均分子量 (A-2-7) Weight average molecular weight

構成本發明所使用之水溶性高分子化合物的以具有羧酸基之單體為必要單體的聚合物、以具有磺酸基之單體為必要單體的聚合物、以具有羧酸基之單體及具有磺酸基之單體為必要單體的共聚物、以具有羧酸基之單體與具有磺酸基之單體及具有醯胺基之單體為必要單體的共聚物的重量平均分子量，分別較佳為1,000~1,000,000，更佳為3,000~800,000，再佳為5,000~600,000。此外，水溶性高分子化合物的重量平均分子量係藉由凝膠滲透層析儀(GPC)在聚丙烯酸換算下所測量。水溶性高分子化合物的重量平均分子量小於1,000的情況下，研磨後的起伏加劇。又，超過1,000,000的情況下，水溶液的黏度變高而難以處理。 The water-soluble polymer compound used in the present invention is composed of a polymer containing a monomer having a carboxylic acid group as an essential monomer, a polymer containing a monomer having a sulfonic acid group as an essential monomer, and a polymer containing a carboxylic acid group as an essential monomer. Copolymers of monomers and monomers with sulfonic acid groups as essential monomers, copolymers of monomers with carboxylic acid groups, monomers with sulfonic acid groups and monomers with amide groups as essential monomers The weight average molecular weight is preferably 1,000~1,000,000, more preferably 3,000~800,000, and still more preferably 5,000~600,000. In addition, the weight average molecular weight of the water-soluble polymer compound is measured by gel permeation chromatography (GPC) in terms of polyacrylic acid. When the weight average molecular weight of the water-soluble polymer compound is less than 1,000, the fluctuation after grinding becomes more severe. In addition, when it exceeds 1,000,000, the viscosity of the aqueous solution becomes high, making it difficult to handle.

(A-2-8)濃度 (A-2-8)Concentration

研磨劑組成物A中的水溶性高分子化合物的濃度，在固體成分換算下為0.0001~3.0質量%，較佳為0.001~2.0質量%，再佳為0.005~1.0質量%。水溶性高分子化合物的濃度少於0.0001質量%的情況下，無法充分得到添加水溶性高分子化合物的效果，多於3.0質量%的情況下，添加水溶性高分子化合物的效果趨向平穩，由於添加多餘的水溶性高分子化合物而不經濟。 The concentration of the water-soluble polymer compound in the abrasive composition A is 0.0001 to 3.0 mass% in terms of solid content, preferably 0.001 to 2.0 mass%, and more preferably 0.005 to 1.0 mass%. When the concentration of the water-soluble polymer compound is less than 0.0001 mass %, the effect of adding the water-soluble polymer compound cannot be fully obtained. When it exceeds 3.0 mass %, the effect of adding the water-soluble polymer compound tends to be stable. Excess water-soluble polymer compounds are uneconomical.

(A-3)有機硫酸酯鹽化合物 (A-3) Organic sulfate ester salt compound

本發明中，在研磨劑組成物A中含有有機硫酸酯鹽化合物作為必要成分。作為有機硫酸酯鹽化合物，可含有下述第一態樣與第二態樣的任一者。 In the present invention, the polishing composition A contains an organic sulfate ester salt compound as an essential component. As the organic sulfate ester salt compound, any one of the following first aspect and second aspect may be included.

(A-3-1)有機硫酸酯鹽化合物(第一態樣) (A-3-1) Organic sulfate ester salt compound (first aspect)

本發明中，作為研磨劑組成物A所使用之有機硫酸酯鹽化合物的第一態樣，較佳係下列通式(1)所表示的化合物。 In the present invention, the first aspect of the organic sulfate ester salt compound used in the polishing composition A is preferably a compound represented by the following general formula (1).

R-O-SO₃M (1) RO-SO ₃ M (1)

若上列通式(1)中R的碳數小於5，則具有因研磨而產生之研磨屑的分散去除能力或防止再附著能力不足的情況，若超過21則具有有機硫酸酯鹽化合物本身在研磨劑組成物中的溶解性/分散穩定性降低，或是使用研磨劑組成物時的溶解性/分散穩定性降低的情況。R的碳數較佳為8~14，再佳為10~14。 If the carbon number of R in the above general formula (1) is less than 5, the dispersion and removal ability of grinding dust generated by grinding or the ability to prevent re-adhesion is insufficient. If it exceeds 21, the organic sulfate ester salt compound itself has insufficient The solubility/dispersion stability in the abrasive composition decreases, or the solubility/dispersion stability decreases when using the abrasive composition. The carbon number of R is preferably 8 to 14, and more preferably 10 to 14.

具體而言，作為R所表示的烷基之例，可列舉：戊基、己基、庚基、辛基、壬基、癸基、十一基、十二基、十三基、十四基、十五基、十六基、十八基、十九基、第三丁基、異辛基、異十二基等。又，作為烯基之例，可列舉油醯基等。又，作為芳基之例，可列舉：苯基、聯苯基、萘基等。又，作為烷基芳基之例，可列舉：甲苯基、二甲苯基、辛基苯基等。從氧化穩定性、分散穩定性的觀點來看，R較佳為烷基。 Specifically, examples of the alkyl group represented by R include: pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, thirteenthyl group, tetradecanyl group, Pentabase, hexadecyl, octadecyl, nonadecayl, tertiary butyl, isooctyl, isododecyl, etc. Examples of the alkenyl group include an oleyl group and the like. Examples of the aryl group include phenyl, biphenyl, naphthyl, and the like. Examples of the alkylaryl group include tolyl, xylyl, octylphenyl, and the like. From the viewpoint of oxidation stability and dispersion stability, R is preferably an alkyl group.

作為上列通式(1)中的M之例，可列舉：鈉或鉀等的鹼金屬、鈣或鎂等的鹼土金屬、銨離子、4級銨離子或三乙醇胺等的有機胺。 Examples of M in the general formula (1) include alkali metals such as sodium and potassium, alkaline earth metals such as calcium and magnesium, ammonium ions, quaternary ammonium ions, and organic amines such as triethanolamine.

作為上列通式(1)所表示之有機硫酸酯鹽化合物的具體例，可列舉：庚基硫酸鹽、辛基硫酸鹽、月桂基硫酸鹽、高級醇(椰子油)硫酸鹽、硬脂醯硫酸鹽等，較佳為使用辛基硫酸鹽、月桂基硫酸鹽、硬脂醯硫酸鹽。上列通式(1)所表示之有機硫酸酯鹽化合物，亦可於本發明之研磨劑組成物中使用1種或組合2種以上使用。 Specific examples of the organic sulfate salt compound represented by the general formula (1) include heptyl sulfate, octyl sulfate, lauryl sulfate, higher alcohol (coconut oil) sulfate, and stearyl sulfate. Sulfates, etc., preferably octyl sulfate, lauryl sulfate, and stearyl sulfate are used. The organic sulfate ester salt compound represented by the above general formula (1) may be used alone or in combination of two or more types in the abrasive composition of the present invention.

研磨劑組成物A中的上列通式(1)所表示之有機硫酸酯鹽化合物的含量通常為0.0001~2.0質量%，較佳為0.0005~1.0質量%。 The content of the organic sulfate ester salt compound represented by the above general formula (1) in the abrasive composition A is usually 0.0001 to 2.0 mass%, preferably 0.0005 to 1.0 mass%.

(A-3-2)有機硫酸酯鹽化合物(第二態樣) (A-3-2) Organic sulfate ester salt compound (second aspect)

作為研磨劑組成物A所使用之有機硫酸酯鹽化合物的第二態樣，較佳為下列通式(2)所表示之化合物。 As the second aspect of the organic sulfate ester salt compound used in the polishing composition A, a compound represented by the following general formula (2) is preferred.

R-O-(AO)_n-SO₃M (2) RO-(AO) _n -SO ₃ M (2)

式中，R表示碳數5~21的直鏈或分支之烷基、烯基、芳基或烷基芳基，AO表示碳數2或3之氧伸烷基，n表示1~30之整數，M表示鹼金屬、鹼土類、銨離子或有機陽離子。 In the formula, R represents a linear or branched alkyl, alkenyl, aryl or alkylaryl group with 5 to 21 carbon atoms, AO represents an oxyalkylene group with 2 or 3 carbon atoms, and n represents an integer from 1 to 30. , M represents alkali metal, alkaline earth, ammonium ion or organic cation.

在上列通式(2)所表示之有機硫酸酯鹽化合物中，R為碳數5~21的直鏈或分支之烷基、烯基、芳基或烷基芳基。R的碳數較佳為8~14，再佳為10~14。又，R較佳為烷基。 In the organic sulfate ester salt compound represented by the above general formula (2), R is a linear or branched alkyl group, alkenyl group, aryl group or alkylaryl group having 5 to 21 carbon atoms. The carbon number of R is preferably 8 to 14, and more preferably 10 to 14. Moreover, R is preferably an alkyl group.

在上列通式(2)中，AO為碳數2或3之氧伸烷基。 In the above general formula (2), AO is an oxyalkylene group having 2 or 3 carbon atoms.

在上列通式(2)中，n為1~30之整數，較佳為2~4。 In the above general formula (2), n is an integer from 1 to 30, preferably 2 to 4.

在上列通式(2)中，作為M的具體例，可列舉：鈉或鉀等的鹼金屬、鈣或鎂等的鹼土金屬、銨離子、4級銨離子或三乙醇胺等的有機胺。 In the above general formula (2), specific examples of M include alkali metals such as sodium and potassium, alkaline earth metals such as calcium and magnesium, ammonium ions, quaternary ammonium ions, and organic amines such as triethanolamine.

作為上列通式(2)所表示之有機硫酸酯鹽化合物，可使用一般已知作為陰離子界面活性劑的水溶性者。在本發明中，上列通式(2)所表示之有機硫酸酯鹽化合物，係使其包含聚氧伸烷基烷醚硫酸酯鹽、聚氧伸烷基烯基醚硫酸酯鹽、聚氧伸烷基芳醚硫酸酯鹽及聚氧伸烷基烷基芳醚硫酸酯鹽的任一種。 As the organic sulfate ester salt compound represented by the above general formula (2), water-soluble compounds generally known as anionic surfactants can be used. In the present invention, the organic sulfate salt compound represented by the above general formula (2) includes polyoxyalkylene alkyl ether sulfate ester salt, polyoxyalkylene alkenyl ether sulfate ester salt, polyoxyalkylene alkenyl ether sulfate ester salt, Either alkylene aryl ether sulfate ester salt or polyoxyalkylene alkyl aryl ether sulfate ester salt.

更具體而言，作為上列通式(2)所表示之有機硫酸酯鹽化合物，可列舉：氧乙烯三癸醚硫酸鹽(每1分子中氧乙烯基為2個或3個)、氧乙烯月桂醚硫酸鹽(每1分子中氧乙烯基為2個或3個)、氧乙烯壬醚硫酸鹽(每1分子中氧乙烯基為3個)、氧乙烯辛基苯基醚硫酸鹽(每1分子中氧乙烯基為3個)、氧乙烯壬基苯基醚硫酸鹽(每1分子中氧乙烯基為3個)等。該等之中，特佳為使用氧乙烯三癸醚硫酸鹽(每1分子中氧乙烯基為3個)、氧乙烯月桂醚硫酸鹽(每1分子中氧乙烯基為3個)、氧乙烯辛基苯基醚硫酸鹽(每1分子中氧乙烯基為3個)、氧乙烯壬基苯基醚硫酸鹽(每1分子中氧乙烯基為3個)。 More specifically, examples of the organic sulfate ester salt compound represented by the above general formula (2) include: oxyethylene triocyl ether sulfate (2 or 3 oxyethylene groups per molecule), oxyethylene Lauryl ether sulfate (there are 2 or 3 oxyethylene groups per molecule), oxyethylene nonyl ether sulfate (there are 3 oxyethylene groups per molecule), oxyethylene octyl phenyl ether sulfate (per molecule has 3 oxyethylene groups) There are 3 oxyethylene groups per molecule), oxyethylene nonylphenyl ether sulfate (there are 3 oxyethylene groups per molecule), etc. Among these, oxyethylene trialcyl ether sulfate (3 oxyethylene groups per molecule), oxyethylene lauryl ether sulfate (3 oxyethylene groups per molecule), oxyethylene Octylphenyl ether sulfate (3 oxyethylene groups per molecule), oxyethylene nonylphenyl ether sulfate (3 oxyethylene groups per molecule).

用於研磨劑組成物A中的上列通式(2)所表示之有機硫酸酯鹽化合物，可使用1種或是組合2種以上使用。又，亦可與上列通式(1)所表示之有機硫酸酯鹽化合物組合使用。 The organic sulfate ester salt compound represented by the above-mentioned general formula (2) used in the polishing composition A can be used alone or in combination of two or more kinds. Furthermore, it may be used in combination with the organic sulfate ester salt compound represented by the above-mentioned general formula (1).

研磨劑組成物A中的上列通式(2)之有機硫酸酯鹽化合物的含量通常為0.0001~2.0質量%，較佳為0.0005~1.0質量%。 The content of the organic sulfate ester compound of the general formula (2) in the abrasive composition A is usually 0.0001 to 2.0 mass%, preferably 0.0005 to 1.0 mass%.

(A-4)酸及/或其鹽 (A-4) Acid and/or its salt

在本發明中，研磨劑組成物A中，可使用酸及/或其鹽用於調整pH或作為任意成分。作為使用之酸及/或其鹽，可列舉：無機酸及/或其鹽與有機酸及/或其鹽。 In the present invention, in the abrasive composition A, an acid and/or its salt can be used for pH adjustment or as an optional component. Examples of acids and/or salts thereof used include inorganic acids and/or salts thereof and organic acids and/or salts thereof.

作為無機酸及/或其鹽，可列舉：硝酸、硫酸、鹽酸、磷酸、膦酸、吡咯啉酸、三聚磷酸等的無機酸及/或其鹽。 Examples of inorganic acids and/or salts thereof include inorganic acids such as nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, phosphonic acid, pyrroline acid, and tripolyphosphoric acid and/or salts thereof.

作為有機酸及/或其鹽，可列舉：穀胺酸、天冬胺酸等的胺基羧酸及/或其鹽、檸檬酸、酒石酸、乙二酸、硝乙酸、馬來酸、蘋果酸、琥珀酸等的羧酸及/或其鹽、有機膦酸及/或其鹽。該等酸及/或其鹽可使用1種或是2種以上。 Examples of organic acids and/or salts thereof include aminocarboxylic acids such as glutamic acid and aspartic acid and/or salts thereof, citric acid, tartaric acid, oxalic acid, nitroacetic acid, maleic acid, and malic acid. , carboxylic acids such as succinic acid and/or their salts, organic phosphonic acids and/or their salts. One type or two or more types of these acids and/or salts thereof may be used.

作為有機膦酸及/或其鹽，可列舉選自2-胺基乙基膦酸、1-羥基亞乙基-1,1-二膦酸、胺基三(亞甲基膦酸)、乙二胺四(亞甲基膦酸)、二伸乙三胺五(亞甲基膦酸)、乙烷-1,1-二膦酸、乙烷-1,1,2-三膦酸、乙烷-1-羥基-1,1,2-三膦酸、乙烷-1,2-二羧基-1,2-二膦酸、甲烷羥基膦酸、2-膦醯基丁烷-1,2-二羧酸、1-膦醯基丁烷-2,3,4-三羧酸、α-甲基膦醯基琥珀酸及其鹽的至少1種以上的化合物。 Examples of organic phosphonic acids and/or salts thereof include those selected from the group consisting of 2-aminoethylphosphonic acid, 1-hydroxyethylene-1,1-diphosphonic acid, aminotris(methylenephosphonic acid), and ethylphosphonic acid. Diamine tetrakis (methylene phosphonic acid), diethylene triamine penta (methylene phosphonic acid), ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, ethane Alkyl-1-hydroxy-1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid, 2-phosphonobutane-1,2 - At least one compound of dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid, α-methylphosphonosuccinic acid and their salts.

將上述化合物組合2種以上使用亦為較佳實施態樣，具體而言，可列舉：硫酸及/或其鹽與有機膦酸及/或其鹽的組合、磷酸及/或其鹽與有機膦酸及/或其鹽的組合等。 It is also a preferred embodiment to use two or more kinds of the above-mentioned compounds in combination. Specific examples include: a combination of sulfuric acid and/or its salts and an organic phosphonic acid and/or its salts, and phosphoric acid and/or its salts and an organic phosphine. Combinations of acids and/or their salts, etc.

(A-5)氧化劑 (A-5) Oxidizing agent

本發明中的研磨劑組成物A亦可含有氧化劑作為研磨促進劑。作為氧化劑，可使用過氧化物、過錳酸或其鹽、鉻酸或其鹽、過氧酸或其鹽、鹵素含氧酸或其鹽、氧酸或其鹽、將該等氧化劑2種以上混合而成者等。 The polishing composition A in the present invention may also contain an oxidizing agent as a polishing accelerator. As the oxidizing agent, peroxide, permanganic acid or its salt, chromic acid or its salt, peroxy acid or its salt, halogen oxyacid or its salt, oxyacid or its salt can be used. Two or more of these oxidizing agents can be used. Mixed ones, etc.

具體而言，可列舉：過氧化氫、過氧化鈉、過氧化鋇、過氧化鉀、過錳酸鉀、鉻酸之金屬鹽、二鉻酸之金屬鹽、過硫酸、過硫酸鈉、過硫酸鉀、過硫酸銨、過氧磷酸、過氧硼酸鈉、過甲酸、過醋酸、次氯酸、次氯酸鈉、次氯酸鈣等。其中較佳為過氧化氫、過硫酸及其鹽、次氯酸及其鹽等，再佳為過氧化氫。 Specific examples include hydrogen peroxide, sodium peroxide, barium peroxide, potassium peroxide, potassium permanganate, metal salts of chromic acid, metal salts of dichromic acid, persulfuric acid, sodium persulfate, and persulfuric acid. Potassium, ammonium persulfate, peroxyphosphoric acid, sodium perborate, performic acid, peracetic acid, hypochlorous acid, sodium hypochlorite, calcium hypochlorite, etc. Among them, hydrogen peroxide, persulfuric acid and its salts, hypochlorous acid and its salts, etc. are preferred, and hydrogen peroxide is still more preferred.

研磨劑組成物A中的氧化劑含量較佳為0.01~10.0質量%。更佳為0.1~5.0質量%。 The oxidizing agent content in the abrasive composition A is preferably 0.01 to 10.0 mass%. More preferably, it is 0.1~5.0% by mass.

(A-6)研磨劑組成物A的物性(pH) (A-6) Physical properties (pH) of abrasive composition A

本發明中的研磨劑組成物A的pH值(25℃)的範圍較佳為0.1~4.0。更佳為0.5~3.0。藉由使研磨劑組成物A的pH值(25℃)為0.1以上，可抑制表面粗糙。藉由使研磨劑組成物A的pH值(25℃)為4.0以下，可抑制研磨速度降低。 The pH value (25°C) of the abrasive composition A in the present invention is preferably in the range of 0.1 to 4.0. More preferably, it is 0.5~3.0. By setting the pH value (25° C.) of the abrasive composition A to 0.1 or more, surface roughness can be suppressed. By setting the pH value (25° C.) of the polishing composition A to 4.0 or less, a decrease in the polishing speed can be suppressed.

(B)研磨劑組成物B (B)Abrasive composition B

本發明的磁碟基板之研磨方法的步驟(3)所使用的研磨劑組成物B係含有膠質氧化矽的水性組成物，其含有以水溶性高分子化合物作為必要成分或任意成分。再者，亦可含有有機硫酸酯鹽化合物、酸及/或其鹽、氧化劑等。 The abrasive composition B used in step (3) of the polishing method of the disk substrate of the present invention is an aqueous composition containing colloidal silica, which contains a water-soluble polymer compound as an essential or optional component. Furthermore, an organic sulfate ester salt compound, an acid and/or its salt, an oxidizing agent, etc. may also be contained.

(B-1)膠質氧化矽 (B-1) Colloidal silicon oxide

研磨劑組成物B所含有之膠質氧化矽的平均粒徑(D50)較佳為10~100nm。更佳為20~80nm。膠質氧化矽可由水玻璃法而得：以矽酸鈉、矽酸鉀等的矽酸鹼金屬鹽為原料，使該原料在水溶液中進行縮合反應而使粒子成長。或者亦可由烷氧矽烷法而得：以四乙氧基矽烷等的烷氧矽烷為原料，藉由使該原料在含有醇等水溶性有機溶劑的水中，以酸或鹼下的水解所進行的縮合反應而使粒子成長。 The average particle size (D50) of the colloidal silica contained in abrasive composition B is preferably 10 to 100 nm. More preferably, it is 20~80nm. Colloidal silicon oxide can be obtained by the water glass method: using alkali metal silicate salts such as sodium silicate and potassium silicate as raw materials, the raw materials undergo a condensation reaction in an aqueous solution to grow particles. Or it can also be obtained by the alkoxysilane method: using alkoxysilane such as tetraethoxysilane as a raw material, and hydrolyzing the raw material in water containing a water-soluble organic solvent such as alcohol under acid or alkali Condensation reaction causes particles to grow.

已知膠質氧化矽有球狀、鏈狀、金平糖型(kompeito-typed)、不規則狀等的形狀，於水中一次粒子進行單分散(monodisperse)而形成膠狀。作為研磨劑組成物B所含有之膠質氧化矽，特佳為球狀或接近球狀的膠質氧化矽。 Colloidal silicon oxide is known to have shapes such as spherical, chain, kompeito-type, and irregular shapes, and the primary particles are monodispersed in water to form a colloidal shape. As the colloidal silica contained in the abrasive composition B, spherical or nearly spherical colloidal silica is particularly preferred.

研磨劑組成物B中的膠質氧化矽的濃度較佳為0.1~20質量%。更佳為0.2~10質量%。 The concentration of colloidal silica in abrasive composition B is preferably 0.1 to 20% by mass. More preferably, it is 0.2~10 mass %.

(B-2)水溶性高分子化合物 (B-2) Water-soluble polymer compound

研磨劑組成物B含有水溶性高分子化合物作為必要成分或任意成分。研磨劑組成物B所含有之水溶性高分子化合物較佳為包含以具有羧酸基之單體為必要單體的聚合物與以具有磺酸基之單體為必要單體的聚合物的混合物及/或以具有羧酸基之單體及具有磺酸基之單體為必要單體的共聚物。又，亦可使用該等以外的單體。作為具有羧酸基之單體及具有磺酸基之單體以外的單體，可舉例如具有醯胺基之單體。 Polishing composition B contains a water-soluble polymer compound as an essential component or an optional component. The water-soluble polymer compound contained in the abrasive composition B is preferably a mixture containing a polymer containing a monomer having a carboxylic acid group as an essential monomer and a polymer containing a monomer having a sulfonic acid group as an essential monomer. And/or a copolymer using a monomer having a carboxylic acid group and a monomer having a sulfonic acid group as essential monomers. In addition, monomers other than these may also be used. Examples of the monomer other than the monomer having a carboxylic acid group and the monomer having a sulfonic acid group include a monomer having a amide group.

(B-2-1)具有羧酸基之單體 (B-2-1) Monomer with carboxylic acid group

水溶性化合物中，具有羧酸基之單體係以酸的狀態存在的比例較多或是以鹽的狀態存在的比例較多，能夠以水溶性高分子化合物的pH值進行評價。作為酸存在的比例越多則pH值越低，作為鹽存在的比例越多則pH值越高。在本發明中，例如，可使用濃度10質量%之水溶性高分子化合物水溶液中的pH值(25℃)在0.1~13之範圍的水溶性高分子化合物。 Among water-soluble compounds, a large proportion of monosystems having a carboxylic acid group exist in an acid state or a large proportion exist in a salt state, and the pH value of the water-soluble polymer compound can be evaluated. The greater the proportion of acid present, the lower the pH value, and the greater the proportion of salt present, the higher the pH value. In the present invention, for example, a water-soluble polymer compound having a pH value (25° C.) in the range of 0.1 to 13 in a water-soluble polymer compound aqueous solution with a concentration of 10% by mass can be used.

(B-2-2)具有磺酸基之單體 (B-2-2) Monomer with sulfonic acid group

(B-2-3)其他單體 (B-2-3)Other monomers

研磨劑組成物B所含有之水溶性高分子化合物中，具有羧酸基之單體及具有磺酸基之單體為必要單體，但亦可使用該等以外的單體。例如，亦可使用具有醯胺基之單體。具體而言，可使用丙烯醯胺、甲基丙烯醯胺、N-烷基丙烯醯胺、N-烷基甲基丙烯醯胺等。 Among the water-soluble polymer compounds contained in the polishing composition B, monomers having a carboxylic acid group and a monomer having a sulfonic acid group are essential monomers, but monomers other than these may also be used. For example, a monomer having a amide group can also be used. Specifically, acrylamide, methacrylamide, N-alkyl acrylamide, N-alkyl methacrylamide, etc. can be used.

(B-2-4)聚合物的混合物 (B-2-4) Polymer mixture

本發明中，研磨劑組成物B所含有的水溶性高分子化合物亦可為包含以具有羧酸基之單體為必要單體的聚合物與以具有磺酸基之單體為必要單體的聚合物的混合物。此情況下，作為構成混合物的聚合物，作為以具有羧酸基之單體為必要單體的聚合物，可列舉：使具有羧酸基之單體進行聚合而得的聚合物、具有羧酸基之單體與具有磺酸基之單體的共聚物、具有羧酸基之單體與其他單體的共聚物、具有羧酸基之單體與具有磺酸基之單體與其他單體的共聚物等。 In the present invention, the water-soluble polymer compound contained in the polishing agent composition B may also be a polymer containing a monomer having a carboxylic acid group as an essential monomer and a monomer having a sulfonic acid group as an essential monomer. Mixture of polymers. In this case, the polymer constituting the mixture includes a polymer obtained by polymerizing a monomer having a carboxylic acid group, a polymer having a carboxylic acid group as an essential monomer, and a polymer having a carboxylic acid group as an essential monomer. Copolymers of monomers with carboxylic acid groups and monomers with sulfonic acid groups, copolymers of monomers with carboxylic acid groups and other monomers, copolymers of monomers with carboxylic acid groups, monomers with sulfonic acid groups and other monomers copolymers, etc.

(B-2-5)共聚物 (B-2-5) copolymer

本發明中，研磨劑組成物B所含有的水溶性高分子化合物亦可為以具有羧酸基之單體及具有磺酸基之單體為必要單體的共聚物。水溶性高分子化合物中，源自具有羧酸基之單體的構成單元的比例較佳為5~95mol%，更佳為8~92mol%，再佳為10~90mol%。源自具有磺酸基之單體的構成單元的比例較佳為5~95mol%，更佳為8~92mol%，再佳為10~90mol%。 In the present invention, the water-soluble polymer compound contained in the polishing agent composition B may be a copolymer containing a monomer having a carboxylic acid group and a monomer having a sulfonic acid group as essential monomers. In the water-soluble polymer compound, the proportion of structural units derived from the monomer having a carboxylic acid group is preferably 5 to 95 mol%, more preferably 8 to 92 mol%, and still more preferably 10 to 90 mol%. The proportion of structural units derived from the monomer having a sulfonic acid group is preferably 5 to 95 mol%, more preferably 8 to 92 mol%, and still more preferably 10 to 90 mol%.

(B-2-6)水溶性高分子化合物的製造方法 (B-2-6) Method for producing water-soluble polymer compounds

本發明中，研磨劑組成物B所含有之水溶性高分子化合物的製造方法，與研磨劑組成物A的情況相同地，較佳為水溶液聚合法，根據水溶液聚合法，可得到形成均勻溶液的水溶性高分子化合物。具體而言，可列舉使用水性溶劑，藉由使用自由基聚合起始劑之自由基聚合來製造水溶性高分子化合物的方法。作為自由基聚合起始劑，可列舉：過硫酸鹽、水溶性過氧化物、油溶性過氧化物、偶氮化合物等。又，作為起始劑，亦可使用水溶性氧化還原系聚合起始劑。亦可將鏈轉移劑適當添加至聚合系中，用於調整水溶性高分子化合物的分子量。聚合反應結束後，可因應需求以鹼性化合物進行中和。 In the present invention, the method for producing the water-soluble polymer compound contained in the polishing composition B is, like the case of the polishing composition A, preferably an aqueous solution polymerization method. According to the aqueous solution polymerization method, a uniform solution can be obtained. Water-soluble polymer compounds. Specific examples include a method of producing a water-soluble polymer compound by radical polymerization using an aqueous solvent and a radical polymerization initiator. Examples of radical polymerization initiators include persulfates, water-soluble peroxides, oil-soluble peroxides, azo compounds, and the like. In addition, as the initiator, a water-soluble redox polymerization initiator can also be used. A chain transfer agent can also be appropriately added to the polymerization system to adjust the molecular weight of the water-soluble polymer compound. After the polymerization reaction is completed, it can be neutralized with an alkaline compound as needed.

(B-2-7)重量平均分子量 (B-2-7) Weight average molecular weight

本發明中，構成研磨劑組成物B所含有之水溶性高分子化合物的以具有羧酸基之單體為必要單體的聚合物、以具有磺酸基之單體為必要單體的聚合物、以具有羧酸基之單體及具有磺酸基之單體為必要單體的共聚物、以具有羧酸基之單體與具有磺酸基之單體及具有醯胺基之單體為必要單體的共聚物的重量平均分子量，較佳係分別為1,000~1,000,000，更佳為3,000~800,000，再佳為5,000~600,000。此外，水溶性高分子化合物的重量平均分子量係藉由凝膠滲透層析儀(GPC)在聚丙烯酸換算下所測量。水溶性高分子化合物的重量平均分子量小於1,000的情況下，研磨後的起伏加劇。又，超過1,000,000的情況下，水溶液的黏度變高而難以處理。 In the present invention, the water-soluble polymer compound contained in the abrasive composition B is a polymer containing a monomer having a carboxylic acid group as an essential monomer, and a polymer containing a monomer having a sulfonic acid group as an essential monomer. , a copolymer that uses a monomer with a carboxylic acid group and a monomer with a sulfonic acid group as essential monomers, a copolymer that uses a monomer with a carboxylic acid group, a monomer with a sulfonic acid group, and a monomer with an amide group. The weight average molecular weight of the copolymer of the necessary monomers is preferably 1,000 to 1,000,000, more preferably 3,000 to 800,000, and still more preferably 5,000 to 600,000. In addition, the weight average molecular weight of the water-soluble polymer compound is measured by gel permeation chromatography (GPC) in terms of polyacrylic acid. When the weight average molecular weight of the water-soluble polymer compound is less than 1,000, fluctuations after grinding become more severe. In addition, when it exceeds 1,000,000, the viscosity of the aqueous solution becomes high, making it difficult to handle.

(B-2-8)濃度 (B-2-8)Concentration

本發明中，研磨劑組成物B所含有之水溶性高分子化合物的濃度，在固體成分換算下為0.0001~3.0質量%，較佳為0.001~2.0質量%，再佳為0.005~1.0質量%。水溶性高分子化合物的濃度少於0.0001質量%的情況下，無法充分得到添加水溶性高分子化合物的效果，多於3.0質量%的情況下，添加水溶性高分子化合物的效果趨向平穩，由於添加多餘的水溶性高分子化合物而不經濟。研磨劑組成物B中所使用的水溶性高分子化合物，可為與研磨劑組成物A所使用的水溶性高分子化合物相同的水溶性高分子化合物，亦可為不同的水溶性高分子化合物。 In the present invention, the concentration of the water-soluble polymer compound contained in the abrasive composition B is 0.0001 to 3.0 mass% in terms of solid content, preferably 0.001 to 2.0 mass%, and more preferably 0.005 to 1.0 mass%. When the concentration of the water-soluble polymer compound is less than 0.0001 mass %, the effect of adding the water-soluble polymer compound cannot be fully obtained. When it exceeds 3.0 mass %, the effect of adding the water-soluble polymer compound tends to be stable. Excess water-soluble polymer compounds are uneconomical. The water-soluble polymer compound used in polishing compound composition B may be the same water-soluble polymer compound as the water-soluble polymer compound used in polishing compound composition A, or may be a different water-soluble polymer compound.

(B-3)有機硫酸酯鹽化合物 (B-3) Organic sulfate ester salt compound

在研磨劑組成物B中，可含有有機硫酸酯鹽化合物作為任意成分。研磨劑組成物B中所使用的有機硫酸酯鹽化合物，可為與研磨劑組成物A所使用的有機硫酸酯鹽化合物相同的有機硫酸酯鹽化合物，亦可為不同的有機硫酸酯鹽化合物。 The abrasive composition B may contain an organic sulfate ester salt compound as an optional component. The organic sulfate ester salt compound used in the polishing agent composition B may be the same organic sulfate ester salt compound as the organic sulfate ester salt compound used in the polishing agent composition A, or may be a different organic sulfate ester salt compound.

(B-4)酸及/或其鹽 (B-4) Acid and/or its salt

研磨劑組成物B可使用酸及/或其鹽用於調整pH或作為任意成分。作為使用之酸及/或其鹽，可列舉：無機酸及/或其鹽與有機酸及/或其鹽。 The abrasive composition B can use an acid and/or its salt for pH adjustment or as an optional component. Examples of acids and/or salts thereof used include inorganic acids and/or salts thereof and organic acids and/or salts thereof.

作為無機酸及/或其鹽，可列舉：硝酸、硫酸、鹽酸、磷酸、膦酸、吡咯啉酸、三聚磷酸等的無機酸及/或其鹽。 Examples of inorganic acids and/or salts thereof include inorganic acids such as nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, phosphonic acid, pyrrolinic acid, and tripolyphosphoric acid and/or salts thereof.

(B-5)氧化劑 (B-5) Oxidizing agent

研磨劑組成物B可含有氧化劑作為任意成分。作為研磨劑組成物B中可含有的氧化劑，可使用過氧化物、過錳酸或其鹽、鉻酸或其鹽、過氧酸或其鹽、鹵素含氧酸或其鹽、氧酸或其鹽、將該等氧化劑2種以上混合而成者等。 The abrasive composition B may contain an oxidizing agent as an optional component. As the oxidizing agent that can be contained in the abrasive composition B, peroxide, permanganic acid or its salt, chromic acid or its salt, peroxy acid or its salt, halogen oxyacid or its salt, oxyacid or its salt can be used. Salt, a mixture of two or more of these oxidants, etc.

研磨劑組成物B中的氧化劑含量較佳為0.01~10.0質量%，再佳為0.05~5.0質量%。 The oxidizing agent content in the abrasive composition B is preferably 0.01 to 10.0 mass%, and more preferably 0.05 to 5.0 mass%.

(B-6)研磨劑組成物B的物性(pH) (B-6) Physical properties (pH) of abrasive composition B

研磨劑組成物B的pH值(25℃)的範圍較佳為0.1~4.0。更佳為0.5~3.0。藉由使研磨劑組成物B的pH值(25℃)為0.1以上，可抑制表面粗糙。藉由使研磨劑組成物B的pH值(25℃)為4.0以下，可抑制研磨速度降低。 The pH value (25°C) of abrasive composition B is preferably in the range of 0.1 to 4.0. More preferably, it is 0.5~3.0. By setting the pH value (25° C.) of the abrasive composition B to 0.1 or more, surface roughness can be suppressed. By setting the pH value (25° C.) of the polishing composition B to 4.0 or less, a decrease in the polishing speed can be suppressed.

[實施例] [Example]

以下，根據實施例具體說明本發明，但本發明並不限定於該等實施例，只要屬於本發明的技術範圍，則能夠以各種態樣實施，此自不待言。 Hereinafter, the present invention will be specifically described based on Examples. However, the present invention is not limited to these Examples, and it goes without saying that it can be implemented in various forms as long as it falls within the technical scope of the present invention.

[研磨劑組成物的製備方法] [Preparation method of abrasive composition]

實施例1~20、比較例1~10所使用的研磨劑組成物，係以表1所記載之含量包含表1所記載之材料的研磨劑組成物。此外，表1中，丙烯酸(具有羧酸基之單體)的簡稱為AA，2-丙烯醯胺-2-甲基丙磺酸(具有磺酸基之單體)的簡稱為ATBS，第三丁基丙烯醯胺(具有醯胺基之單體)的簡稱為TBAA。又，各實施例與各比較例的研磨試驗結果顯示於表2、表3。此外，聚氧乙烯三癸醚硫酸鈉係第二態樣的有機硫酸酯鹽化合物，月桂基硫酸鈉係第一態樣的有機硫酸酯鹽化合物。又，合成編號1~4係以具有羧酸基之單體及具有磺酸基之單體為必要單體的共聚物的水溶性高分子化合物。合成編號5、6為均聚物。又，實施例19、20中，水溶性高分子化合物係包含以具有羧酸基之單體為必要單體的聚合物與以具有磺酸基之單體為必要單體的聚合物的混合物。合成編號7係以具有羧酸基之單體與具有磺酸基之單體及具有醯胺基之單體為必要單體的共聚物的水溶性高分子化合物。 The abrasive compositions used in Examples 1 to 20 and Comparative Examples 1 to 10 contain the materials described in Table 1 in the contents described in Table 1. In addition, in Table 1, the abbreviation of acrylic acid (monomer having a carboxylic acid group) is AA, the abbreviation of 2-acrylamide-2-methylpropanesulfonic acid (monomer having a sulfonic acid group) is ATBS, and the third The abbreviation of butylacrylamide (monomer with amide group) is TBAA. Moreover, the polishing test results of each Example and each Comparative Example are shown in Table 2 and Table 3. In addition, sodium polyoxyethylene trialcyl ether sulfate is an organic sulfate ester salt compound of the second aspect, and sodium lauryl sulfate is an organic sulfate ester salt compound of the first aspect. In addition, synthesis numbers 1 to 4 are water-soluble polymer compounds of copolymers using a monomer having a carboxylic acid group and a monomer having a sulfonic acid group as essential monomers. Synthesis numbers 5 and 6 are homopolymers. Moreover, in Examples 19 and 20, the water-soluble polymer compound contains a mixture of a polymer containing a monomer having a carboxylic acid group as an essential monomer and a polymer containing a monomer having a sulfonic acid group as an essential monomer. Synthesis No. 7 is a water-soluble polymer compound that is a copolymer of a monomer having a carboxylic acid group, a monomer having a sulfonic acid group, and a monomer having an amide group as essential monomers.

AA：丙烯酸 AA: acrylic

ATBS：2-丙烯醯胺-2-甲基丙磺酸 ATBS: 2-Acrylamide-2-methylpropanesulfonic acid

TBAA：第三丁基丙烯醯胺 TBAA: tertiary butylacrylamide

[氧化鋁粒子的平均粒徑] [Average particle size of alumina particles]

氧化鋁粒子的平均粒徑係使用雷射繞射式粒度分布測量機(島津製作所股份有公司製SALD2200)進行測量。氧化鋁粒子的平均粒徑，係以體積為基準而從小粒徑側開始的累積粒徑分布成為50%的平均粒徑(D50)。 The average particle diameter of the alumina particles was measured using a laser diffraction particle size distribution measuring machine (SALD2200 manufactured by Shimadzu Corporation). The average particle diameter of alumina particles is the average particle diameter (D50) at which the cumulative particle diameter distribution from the small particle diameter side becomes 50% based on the volume.

[膠質氧化矽的平均粒徑] [Average particle size of colloidal silicon oxide]

膠質氧化矽的粒徑(海伍德(Heywood)直徑)係使用穿透式電子顯微鏡(TEM)(日本電子股份有公司製、穿透式電子顯微鏡JEM2000FX(200kV)拍攝倍率10萬倍視野，並使用分析軟體(Mountech Co.,Ltd.製、Mac-View Ver.4.0)分析該影像，藉此測量海伍德直徑(投射面積等效圓直徑)。膠質氧化矽的平均粒徑係在上述方法中分析2000個左右的膠質氧化矽的粒徑，其係使用上述分析軟體(Mountech Co.,Ltd.製、Mac-View Ver.4.0)，算出從小粒徑側開始的累積粒徑分布(累積體積基準)成為50%的粒徑而得的平均粒徑(D50)。 The particle size (Heywood diameter) of colloidal silicon oxide was measured using a transmission electron microscope (TEM) (transmission electron microscope JEM2000FX (200kV) manufactured by JEOL Ltd.) with a magnification of 100,000 times, and using The image was analyzed by analysis software (Mac-View Ver.4.0 manufactured by Mountech Co., Ltd.) to measure the Heywood diameter (equivalent circle diameter of projected area). The average particle size of colloidal silicon oxide was analyzed by the above method. The particle size of colloidal silica is approximately 2,000 particles, and the cumulative particle size distribution (cumulative volume basis) from the small particle size side is calculated using the above-mentioned analysis software (Mac-View Ver.4.0 manufactured by Mountech Co., Ltd.). The average particle size (D50) obtained by becoming 50% of the particle size.

[重量平均分子量] [weight average molecular weight]

水溶性高分子化合物的重量平均分子量係藉由凝膠滲透層析儀(GPC)在聚丙烯酸換算下進行測量，以下顯示GPC測量條件。 The weight average molecular weight of the water-soluble polymer compound is measured by gel permeation chromatography (GPC) in terms of polyacrylic acid. The GPC measurement conditions are shown below.

[GPC條件] [GPC conditions]

管柱：G4000PWXL(Tosoh Corporation製)+G2500PWXL(Tosoh Corporation製) Column: G4000PWXL (manufactured by Tosoh Corporation) + G2500PWXL (manufactured by Tosoh Corporation)

溶析液：0.2M磷酸緩衝劑/乙腈=9/1(容積比) Eluate: 0.2M phosphate buffer/acetonitrile=9/1 (volume ratio)

流速：1.0ml/min Flow rate: 1.0ml/min

溫度：40℃ Temperature: 40℃

檢測：210nm(UV) Detection: 210nm (UV)

樣本：濃度5mg/ml(注入量100μl) Sample: concentration 5mg/ml (injection volume 100μl)

校正曲線用聚合物：聚丙烯酸分子量(峰頂分子量：Mp)11.5萬、2.8 萬、4100、1250(創和科學股份有限公司、American Polymer Standards Corp) Polymer for calibration curve: polyacrylic acid molecular weight (peak molecular weight: Mp) 115,000, 28,000, 4100, 1250 (American Polymer Standards Corp.)

[研磨條件] [Grinding conditions]

將無電解鎳-磷鍍覆的外徑95mm之鋁碟作為研磨對象，在下述研磨條件下進行研磨。 An electroless nickel-phosphorus plated aluminum disc with an outer diameter of 95 mm was used as the polishing object and polished under the following polishing conditions.

[前段研磨條件] [Preliminary grinding conditions]

研磨機：SpeedFam Company Limited製、9B雙面研磨機 Grinding machine: Manufactured by SpeedFam Company Limited, 9B double-sided grinder

研磨墊：FILWEL CO.,LTD.製、P1墊片 Polishing pad: Made by FILWEL CO., LTD., P1 gasket

壓板旋轉數：上壓板 -7.5rpm Number of platen rotations: Upper platen -7.5rpm

下壓板 22.5rpm Lower platen 22.5rpm

研磨劑組成物供給量：100ml/min Abrasive composition supply volume: 100ml/min

研磨時間：4.5分 Grinding time: 4.5 minutes

加工壓力：100g/cm² Processing pressure: 100g/cm ²

此外，前段研磨中使用研磨劑組成物A。 In addition, abrasive composition A was used in the previous stage of polishing.

[沖洗條件] [Flushing conditions]

研磨機：與前段研磨相同 Grinding machine: same as the previous grinding stage

研磨墊：與前段研磨相同 Polishing pad: Same as the previous grinding section

壓板旋轉數：與前段研磨相同 Number of platen rotations: Same as the previous grinding stage

沖洗液供給量：3L/min Flushing liquid supply volume: 3L/min

沖洗時間：20秒 Rinse time: 20 seconds

加工壓力：15g/cm² Processing pressure: 15g/cm ²

此外，沖洗液使用純水。 In addition, pure water is used as the rinse solution.

[後段研磨條件] [Latter stage grinding conditions]

研磨時間：80秒 Grinding time: 80 seconds

加工壓力：100g/cm² Processing pressure: 100g/cm ²

此外，後段研磨中使用研磨劑組成物B。 In addition, abrasive composition B is used in the subsequent polishing step.

在上述研磨條件下進行研磨試驗的結果顯示於表2、表3。 The results of the polishing test performed under the above-mentioned polishing conditions are shown in Table 2 and Table 3.

[研磨速度比] [Grinding speed ratio]

研磨速度係測量研磨後減少的鋁碟質量，再依據下式而算出。 The grinding speed is measured by measuring the mass of the aluminum disc reduced after grinding, and then calculated according to the following formula.

研磨速度(μm/min)=鋁碟質量減少量(g)/研磨時間(min)/鋁碟單面的面積(cm²)/無電解鎳-磷鍍覆皮膜的密度(g/cm³)/2×10⁴ Grinding speed (μm/min) = mass reduction of aluminum disc (g)/polishing time (min)/area of one side of aluminum disc (cm ² )/density of electroless nickel-phosphorus plating film (g/cm ³ ) /2×10 ⁴

(其中，上式中，鋁碟單面的面積為65.9cm²，無電解鎳-磷鍍覆皮膜的密度為8.0g/cm³) (Among them, in the above formula, the area of one side of the aluminum disk is 65.9cm ² and the density of the electroless nickel-phosphorus plating film is 8.0g/cm ³ )

研磨速度比係將使用上式所求出的比較例2之研磨速度設為1(基準)時的相對值。比較例2的實測值為0.320μm/min。 The polishing speed ratio is a relative value when the polishing speed of Comparative Example 2 calculated using the above formula is set to 1 (standard). The actual measured value of Comparative Example 2 was 0.320 μm/min.

[起伏] [Ups and downs]

鋁碟的起伏係使用利用AMETEK,Inc.製掃描式白色干涉法的三維表面結構分析顯微鏡進行測量。測量條件為AMETEK,Inc.製測量裝置(New View 8300(透鏡：1.4倍、變焦：1.0倍))、波長500~1000μm，測量區為6mm×6mm，使用AMETEK,Inc.製分析軟體(Mx)進行分析。此外，表2、表3所示的值係將比較例2的起伏設為1(基準)時的相對值。比較例2的實測值為1.66□。 The undulations of the aluminum disc were measured using a three-dimensional surface structure analysis microscope using a scanning white interference method manufactured by AMETEK, Inc. The measurement conditions are a measurement device (New View 8300 (lens: 1.4x, zoom: 1.0x)) made by AMETEK, Inc., a wavelength of 500~1000 μm, a measurement area of 6mm×6mm, and analysis software (Mx) made by AMETEK, Inc. Perform analysis. In addition, the values shown in Table 2 and Table 3 are relative values when the fluctuation in Comparative Example 2 is set to 1 (standard). The actual measured value of Comparative Example 2 was 1.66□.

[滾降比] [roll-off ratio]

作為端面形狀的評價，係測量以數值化呈現端面塌陷程度的滾降。滾降係使用AMETEK,Inc.製測量裝置(New View 8300(透鏡：1.4倍、變焦：1.0倍)與AMETEK,Inc.製分析軟體(Mx)進行測量。 As an evaluation of the end surface shape, roll-off is measured to numerically represent the degree of end surface collapse. The roll-off system was measured using a measuring device (New View 8300 (lens: 1.4x, zoom: 1.0x) manufactured by AMETEK, Inc.) and analysis software (Mx) manufactured by AMETEK, Inc.

使用圖1對滾降的測量方法進行說明。圖1係表示研磨的對象物，即經無電解鎳-磷鍍覆的外徑95mm之鋁碟中，通過碟片中心且相對於經研磨之表面垂直的剖面圖。在測量滾降時，首先沿著碟片的外周端設置垂線h，從垂線h朝向經研磨之表面上的碟片之中心設置平行於垂線h且與垂線h的距離為3.90mm的線j，將碟片剖面的線與線j相交處作為點A。又，設置平行於垂線h且與垂線h的距離為0.30mm的線k，將碟片剖面的線與線k相交處作為點B。設置將點A與點B連結的線m,再設置垂直於線m的線t，將碟片剖面的線與線t相交處作為點C，並將線m與線t相交處作為點D。然後，測量點C-D間的距離達到最大時的距離作為滾降。 The measurement method of roll-off will be explained using Figure 1. Figure 1 is a cross-sectional view of an object for grinding, that is, an aluminum disc with an outer diameter of 95 mm coated with electroless nickel-phosphorus, passing through the center of the disc and perpendicular to the ground surface. When measuring roll-off, first set a vertical line h along the outer peripheral end of the disc, and set a line j parallel to the vertical line h and 3.90 mm away from the vertical line h from the vertical line h toward the center of the disc on the ground surface. Let the intersection of the disc section line and line j be regarded as point A. In addition, a line k is set parallel to the vertical line h and the distance from the vertical line h is 0.30 mm, and the intersection of the disc cross-section line and the line k is defined as point B. Set a line m connecting point A and point B, and then set a line t perpendicular to line m. Let the intersection of the disc cross section line and line t be point C, and let the intersection of line m and line t be point D. Then, the distance when the distance between points C-D reaches the maximum is measured as the roll-off.

滾降比係將使用上述方法所測量的比較例2之滾降設為1(基準)時的相對值。比較例2的實測值為154Å。The roll-off ratio is a relative value when the roll-off of Comparative Example 2 measured using the above method is set to 1 (standard). The measured value of Comparative Example 2 is 154Å.

AA：丙烯酸 AA: acrylic

TBAA：第三丁基丙烯醯胺 TBAA: tertiary butylacrylamide

330T：聚氧乙烯三癸醚硫酸鈉 330T: Polyoxyethylene Tridecyl Ether Sulfate Sodium

LS-30：月桂基硫酸鈉 LS-30: Sodium Lauryl Sulfate

AA：丙烯酸 AA: acrylic

TBAA：第三丁基丙烯醯胺 TBAA: tertiary butylacrylamide

LS-30：月桂基硫酸鈉 LS-30: Sodium Lauryl Sulfate

[研究] [Research]

相對於比較例1，實施例1係在前段研磨中添加水溶性高分子化合物的實驗，其研磨速度、起伏、滾降皆有所改善。又，相對於比較例3，實施例1係添加有機硫酸酯鹽化合物的結果，此情況下其研磨速度、起伏、滾降亦皆有所改善。 Compared with Comparative Example 1, Example 1 is an experiment in which a water-soluble polymer compound is added in the front stage of grinding, and the grinding speed, undulation, and roll-off are all improved. In addition, compared to Comparative Example 3, Example 1 is the result of adding an organic sulfate ester salt compound. In this case, the polishing speed, undulation, and roll-off are also improved.

相對於比較例2，實施例2係在前段研磨中添加水溶性高分子化合物的實驗，其研磨速度、起伏、滾降皆有所改善。又，相對於比較例3，實施例2係添加有機硫酸酯鹽化合物的結果，此情況下其研磨速度、起伏、滾降亦皆有所改善。 Compared with Comparative Example 2, Example 2 is an experiment in which a water-soluble polymer compound is added in the front stage of grinding, and the grinding speed, undulation, and roll-off are all improved. In addition, compared to Comparative Example 3, Example 2 is the result of adding an organic sulfate ester salt compound. In this case, the polishing speed, fluctuation, and roll-off are also improved.

相對於比較例2，實施例3係在前段研磨中添加水溶性高分子化合物的實驗，其研磨速度、起伏、滾降皆有所改善。又，相對於比較例4，實施例3係添加有機硫酸酯鹽化合物的實驗，此情況下其研磨速度、起伏、滾降亦皆有所改善。 Compared with Comparative Example 2, Example 3 is an experiment in which a water-soluble polymer compound is added in the front stage of grinding, and the grinding speed, undulation, and roll-off are all improved. In addition, compared to Comparative Example 4, Example 3 is an experiment in which an organic sulfate ester salt compound is added. In this case, the polishing speed, undulation, and roll-off are also improved.

相對於比較例2，實施例4係在前段研磨中添加水溶性高分子化合物的實驗，其研磨速度相同，而起伏與滾降有所改善。 Compared with Comparative Example 2, Example 4 is an experiment in which a water-soluble polymer compound is added in the front stage of grinding. The grinding speed is the same, but the undulation and roll-off are improved.

相對於比較例2，實施例5係在前段研磨中添加水溶性高分子化合物的實驗，其研磨速度、起伏、滾降皆有所改善。 Compared with Comparative Example 2, Example 5 is an experiment in which a water-soluble polymer compound is added in the front stage of grinding, and the grinding speed, undulation, and roll-off are all improved.

實施例6係使實施例5所使用之水溶性高分子化合物的組成變化而使用由3種單體成分所構成之共聚物的實驗。 Example 6 is an experiment in which the composition of the water-soluble polymer compound used in Example 5 was changed and a copolymer composed of three monomer components was used.

相對於比較例1，實施例7係在後段研磨中添加水溶性高分子化合物的實驗，其研磨速度、起伏、滾降皆有所改善。又，相對於比較例5，實施例7係添加有機硫酸酯鹽化合物的實驗，其研磨速度、起伏、滾降皆有所改善。 Compared with Comparative Example 1, Example 7 is an experiment in which a water-soluble polymer compound is added in the later stage of grinding, and the grinding speed, undulation, and roll-off are all improved. In addition, compared to Comparative Example 5, Example 7 was an experiment in which an organic sulfate ester compound was added, and the polishing speed, undulation, and roll-off were all improved.

相對於比較例2，實施例8係在後段研磨中添加水溶性高分子化合物的實驗，其研磨速度、起伏、滾降皆有所改善。又，相對於比較例5，實施例8係添加有機硫酸酯鹽化合物的實驗，其研磨速度、起伏、滾降皆有所改善。 Compared with Comparative Example 2, Example 8 was an experiment in which a water-soluble polymer compound was added in the subsequent grinding stage, and the grinding speed, undulation, and roll-off were all improved. In addition, compared to Comparative Example 5, Example 8 was an experiment in which an organic sulfate ester compound was added, and the polishing speed, undulation, and roll-off were all improved.

相對於比較例2，實施例9係在後段研磨中添加水溶性高分子化合物的實驗，其研磨速度、起伏、滾降皆有所改善。又，相對於比較例6，實施例9係添加有機硫酸酯鹽化合物的實驗，其研磨速度、起伏、滾降皆有所改善。 Compared with Comparative Example 2, Example 9 is an experiment in which a water-soluble polymer compound is added in the later stage of grinding, and the grinding speed, fluctuation, and roll-off are all improved. In addition, compared to Comparative Example 6, Example 9 was an experiment in which an organic sulfate ester compound was added, and the polishing speed, undulation, and roll-off were all improved.

相對於比較例2，實施例10係在後段研磨中添加水溶性高分子化合物的實驗，其研磨速度、起伏、滾降皆有所改善。 Compared with Comparative Example 2, Example 10 is an experiment in which a water-soluble polymer compound is added in the later stage of grinding, and the grinding speed, undulation, and roll-off are all improved.

相對於比較例2，實施例11係在後段研磨中添加水溶性高分子化合物的實驗，其研磨速度、起伏、滾降皆有所改善。 Compared with Comparative Example 2, Example 11 is an experiment in which a water-soluble polymer compound is added in the later stage of grinding, and the grinding speed, undulation, and roll-off are all improved.

實施例12係使實施例11所使用之水溶性高分子化合物的組成變化而使用由3種單體成分所構成之共聚物的實驗。 Example 12 is an experiment in which the composition of the water-soluble polymer compound used in Example 11 was changed and a copolymer composed of three monomer components was used.

相對於比較例1，實施例13係在前段研磨及後段研磨中添加水溶性高分子化合物的實驗，其研磨速度、起伏、滾降皆有所改善。又，相對於比較例9，實施例13係添加有機硫酸酯鹽化合物的實驗，其研磨速度、起伏、滾降皆有所改善。 Compared with Comparative Example 1, Example 13 is an experiment in which a water-soluble polymer compound was added in the front-stage grinding and the back-stage grinding. The grinding speed, undulation, and roll-off were all improved. In addition, compared to Comparative Example 9, Example 13 was an experiment in which an organic sulfate ester compound was added, and the polishing speed, undulation, and roll-off were all improved.

相對於比較例2，實施例14係在前段研磨及後段研磨中添加水溶性高分子化合物的實驗，其研磨速度、起伏、滾降皆有所改善。又，相對於比較例9，實施例14係添加有機硫酸酯鹽化合物的實驗，其研磨速度、起伏、滾降皆有所改善。 Compared with Comparative Example 2, Example 14 is an experiment in which a water-soluble polymer compound was added in the front-stage grinding and the back-stage grinding. The grinding speed, undulation, and roll-off were all improved. In addition, compared to Comparative Example 9, Example 14 was an experiment in which an organic sulfate ester compound was added, and the polishing speed, undulation, and roll-off were all improved.

相對於比較例2，實施例15係在前段研磨及後段研磨中添加水溶性高分子化合物的實驗，其研磨速度、起伏、滾降皆有所改善。又，相對於比較例10，實施例15係添加有機硫酸酯鹽化合物的實驗，其研磨速度、起伏、滾降皆有所改善。 Compared with Comparative Example 2, Example 15 is an experiment in which a water-soluble polymer compound was added in the front-stage grinding and the back-stage grinding. The grinding speed, undulation, and roll-off were all improved. In addition, compared to Comparative Example 10, Example 15 was an experiment in which an organic sulfate ester compound was added, and the polishing speed, undulation, and roll-off were all improved.

相對於比較例2，實施例16係在前段研磨及後段研磨中添加水溶性高分子化合物的實驗，其研磨速度、起伏、滾降皆有所改善。 Compared with Comparative Example 2, Example 16 is an experiment in which a water-soluble polymer compound was added in the front-stage grinding and the back-stage grinding. The grinding speed, undulation, and roll-off were all improved.

相對於比較例2，實施例17係在前段研磨及後段研磨中添加水溶性高分子化合物的實驗，其研磨速度、起伏、滾降皆有所改善。 Compared with Comparative Example 2, Example 17 was an experiment in which a water-soluble polymer compound was added in the front-stage grinding and the back-stage grinding. The grinding speed, undulation, and roll-off were all improved.

實施例18係使實施例17所使用之水溶性高分子化合物的組成變化而使用由3種單體成分所構成之共聚物的實驗。 Example 18 is an experiment in which the composition of the water-soluble polymer compound used in Example 17 was changed and a copolymer composed of three monomer components was used.

相對於比較例1，實施例19係在後段研磨中添加AA均聚物與ATBS均聚物之混合物的實驗，其研磨速度、起伏、滾降皆有所改善。 Compared with Comparative Example 1, Example 19 was an experiment in which a mixture of AA homopolymer and ATBS homopolymer was added in the later grinding stage. The grinding speed, undulation, and roll-off were all improved.

相對於比較例2，實施例20係在後段研磨中添加AA均聚物與ATBS均聚物之混合物的實驗，其研磨速度、起伏、滾降皆有所改善。又，比較例7係在後段研磨中添加AA均聚物的實驗，即使相對於此，實施例20的研磨速度、起伏、滾降亦皆有所改善。再者，比較例8係在後段研磨中添加ATBS均聚物的實驗，即使相對於此，實施例20的研磨速度、起伏、滾降亦皆有所改善。 Compared with Comparative Example 2, Example 20 is an experiment in which a mixture of AA homopolymer and ATBS homopolymer is added in the later grinding stage, and the grinding speed, undulation, and roll-off are all improved. In addition, Comparative Example 7 was an experiment in which AA homopolymer was added in the later stage of polishing. Even compared to this, the polishing speed, undulation, and roll-off of Example 20 were all improved. Furthermore, Comparative Example 8 is an experiment in which ATBS homopolymer was added in the later stage of polishing. Even compared to this, the polishing speed, undulation, and roll-off of Example 20 were all improved.

由以上明顯可知，藉由本申請發明之研磨方法，可改善研磨速度、起伏、滾降的全部性能。藉由本申請發明，能夠高生產性地製造多段研磨方式中的粗研磨步驟後基板表面上的起伏與滾降減少的基板。 From the above, it is obvious that the grinding method of the present invention can improve the overall performance of grinding speed, undulation, and roll-off. According to the invention of the present application, it is possible to produce a substrate with reduced undulations and roll-off on the surface of the substrate after the rough polishing step in the multi-stage polishing method with high productivity.

[產業上的可利用性] [Industrial availability]

本發明之基板研磨方法可用於半導體、硬碟等磁記錄媒體等的電子零件的研磨。特別可用於玻璃磁碟基板或鋁製磁碟基板等的磁記錄媒體用基板的表面研磨。再者，可用於在鋁合金製基板表面上形成無電解鎳-磷鍍覆皮膜之磁記錄媒體用鋁製磁碟基板的表面研磨。 The substrate polishing method of the present invention can be used for polishing electronic components such as semiconductors and magnetic recording media such as hard disks. It is particularly useful for surface polishing of magnetic recording medium substrates such as glass disk substrates and aluminum disk substrates. Furthermore, it can be used for surface polishing of aluminum disk substrates for magnetic recording media in which an electroless nickel-phosphorus plating film is formed on the surface of an aluminum alloy substrate.

A、B、C、D‧‧‧點 Point A, B, C, D‧‧‧

h‧‧‧垂線 h‧‧‧vertical line

j、k、m、t‧‧‧線 j, k, m, t‧‧‧ line

Claims

一種磁碟基板之研磨方法，其具有下述(1)~(3)的步驟，且以同一研磨機進行各步驟(1)~(3)：(1)將含有氧化鋁粒子、水溶性高分子化合物、有機硫酸酯鹽化合物及水的研磨劑組成物A供給至研磨機，進行磁碟基板之前段研磨的步驟，其中該水溶性高分子化合物係以具有羧酸基之單體及具有磺酸基之單體為必要單體的共聚物；(2)將步驟(1)所得到的該磁碟基板進行沖洗處理的步驟；以及(3)將含有膠質氧化矽及水的研磨劑組成物B供給至研磨機，進行該磁碟基板之後段研磨的步驟。 A grinding method for a magnetic disk substrate, which has the following steps (1) to (3), and uses the same grinder to perform each step (1) to (3): (1) grinding alumina particles containing highly water-soluble The abrasive composition A of a molecular compound, an organic sulfate ester salt compound and water is supplied to a grinder to perform the step of grinding the disk substrate in the front stage, wherein the water-soluble polymer compound is composed of a monomer with a carboxylic acid group and a sulfonate The acid-based monomer is a copolymer of the necessary monomer; (2) the step of rinsing the disk substrate obtained in step (1); and (3) the abrasive composition containing colloidal silica and water B is supplied to the grinding machine, and the next step of grinding the disk substrate is performed.

一種磁碟基板之研磨方法，其具有下述(1)~(3)的步驟，且以同一研磨機進行各步驟(1)~(3)：(1)將含有氧化鋁粒子、有機硫酸酯鹽化合物及水的研磨劑組成物A供給至研磨機，進行磁碟基板之前段研磨的步驟；(2)將步驟(1)所得到的該磁碟基板進行沖洗處理的步驟；以及(3)將含有膠質氧化矽、水溶性高分子化合物及水的研磨劑組成物B供給至研磨機，進行該磁碟基板之後段研磨的步驟，其中該水溶性高分子化合物係以具有羧酸基之單體及具有磺酸基之單體為必要單體的共聚物。 A grinding method for a magnetic disk substrate, which has the following steps (1) to (3), and uses the same grinder to perform each step (1) to (3): (1) grinding alumina particles, organic sulfate The abrasive composition A of the salt compound and water is supplied to the grinder to perform the step of grinding the disk substrate in the previous stage; (2) the step of rinsing the disk substrate obtained in step (1); and (3) The abrasive composition B containing colloidal silica, a water-soluble polymer compound and water is supplied to the grinder to perform the subsequent step of grinding the disk substrate, wherein the water-soluble polymer compound is a monomer having a carboxylic acid group. The monomer and the monomer with sulfonic acid group are copolymers of essential monomers.

一種磁碟基板之研磨方法，其具有下述(1)~(3)的步驟，且以同一研磨機進行各步驟(1)~(3)：(1)將含有氧化鋁粒子、水溶性高分子化合物、有機硫酸酯鹽化合物及水的研磨劑組成物A供給至研磨機，進行磁碟基板之前段研磨的步驟，其中該水溶性高分子化合物係以具有羧酸基之單體及具有磺酸基之單體為必要單體的共聚物； (2)將步驟(1)所得到的該磁碟基板進行沖洗處理的步驟；以及(3)將含有膠質氧化矽、水溶性高分子化合物及水的研磨劑組成物B供給至研磨機，進行該磁碟基板之後段研磨的步驟，其中該水溶性高分子化合物係以具有羧酸基之單體及具有磺酸基之單體為必要單體的共聚物。 A method for grinding a disk substrate, which has the following steps (1) to (3), and uses the same grinder to perform each step (1) to (3): (1) grinding alumina particles containing highly water-soluble The abrasive composition A of a molecular compound, an organic sulfate ester salt compound and water is supplied to a grinder to perform the step of grinding the disk substrate in the front stage, wherein the water-soluble polymer compound is composed of a monomer with a carboxylic acid group and a sulfonate The acid-based monomer is a copolymer of essential monomers; (2) The step of rinsing the disk substrate obtained in step (1); and (3) Supplying the abrasive composition B containing colloidal silica, a water-soluble polymer compound and water to a grinder, and performing In the subsequent grinding step of the magnetic disk substrate, the water-soluble polymer compound is a copolymer with a monomer having a carboxylic acid group and a monomer having a sulfonic acid group as essential monomers.

一種磁碟基板之研磨方法，其具有下述(1)~(3)的步驟，且以同一研磨機進行各步驟(1)~(3)：(1)將含有氧化鋁粒子、水溶性高分子化合物、有機硫酸酯鹽化合物及水的研磨劑組成物A供給至研磨機，進行磁碟基板之前段研磨的步驟，其中該水溶性高分子化合物係包含以具有羧酸基之單體為必要單體的聚合物與以具有磺酸基之單體為必要單體的聚合物的混合物；(2)將步驟(1)所得到的該磁碟基板進行沖洗處理的步驟；以及(3)將含有膠質氧化矽及水的研磨劑組成物B供給至研磨機，進行該磁碟基板之後段研磨的步驟。 A grinding method for a magnetic disk substrate, which has the following steps (1) to (3), and uses the same grinder to perform each step (1) to (3): (1) grinding alumina particles containing highly water-soluble The abrasive composition A of a molecular compound, an organic sulfate ester salt compound and water is supplied to a grinder to perform the step of grinding the disk substrate in the front stage, wherein the water-soluble polymer compound must contain a monomer having a carboxylic acid group. A mixture of a monomer polymer and a polymer containing a monomer having a sulfonic acid group as an essential monomer; (2) a step of rinsing the disk substrate obtained in step (1); and (3) rinsing the disk substrate obtained in step (1); The abrasive composition B containing colloidal silica and water is supplied to the grinder, and the subsequent step of grinding the disk substrate is performed.

一種磁碟基板之研磨方法，其具有下述(1)~(3)的步驟，且以同一研磨機進行各步驟(1)~(3)：(1)將含有氧化鋁粒子、有機硫酸酯鹽化合物及水的研磨劑組成物A供給至研磨機，進行磁碟基板之前段研磨的步驟；(2)將步驟(1)所得到的該磁碟基板進行沖洗處理的步驟；以及(3)將含有膠質氧化矽、水溶性高分子化合物及水的研磨劑組成物B供給至研磨機，進行該磁碟基板之後段研磨的步驟，其中該水溶性高分子化合物係包含以具有羧酸基之單體為必要單體的聚合物與以具有磺酸基之單體為必要單體的聚合物的混合物。 A grinding method for a magnetic disk substrate, which has the following steps (1) to (3), and uses the same grinder to perform each step (1) to (3): (1) grinding alumina particles, organic sulfate The abrasive composition A of the salt compound and water is supplied to the grinder to perform the step of grinding the disk substrate in the previous stage; (2) the step of rinsing the disk substrate obtained in step (1); and (3) The abrasive composition B containing colloidal silica, a water-soluble polymer compound and water is supplied to the grinder to perform the subsequent grinding step of the disk substrate, wherein the water-soluble polymer compound contains a carboxylic acid group. A mixture of a polymer in which a monomer is an essential monomer and a polymer in which a monomer having a sulfonic acid group is an essential monomer.

一種磁碟基板之研磨方法，其具有下述(1)~(3)的步驟，且以同一研磨機進行各步驟(1)~(3)： (1)將含有氧化鋁粒子、水溶性高分子化合物、有機硫酸酯鹽化合物及水的研磨劑組成物A供給至研磨機，進行磁碟基板之前段研磨的步驟，其中該水溶性高分子化合物係包含以具有羧酸基之單體為必要單體的聚合物與以具有磺酸基之單體為必要單體的聚合物的混合物；(2)將步驟(1)所得到的該磁碟基板進行沖洗處理的步驟；以及(3)將含有膠質氧化矽、水溶性高分子化合物及水的研磨劑組成物B供給至研磨機，進行該磁碟基板之後段研磨的步驟，其中該水溶性高分子化合物係包含以具有羧酸基之單體為必要單體的聚合物與以具有磺酸基之單體為必要單體的聚合物的混合物。 A method for grinding a disk substrate, which has the following steps (1) to (3), and uses the same grinding machine to perform each step (1) to (3): (1) The abrasive composition A containing alumina particles, a water-soluble polymer compound, an organic sulfate compound and water is supplied to a grinder to perform the step of grinding the disk substrate in the front stage, wherein the water-soluble polymer compound It is a mixture containing a polymer containing a monomer having a carboxylic acid group as an essential monomer and a polymer containing a monomer having a sulfonic acid group as an essential monomer; (2) the magnetic disk obtained in step (1) The step of rinsing the substrate; and (3) supplying the abrasive composition B containing colloidal silica, a water-soluble polymer compound and water to a grinder to perform a subsequent step of grinding the disk substrate, wherein the water-soluble polymer The polymer compound contains a mixture of a polymer containing a monomer having a carboxylic acid group as an essential monomer and a polymer containing a monomer having a sulfonic acid group as an essential monomer.

如請求項1至3中任一項之磁碟基板之研磨方法，其中，該水溶性高分子化合物的重量平均分子量為1,000~1,000,000。 The method for polishing a disk substrate according to any one of claims 1 to 3, wherein the weight average molecular weight of the water-soluble polymer compound is 1,000~1,000,000.

如請求項1至3中任一項之磁碟基板之研磨方法，其中，該水溶性高分子化合物，即以具有羧酸基之單體及具有磺酸基之單體為必要單體的共聚物，係以具有羧酸基之單體與具有磺酸基之單體及具有醯胺基之單體為必要單體的共聚物，且其重量平均分子量為1,000~1,000,000。 The method for polishing a disk substrate according to any one of claims 1 to 3, wherein the water-soluble polymer compound is a copolymer of a monomer having a carboxylic acid group and a monomer having a sulfonic acid group as essential monomers. It is a copolymer with a monomer having a carboxylic acid group, a monomer having a sulfonic acid group and a monomer having an amide group as essential monomers, and its weight average molecular weight is 1,000~1,000,000.

如請求項1至3中任一項之磁碟基板之研磨方法，其中，該具有羧酸基之單體係選自丙烯酸或其鹽、甲基丙烯酸或其鹽的單體，該水溶性高分子化合物中源自具有羧酸基之單體的構成單元的比例為5~95mol%。 The method for polishing a magnetic disk substrate according to any one of claims 1 to 3, wherein the monomer having a carboxylic acid group is selected from the group consisting of acrylic acid or its salts, methacrylic acid or its salts, and the water-soluble monomer is high The proportion of structural units derived from monomers having carboxylic acid groups in the molecular compound is 5 to 95 mol%.

如請求項1至3中任一項之磁碟基板之研磨方法，其中，該具有磺酸基之單體係選自異戊二烯磺酸、2-丙烯醯胺-2-甲基丙磺酸、2-甲基丙烯醯胺-2-甲基丙磺酸、苯乙烯磺酸、乙烯磺酸、烯丙基磺酸、異戊烯磺酸、乙烯萘磺酸及該等之鹽的單體，該水溶性高分子化合物中源自具有磺酸基之單體的構成單元的比例為 5~95mol%。 The method for polishing a disk substrate according to any one of claims 1 to 3, wherein the monosystem with a sulfonic acid group is selected from the group consisting of isoprene sulfonic acid and 2-acrylamide-2-methylpropanesulfonate. Acid, 2-methacrylamide-2-methylpropanesulfonic acid, styrenesulfonic acid, ethylenesulfonic acid, allylsulfonic acid, isopentenesulfonic acid, vinylnaphthalenesulfonic acid and their salts body, the proportion of structural units derived from monomers having sulfonic acid groups in the water-soluble polymer compound is 5~95mol%.

如請求項8之磁碟基板之研磨方法，其中，該具有醯胺基之單體係選自丙烯醯胺、甲基丙烯醯胺、N-烷基丙烯醯胺、N-烷基甲基丙烯醯胺的單體。 The method for polishing a magnetic disk substrate according to claim 8, wherein the monosystem having an amide group is selected from the group consisting of acrylamide, methacrylamide, N-alkyl acrylamide, and N-alkyl methacrylamide. Monomer of amide.

如請求項4至6中任一項之磁碟基板之研磨方法，其中，該水溶性高分子化合物的重量平均分子量分別為1,000~1,000,000，以具有羧酸基之單體為必要單體的聚合物的比例為5~95質量%，且以具有磺酸基之單體為必要單體的聚合物的比例為5~95質量%。 The method for polishing a disk substrate according to any one of claims 4 to 6, wherein the weight average molecular weight of the water-soluble polymer compound is 1,000 to 1,000,000, and a monomer having a carboxylic acid group is the necessary monomer for polymerization. The proportion of the polymer is 5 to 95 mass %, and the proportion of the polymer containing a monomer having a sulfonic acid group as an essential monomer is 5 to 95 mass %.

如請求項1至6中任一項之磁碟基板之研磨方法，其中，該有機硫酸酯鹽化合物係以下列通式(1)表示：R-O-SO₃M (1)式中，R表示碳數5~21的直鏈或分支之烷基、烯基、芳基或烷基芳基，M表示鹼金屬、鹼土金屬、銨離子或有機陽離子。 The method for polishing a disk substrate according to any one of claims 1 to 6, wherein the organic sulfate ester salt compound is represented by the following general formula (1): RO-SO ₃ M (1) In the formula, R represents carbon A linear or branched alkyl, alkenyl, aryl or alkylaryl group with a number of 5 to 21, M represents an alkali metal, alkaline earth metal, ammonium ion or organic cation.

如請求項1至6中任一項之磁碟基板之研磨方法，其中，該有機硫酸酯鹽化合物係以下列通式(2)表示：R-O-(AO)_n-SO₃M (2)式中，R表示碳數5~21的直鏈或分支之烷基、烯基、芳基或烷基芳基，AO表示碳數2或3之氧伸烷基，n表示1~30之整數，M表示鹼金屬、鹼土金屬、銨離子或有機陽離子。 The method for polishing a disk substrate according to any one of claims 1 to 6, wherein the organic sulfate ester salt compound is represented by the following general formula (2): RO-(AO) _n -SO ₃ M (2) Formula Among them, R represents a linear or branched alkyl, alkenyl, aryl or alkylaryl group with 5 to 21 carbon atoms, AO represents an oxyalkylene group with 2 or 3 carbon atoms, n represents an integer from 1 to 30, M represents an alkali metal, alkaline earth metal, ammonium ion or organic cation.

如請求項1至6中任一項之磁碟基板之研磨方法，其中，該研磨劑組成物A及該研磨劑組成物B進一步含有酸及/或其鹽，且pH值(25℃)在0.1~4.0的範圍。 The method for polishing a disk substrate according to any one of claims 1 to 6, wherein the abrasive composition A and the abrasive composition B further contain an acid and/or its salt, and the pH value (25°C) is between The range is 0.1~4.0.

如請求項1至6中任一項之磁碟基板之研磨方法，其中，該研磨劑組成物A及該研磨劑組成物B進一步含有氧化劑。 The method for polishing a magnetic disk substrate according to any one of claims 1 to 6, wherein the abrasive Composition A and the abrasive composition B further contain an oxidizing agent.

如請求項1至6中任一項之磁碟基板之研磨方法，其中，針對在鋁合金基板的表面形成有鎳-磷鍍覆皮膜的磁記錄媒體用磁碟基板，以多段研磨方式進行研磨時，係在最終研磨步驟之前的研磨步驟中進行。 The method for polishing a magnetic disk substrate according to any one of claims 1 to 6, wherein the magnetic disk substrate for a magnetic recording medium having a nickel-phosphorus plating film formed on the surface of the aluminum alloy substrate is polished in a multi-stage polishing manner. When, it is carried out in the grinding step before the final grinding step.

一種磁碟基板用研磨劑組成物，係在如請求項2或3之磁碟基板之研磨方法中，步驟(3)所使用的研磨劑組成物B，其含有膠質氧化矽、水溶性高分子化合物及水，其中該水溶性高分子化合物係以具有羧酸基之單體及具有磺酸基之單體為必要單體的共聚物。 An abrasive composition for magnetic disk substrates. In the polishing method of magnetic disk substrates as claimed in claim 2 or 3, the abrasive composition B used in step (3) contains colloidal silicon oxide and water-soluble polymers. A compound and water, wherein the water-soluble polymer compound is a copolymer with a monomer having a carboxylic acid group and a monomer having a sulfonic acid group as essential monomers.

如請求項18之磁碟基板用研磨劑組成物，其中，該水溶性高分子化合物的其重量平均分子量為1,000~1,000,000。 As claimed in claim 18, the abrasive composition for magnetic disk substrates, wherein the weight average molecular weight of the water-soluble polymer compound is 1,000~1,000,000.

如請求項18之磁碟基板用研磨劑組成物，其中，該水溶性高分子化合物，即以具有羧酸基之單體及具有磺酸基之單體為必要單體的共聚物，係以具有羧酸基之單體與具有磺酸基之單體及具有醯胺基之單體為必要單體的共聚物，且其重量平均分子量為1,000~1,000,000。 As claimed in Claim 18, the abrasive composition for magnetic disk substrates, wherein the water-soluble polymer compound, that is, a copolymer with a monomer having a carboxylic acid group and a monomer having a sulfonic acid group as essential monomers, is A copolymer of a monomer with a carboxylic acid group, a monomer with a sulfonic acid group and a monomer with an amide group is an essential monomer, and its weight average molecular weight is 1,000~1,000,000.

如請求項18之磁碟基板用研磨劑組成物，其中，該具有羧酸基之單體係選自丙烯酸或其鹽、甲基丙烯酸或其鹽的單體，該水溶性高分子化合物中源自具有羧酸基之單體的構成單元的比例為5~95mol%。 The abrasive composition for disk substrates of claim 18, wherein the monomer having a carboxylic acid group is selected from the group consisting of acrylic acid or its salts, methacrylic acid or its salts, and the source of the water-soluble polymer compound is The proportion of structural units derived from the monomer having a carboxylic acid group is 5 to 95 mol%.

如請求項18之磁碟基板用研磨劑組成物，其中，該具有磺酸基之單體係選自異戊二烯磺酸、2-丙烯醯胺-2-甲基丙磺酸、2-甲基丙烯醯胺-2-甲基丙磺酸、苯乙烯磺酸、乙烯磺酸、烯丙基磺酸、異戊烯磺酸、乙烯萘磺酸及該等之鹽的單體，該水溶性高分子化合物中源自具有磺酸基之單體的構成單元的比例為5~95mol%。 The abrasive composition for disk substrates of claim 18, wherein the monosystem with a sulfonic acid group is selected from isoprene sulfonic acid, 2-acrylamide-2-methylpropanesulfonic acid, 2- Methacrylamide - monomer of 2-methylpropanesulfonic acid, styrenesulfonic acid, vinylsulfonic acid, allylsulfonic acid, isopentenesulfonic acid, vinylnaphthalenesulfonic acid and their salts, the water-soluble The proportion of structural units derived from monomers having sulfonic acid groups in the polymer compound is 5 to 95 mol%.

如請求項20之磁碟基板用研磨劑組成物，其中，該具有醯胺基之單體係選自丙烯醯胺、甲基丙烯醯胺、N-烷基丙烯醯胺、N-烷基甲基丙烯醯胺的單體。 As claimed in claim 20, the abrasive composition for magnetic disk substrates, wherein the monosystem having an amide group is selected from the group consisting of acrylamide, methacrylamide, N-alkyl acrylamide, and N-alkylmethacrylamide. Monomer of acrylamide.

一種磁碟基板用研磨劑組成物，係如請求項5或6之磁碟基板之研磨方法的步驟(3)所使用的研磨劑組成物B，其中，該水溶性高分子化合物的重量平均分子量分別為1,000~1,000,000，以具有羧酸基之單體為必要單體的聚合物的比例為5~95質量%，且以具有磺酸基之單體為必要單體的聚合物的比例為5~95質量%。 An abrasive composition for magnetic disk substrates, which is the abrasive composition B used in step (3) of the polishing method for magnetic disk substrates as claimed in claim 5 or 6, wherein the weight average molecular weight of the water-soluble polymer compound They are 1,000~1,000,000 respectively, the ratio of polymers using monomers with carboxylic acid groups as essential monomers is 5~95% by mass, and the ratio of polymers using monomers with sulfonic acid groups as essential monomers is 5 ~95% by mass.