TW201522597A - Method for producing polishing liquid composition - Google Patents

Method for producing polishing liquid composition Download PDF

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TW201522597A
TW201522597A TW103136875A TW103136875A TW201522597A TW 201522597 A TW201522597 A TW 201522597A TW 103136875 A TW103136875 A TW 103136875A TW 103136875 A TW103136875 A TW 103136875A TW 201522597 A TW201522597 A TW 201522597A
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polishing
acid
less
filter
producing
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TW103136875A
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TWI639690B (en
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Kanji Sato
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Kao Corp
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    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B5/00—Recording by magnetisation or demagnetisation of a record carrier; Reproducing by magnetic means; Record carriers therefor
    • G11B5/84—Processes or apparatus specially adapted for manufacturing record carriers
    • G11B5/8404—Processes or apparatus specially adapted for manufacturing record carriers manufacturing base layers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • C09K3/1454—Abrasive powders, suspensions and pastes for polishing
    • C09K3/1463—Aqueous liquid suspensions
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09G—POLISHING COMPOSITIONS; SKI WAXES
    • C09G1/00—Polishing compositions
    • C09G1/02—Polishing compositions containing abrasives or grinding agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • C09K3/1409—Abrasive particles per se

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Manufacturing & Machinery (AREA)
  • Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)
  • Manufacturing Of Magnetic Record Carriers (AREA)
  • Grinding-Machine Dressing And Accessory Apparatuses (AREA)

Abstract

This method for producing a polishing liquid composition comprises a step for filtering a silica dispersion liquid to be processed, which contains colloidal silica, with use of a filter containing a filtration assistant. The colloidal silica has an average particle diameter of primary particles of from 1 nm to 50 nm (inclusive) as determined by a titration method, and the filtration assistant has a hydroxyl group density of 0.40 x 10-5 mol/m2 or more. It is preferable that the ratio of the average particle diameter of primary particles of the colloidal silica as determined by a titration method to the average particle diameter of the filtration assistant as determined by a laser particle size distribution measuring instrument is from 1.20 x 10-3 to 4.20 x 10-3 (inclusive).

Description

研磨液組合物之製造方法 Method for producing polishing liquid composition

本揭示係關於一種研磨液組合物之製造方法、研磨液組合物、磁碟基板之製造方法等。 The present disclosure relates to a method for producing a polishing liquid composition, a polishing liquid composition, a method for producing a magnetic disk substrate, and the like.

近年來對於記憶體硬碟驅動器要求高容量、小型化，為了提高記錄密度，要求降低磁頭之飛行高度，而縮小單位記錄面積。伴隨於此，於磁碟用基板之製造步驟中，對研磨後所要求之表面品質亦逐年變嚴格。即，根據磁頭之低飛行高度化，必須減少表面粗糙度、微小起伏、滾邊及突起，根據單位記錄面積之減少，容許之每個基板面之刮痕數量減少，其大小與深度越發變小。 In recent years, high-capacity and miniaturization have been required for a memory hard disk drive, and in order to increase the recording density, it is required to reduce the flying height of the magnetic head and to reduce the unit recording area. Along with this, in the manufacturing process of the substrate for a magnetic disk, the surface quality required after polishing is also stricter year by year. That is, according to the low flying height of the magnetic head, it is necessary to reduce surface roughness, minute undulations, piping, and protrusions, and the number of scratches per substrate surface is allowed to decrease according to the reduction in the unit recording area, and the size and depth thereof become smaller.

又，於半導體領域，向高積體化與高速化方向發展，尤其是高積體化要求配線之微細化。其結果為，於半導體基板之製造製程中，對光阻劑進行曝光時之焦點深度變淺，而期待更進一步之表面平滑性。 In addition, in the field of semiconductors, development has been progressing toward high integration and high speed, and in particular, wiring is required to be miniaturized. As a result, in the manufacturing process of the semiconductor substrate, the depth of focus when the photoresist is exposed is lightened, and further surface smoothness is expected.

對於此種要求，以提高表面平滑性為目的，為了謀求被研磨物之表面所產生之損傷(刮痕)之減少，提出有使用離心分離或多段過濾而減少粗大粒子數量之研磨液組合物及其製造方法(例如專利文獻1及2)。又，提出有使矽溶膠通過矽藻土過濾器之研磨用矽溶膠之製造方法(例如專利文獻3及4)。 In order to improve the surface smoothness, in order to improve the surface smoothness, a polishing liquid composition which reduces the number of coarse particles by centrifugation or multi-stage filtration is proposed in order to reduce the damage (scratches) generated on the surface of the object to be polished. A manufacturing method thereof (for example, Patent Documents 1 and 2). Further, a method for producing a ruthenium sol for polishing which passes a ruthenium sol through a diatomaceous earth filter has been proposed (for example, Patent Documents 3 and 4).

先前技術文獻 Prior technical literature 專利文獻 Patent literature

專利文獻1：日本專利特開2006-075975號公報 Patent Document 1: Japanese Patent Laid-Open Publication No. 2006-075975

專利文獻2：日本專利特開2006-136996號公報 Patent Document 2: Japanese Patent Laid-Open No. 2006-136996

專利文獻3：日本專利特開2012-086357號公報 Patent Document 3: Japanese Patent Laid-Open Publication No. 2012-086357

專利文獻4：日本專利特開2007-099586號公報 Patent Document 4: Japanese Patent Laid-Open No. 2007-099586

為了應對更高容量、更高積體等高密度化，需進一步減少基板表面之刮痕數量。刮痕之原因之一係膠體二氧化矽中所含之粗大粒子或凝膠化物。供給至市場之一般膠體二氧化矽包含粗大粒子或凝膠化物。於先前之粗大粒子或凝膠化物之去除方法中，由於需藉由離心分離或多段過濾對研磨材料分散液原料進行處理，故而生產時間較長，而成為高成本。 In order to cope with higher density and higher density, it is necessary to further reduce the number of scratches on the surface of the substrate. One of the causes of the scratch is a coarse particle or a gelate contained in the colloidal cerium oxide. The general colloidal cerium oxide supplied to the market contains coarse particles or gelates. In the prior method of removing coarse particles or gels, since the raw material of the abrasive material is processed by centrifugation or multi-stage filtration, the production time is long and the cost is high.

本發明之一態樣係關於一種研磨液組合物之製造方法，其可有效率地去除含有膠體二氧化矽之被處理二氧化矽分散液中之粗大粒子或凝膠化物，藉此，過濾精度較高，可減少研磨後之基板表面之刮痕數量。 One aspect of the present invention relates to a method for producing a polishing liquid composition which can efficiently remove coarse particles or gelled substances in a treated cerium oxide dispersion containing colloidal cerium oxide, whereby filtration precision Higher, reducing the number of scratches on the surface of the substrate after grinding.

本發明係關於一種研磨液組合物之製造方法(以下亦稱為「本揭示之研磨液組合物之製造方法」)，其包括利用包含過濾助劑之過濾器對含有膠體二氧化矽之被處理二氧化矽分散液進行過濾處理之步驟。於本揭示之研磨液組合物之製造方法中，膠體二氧化矽之藉由滴定法所求得之一次粒子之平均粒徑為1nm以上且50nm以下。又，上述過濾助劑之羥基密度為0.40×10-5mol/m2以上。 The present invention relates to a method for producing a polishing liquid composition (hereinafter also referred to as "the method for producing a polishing liquid composition of the present invention"), which comprises treating a gel containing cerium oxide with a filter containing a filter aid. The step of filtering the cerium oxide dispersion. In the method for producing a polishing composition according to the present disclosure, the average particle diameter of the primary particles obtained by the titration method of the colloidal cerium oxide is 1 nm or more and 50 nm or less. Further, the filter aid has a hydroxyl group density of 0.40 × 10 -5 mol/m 2 or more.

本發明於另一態樣中係關於一種研磨液組合物，其係藉由或可藉由本揭示之研磨液組合物之製造方法而製造。 In another aspect, the present invention relates to a polishing composition prepared by or by the method of producing a polishing composition of the present disclosure.

本發明於另一態樣中係關於一種磁碟基板之製造方法，其包括 將藉由本揭示之研磨液組合物之製造方法所獲得之研磨液組合物供給至被研磨基板之研磨對象面，藉此對上述研磨對象面進行研磨之步驟。 In another aspect, the present invention relates to a method of manufacturing a disk substrate, including The polishing liquid composition obtained by the method for producing a polishing composition of the present invention is supplied to a polishing target surface of a substrate to be polished, thereby polishing the polishing target surface.

本發明於另一態樣中係關於一種用於本揭示之研磨液組合物之製造方法的過濾助劑，該過濾助劑之羥基密度為0.40×10-5mol/m2以上。 In another aspect, the present invention relates to a filter aid for use in the method for producing a polishing composition of the present invention, which has a hydroxyl group density of 0.40 x 10 -5 mol/m 2 or more.

本發明於另一態樣中係關於一種用於本揭示之研磨液組合物之製造方法的過濾助劑之製造方法，其包括將羥基密度未達0.40×10-5mol/m2之矽藻土與酸水溶液進行混合後，對上述矽藻土進行脫酸處理之步驟。 In another aspect, the present invention relates to a method for producing a filtration aid for use in a method for producing a polishing composition of the present invention, which comprises a diatom having a hydroxyl group density of less than 0.40×10 -5 mol/m 2 After the soil is mixed with the aqueous acid solution, the above-mentioned diatomaceous earth is subjected to a step of deacidification treatment.

根據本揭示，可有效地去除含有膠體二氧化矽之被處理二氧化矽分散液中之粗大粒子或凝膠化物，藉此可發揮出可製造過濾精度較高，可減少研磨後之基板表面之刮痕數量之研磨液組合物的效果。 According to the present disclosure, coarse particles or gels in the treated cerium oxide dispersion containing colloidal cerium oxide can be effectively removed, thereby achieving high filtration precision and reducing the surface of the polished substrate. The effect of the number of scratches on the slurry composition.

於本發明中，作為包含過濾助劑之過濾器(以下亦稱為「含過濾助劑之過濾器」)中之過濾助劑，使用將羥基密度控制為特定值以上之過濾助劑。因此，於膠體二氧化矽之一次粒子之平均粒徑為1nm以上且50nm以下之情形時，粗大粒子及凝膠化物之利用含過濾助劑之過濾器時之過濾精度較高。因此，若使用藉由本發明之研磨液組合物之製造方法而製造之研磨液組合物，則可減少研磨後之基板表面之刮痕。 In the present invention, as the filter aid in the filter containing the filter aid (hereinafter also referred to as "filter containing filter aid"), a filter aid which controls the density of the hydroxyl group to a specific value or more is used. Therefore, when the average particle diameter of the primary particles of the colloidal cerium oxide is 1 nm or more and 50 nm or less, the filtration precision of the coarse particles and the gelled product using the filter containing the filter aid is high. Therefore, when the polishing liquid composition produced by the method for producing a polishing liquid composition of the present invention is used, scratches on the surface of the substrate after polishing can be reduced.

於本揭示中，所謂「粗大粒子」係指粒徑為0.5μm以上之粗大之膠體二氧化矽粒子。又，於本揭示中，所謂「凝膠化物」係指0.05~ 0.5μm之二氧化矽凝集體。研磨液組合物中之粗大粒子及凝膠化物之量可藉由下述「0.45μm過濾器液體透過量」進行評價。 In the present disclosure, the term "coarse particles" means coarse colloidal cerium oxide particles having a particle diameter of 0.5 μm or more. Moreover, in the present disclosure, the term "gelated" means 0.05~ 0.5 μm of cerium oxide aggregate. The amount of coarse particles and gelation in the polishing composition can be evaluated by the following "0.45 μm filter liquid permeation amount".

於本揭示中，所謂「刮痕」，係於記憶體硬碟基板或半導體元件用基板中對高密度化或高積體化變得較重要之物性，係深度為1nm以上且未達100nm、寬度為5nm以上且未達500nm、長度為100μm以上之基板表面之微細損傷。該刮痕可使用下述實施例中記載之光學式全面缺陷檢查機(OSA6100：KLA-Tencor製造)及原子力顯微鏡(AFM，Atomic Force Microscope)進行檢測。 In the present disclosure, the "scratch" is a physical property that is important for high density or high integration in a memory hard disk substrate or a substrate for a semiconductor element, and has a depth of 1 nm or more and less than 100 nm. Fine damage of the surface of the substrate having a width of 5 nm or more and less than 500 nm and a length of 100 μm or more. This scratch can be detected using an optical total defect inspection machine (OSA6100: manufactured by KLA-Tencor) and an atomic force microscope (AFM, Atomic Force Microscope) described in the following examples.

於本揭示中，所謂「過濾精度」意指利用含過濾助劑之過濾器而過濾粗大粒子及凝膠化物之程度，所謂「過濾精度」較高，意指利用含過濾助劑之過濾器所獲得之粗大粒子及凝膠化物之捕捉率較高。 「過濾精度」可根據藉由使研磨液組合物或二氧化矽分散液於固定之壓力下，透過特定之含過濾助劑之過濾器而測定之直至該含過濾助劑之過濾器阻塞為止之液體透過量(g)加以評價。該液體透過量可表示為微過濾值(MF(microfiltration)值)。液體透過量越大、即MF值越大，表示粗大粒子及凝膠化物越不會混入至研磨液組合物或二氧化矽分散液中，過濾精度越高。因此，於上述MF值與刮痕數量之間，存在MF值越大，刮痕數量亦變得越少之關聯性。可認為MF值較大之二氧化矽分散液係可減少刮痕數量之二氧化矽分散液。又，可認為使用MF值較大之二氧化矽分散液所製備之研磨液組合物係可減少刮痕數量之研磨液組合物。 In the present disclosure, the term "filtering accuracy" means the degree of filtering coarse particles and gelled materials by using a filter containing a filter aid, and the so-called "filtering accuracy" is high, meaning that a filter containing a filter aid is used. The obtained coarse particles and gels have a high capture rate. The "filtering accuracy" can be determined by passing the slurry composition or the cerium oxide dispersion through a specific filter containing a filter aid under a fixed pressure until the filter containing the filter aid is blocked. The liquid permeation amount (g) was evaluated. The liquid permeation amount can be expressed as a microfiltration value (MF (microfiltration value)). The larger the liquid permeation amount, that is, the larger the MF value, the less the coarse particles and the gelate are mixed into the polishing liquid composition or the ceria dispersion, and the filtration precision is higher. Therefore, between the above MF value and the number of scratches, there is a correlation that the MF value is larger and the number of scratches becomes smaller. It is considered that the cerium oxide dispersion having a large MF value can reduce the number of scratches of the cerium oxide dispersion. Further, it is considered that the polishing liquid composition prepared by using the cerium oxide dispersion having a large MF value is a polishing liquid composition capable of reducing the number of scratches.

本發明之刮痕數量之減少之機制推測如下。於使用含過濾助劑之過濾器，自含有膠體二氧化矽之被處理二氧化矽分散液去除膠體二氧化矽之粗大粒子及凝膠化物之情形時，利用含過濾助劑之過濾器之過濾助劑本身所存在之次微米小孔，或於含過濾助劑之過濾器包含過濾助劑層(濾餅層)之情形時，利用由該過濾助劑層之內部之過濾助劑 形成之粒子間間隙等，捕捉上述粗大粒子及凝膠化物。但是，於本發明中，使用與先前使用之過濾助劑相比，表面之羥基密度更高，該羥基密度為0.40×10-5mol/m2以上之過濾助劑。因此，關於過濾助劑與二述粗大粒子及凝膠化物藉由各自具有之羥基而相互作用從而進行氫鍵結之頻度，本發明中使用之過濾助劑高於先前以來使用之過濾助劑。因此，於本發明中，藉由上述相互作用而助長利用上述小孔或上述粒子間間隙等物理障壁所進行之捕捉，更有效地進行上述粗大粒子及凝膠化物之捕捉。認為其結果為，研磨液組合物及二氧化矽分散液之上述過濾精度變高，而可減少刮痕數量。但是，本發明並不限定於該等機制而解釋。 The mechanism for reducing the number of scratches of the present invention is presumed as follows. In the case of removing coarse particles and gels of colloidal cerium oxide from a treated cerium oxide dispersion containing colloidal cerium oxide using a filter containing a filter aid, filtration using a filter containing a filter aid Submicron pores present in the additive itself, or in the case where the filter containing the filter aid comprises a filter aid layer (filter cake layer), the particles formed by the filter aid inside the filter aid layer are used. Interstitial gaps, etc., capture the above coarse particles and gels. However, in the present invention, a filter aid having a higher hydroxyl group density on the surface than the previously used filter aid and having a hydroxyl group density of 0.40 × 10 -5 mol/m 2 or more is used. Therefore, with respect to the frequency with which the filter aid and the two coarse particles and the gelate interact by the respective hydroxyl groups to perform hydrogen bonding, the filter aid used in the present invention is higher than the filter aid previously used. Therefore, in the present invention, the above-described interaction promotes the capture by the physical barrier such as the small holes or the inter-particle gap, and the coarse particles and the gelation are more efficiently captured. As a result, it is considered that the above-described filtration precision of the polishing liquid composition and the ceria dispersion is increased, and the number of scratches can be reduced. However, the invention is not limited to the explanation of such mechanisms.

[過濾助劑] [Filter Aid]

於一個或複數個實施形態中，作為用於本揭示之研磨液組合物之製造方法之過濾助劑，可列舉矽藻土、二氧化矽、高嶺土、酸性白土、波來鐵、膨潤土、滑石等不溶性之礦物性物質。就減少粗大粒子及凝膠化物，及減少研磨後之基板表面之刮痕之觀點而言，上述過濾助劑中，較佳為二氧化矽、矽藻土、波來鐵，更佳為矽藻土、波來鐵，進而較佳為矽藻土。 In one or a plurality of embodiments, examples of the filter aid used in the method for producing the polishing liquid composition of the present invention include diatomaceous earth, cerium oxide, kaolin, acid white clay, bun iron, bentonite, talc, and the like. Insoluble mineral matter. From the viewpoint of reducing coarse particles and gelation, and reducing scratches on the surface of the substrate after polishing, the filter aid is preferably cerium oxide, diatomaceous earth, and ferrocene, more preferably diatomaceous algae. Soil, Bora iron, and further preferably diatomaceous earth.

關於過濾助劑(較佳為矽藻土)之羥基密度，就提高過濾精度之觀點而言為0.40×10-5mol/m2以上，較佳為0.41×10-5mol/m2以上，更佳為0.43×10-5mol/m2以上，就提高生產性之觀點而言，較佳為2.0×10-5mol/m2以下，更佳為1.5×10-5mol/m2以下。過濾助劑之羥基密度可藉由實施例中記載之方法而求出。過濾助劑之羥基密度之控制可藉由下述方式進行。 The hydroxyl density of the filter aid (preferably diatomaceous earth) is 0.40 × 10 -5 mol / m 2 or more, preferably 0.41 × 10 -5 mol / m 2 or more, from the viewpoint of improving the filtration accuracy. More preferably, it is 0.43 × 10 -5 mol/m 2 or more, and from the viewpoint of improving productivity, it is preferably 2.0 × 10 -5 mol / m 2 or less, more preferably 1.5 × 10 -5 mol / m 2 or less. . The hydroxyl density of the filter aid can be determined by the method described in the examples. The control of the hydroxyl density of the filter aid can be carried out in the following manner.

於提高矽土之羥基密度之情形時，例如將市售之矽藻土與酸水溶液充分地混合後，將該混合液靜置特定時間，繼而進行脫酸處理。根據該方法，對於過濾助劑，可在不使平均孔徑、孔隙體積及CV值 等物性變化之情況下對矽藻土導入羥基，故而較佳。因此，若使用藉由本發明之研磨液組合物之製造方法所製造之研磨液組合物，則可同時實現與使用未將羥基密度控制為0.40×10-5mol/m2以上之先前過濾助劑所製造之研磨液組合物同等之研磨速度下之研磨與刮痕減少。 In the case of increasing the density of the hydroxyl group of the alumina, for example, the commercially available diatomaceous earth is sufficiently mixed with the aqueous acid solution, and then the mixture is allowed to stand for a specific period of time, followed by deacidification treatment. According to this method, it is preferred that the filter aid can introduce a hydroxyl group to the diatomaceous earth without changing the physical properties such as the average pore diameter, the pore volume, and the CV value. Therefore, when the polishing liquid composition produced by the method for producing a polishing liquid composition of the present invention is used, it is possible to simultaneously achieve and use a previous filtration aid which does not control the density of the hydroxyl group to 0.40 × 10 -5 mol/m 2 or more. The polishing liquid composition produced has a reduction in grinding and scratching at the same polishing speed.

於脫酸處理中，利用離子交換水或超純水而清洗矽藻土，反覆進行該清洗直至用於清洗之離子交換水或超純水成為大致中性。具體而言，自靜置後之包含矽藻土及酸水溶液之混合液去除上清液後，於去除了上清液之混合液之殘渣(矽藻土)中添加離子交換水或超純水，充分地進行攪拌、混合。繼而，將混合液靜置特定時間後，自靜置後之混合液去除上清液。反覆進行該操作直至上清液成為中性(pH值=5~8)。於上述之利用離子交換水或超純水所進行之矽藻土之清洗後，將矽藻土過濾至濾紙上，例如藉由自然乾燥使矽藻土乾燥，藉此獲得與未進行利用酸之處理之矽藻土相比羥基密度更高之矽藻土。羥基之導入量可藉由酸水溶液中之酸之濃度或矽藻土向酸水溶液之浸漬時間等進行控制。羥基密度變高之機制雖然無法斷定，但推測為下述2個機制。 In the deacidification treatment, the diatomaceous earth is washed with ion-exchanged water or ultrapure water, and the washing is repeated until the ion-exchanged water or ultrapure water used for washing becomes substantially neutral. Specifically, after removing the supernatant from the mixture containing the diatomaceous earth and the aqueous acid solution after standing, the ion exchange water or ultrapure water is added to the residue (diatomaceous earth) of the mixed liquid from which the supernatant is removed. , fully stir and mix. Then, after the mixture was allowed to stand for a certain period of time, the supernatant was removed from the mixture after standing. This operation was repeated until the supernatant became neutral (pH = 5 to 8). After washing the diatomaceous earth by ion exchange water or ultrapure water, the diatomaceous earth is filtered onto the filter paper, for example, by drying the diatomaceous earth by natural drying, thereby obtaining and not using the acid. The treated diatomaceous earth has a higher density of diatomaceous earth than the diatomaceous earth. The amount of introduction of the hydroxyl group can be controlled by the concentration of the acid in the aqueous acid solution or the immersion time of the diatomaceous earth to the aqueous acid solution. Although the mechanism for increasing the density of hydroxyl groups cannot be determined, it is presumed to be the following two mechanisms.

藉由於水溶液中之利用酸所進行之處理，存在於矽藻土之表面之Al2O3、FeO2、MgO等氧化金屬溶出，藉此出現矽藻土之新表面，因此羥基密度變高。 By the treatment with an acid in the aqueous solution, the oxidized metal such as Al 2 O 3 , FeO 2 or MgO which is present on the surface of the diatomaceous earth is eluted, whereby a new surface of the diatomaceous earth is formed, so that the hydroxyl group density becomes high.

又，於水溶液中，形成矽藻土之骨架的與氧原子鍵結之Al、Fe、Mg等金屬種與該氧原子之鍵斷裂，水溶液中之氫離子與該氧原子鍵結，藉此羥基密度變高。 Further, in the aqueous solution, a metal species such as Al, Fe, or Mg bonded to an oxygen atom in the skeleton of the diatomaceous earth is broken with a bond of the oxygen atom, and hydrogen ions in the aqueous solution are bonded to the oxygen atom, whereby the hydroxyl group is bonded thereto. The density becomes higher.

用於上述酸水溶液之調整之酸可列舉無機酸及有機酸。作為無機酸，較佳為礦酸。又，已知有機酸可利用各種有機酸，但矽藻土之羥基密度之提高存在與酸解離常數(pKa)之較強之相互關係。即，就提高矽藻土之羥基密度之觀點而言，上述有機酸之pKa較佳為未達 5，更佳為更低。下限值並無特別限定，就實用上而言，上述有機酸之pKa較佳為1以上。 The acid used for the adjustment of the above aqueous acid solution may, for example, be an inorganic acid or an organic acid. As the inorganic acid, a mineral acid is preferred. Further, it is known that various organic acids can be used for the organic acid, but the increase in the hydroxyl density of the diatomaceous earth has a strong correlation with the acid dissociation constant (pKa). That is, from the viewpoint of increasing the density of the hydroxyl group of the diatomaceous earth, the pKa of the above organic acid is preferably not reached. 5, better for the lower. The lower limit is not particularly limited, and practically, the pKa of the organic acid is preferably 1 or more.

就上述觀點而言，於一個或複數個實施形態中，用於上述酸水溶液之調整之具體之酸就提高過濾精度與減少刮痕數量之觀點而言，較佳為選自由鹽酸、硝酸、磷酸、1-羥基亞乙基-1,1-二膦酸等膦酸、次膦酸、及pKa未達4之有機酸所組成之群中之至少1種，更佳為選自由鹽酸、硝酸、磷酸、膦酸、次膦酸、及pKa未達3.5之有機酸所組成之群中之至少1種，進而較佳為選自由硝酸、磷酸、膦酸、次膦酸、及pKa為3.1以下之有機酸所組成之群中之至少1種，進而更佳為選自由膦酸、及次膦酸所組成之群中之至少1種。 In view of the above, in one or more embodiments, the specific acid used for the adjustment of the aqueous acid solution is preferably selected from the group consisting of hydrochloric acid, nitric acid, and phosphoric acid from the viewpoint of improving filtration accuracy and reducing the number of scratches. At least one of a group consisting of a phosphonic acid such as 1-hydroxyethylidene-1,1-diphosphonic acid, a phosphinic acid, and an organic acid having a pKa of less than 4, more preferably selected from the group consisting of hydrochloric acid and nitric acid. At least one selected from the group consisting of phosphoric acid, phosphonic acid, phosphinic acid, and an organic acid having a pKa of less than 3.5, more preferably selected from the group consisting of nitric acid, phosphoric acid, phosphonic acid, phosphinic acid, and pKa of 3.1 or less. At least one of the group consisting of organic acids is more preferably at least one selected from the group consisting of phosphonic acid and phosphinic acid.

上述酸水溶液中之酸之濃度就確保充分之金屬種之溶出量，提高羥基密度之觀點而言，較佳為0.05mol/L以上，更佳為0.1mol/L以上，進而較佳為0.15mol/L以上，就抑制金屬種之過度溶出之觀點而言，較佳為2.0mol/L以下，更佳為1.0mol/l以下。 The concentration of the acid in the aqueous acid solution is preferably 0.05 mol/L or more, more preferably 0.1 mol/L or more, and still more preferably 0.15 mol from the viewpoint of ensuring a sufficient elution amount of the metal species and increasing the density of the hydroxyl group. From the viewpoint of suppressing excessive elution of the metal species, it is preferably 2.0 mol/L or less, more preferably 1.0 mol/l or less.

上述酸水溶液中之酸之量就確保充分之金屬種之溶出量，提高羥基密度之觀點而言，於使用3.5質量%之酸水溶液之情形時，相對於混合之矽藻土100質量份，較佳為200質量份以上，更佳為500質量份以上，進而較佳為10000質量份以上。 The amount of the acid in the aqueous acid solution ensures sufficient elution amount of the metal species and increases the density of the hydroxyl group. When a 3.5% by mass aqueous acid solution is used, 100 parts by mass of the mixed diatomaceous earth is used. It is preferably 200 parts by mass or more, more preferably 500 parts by mass or more, and still more preferably 10,000 parts by mass or more.

於上述利用酸之處理中，矽土與酸水溶液之混合液之靜置時間就確保充分之金屬種之溶出量，提高羥基密度之觀點而言，較佳為5分鐘以上，更佳為30分鐘以上，進而較佳為1小時以上，就生產性之觀點而言，較佳為72小時以下。 In the above treatment with an acid, the standing time of the mixture of the alumina and the aqueous acid solution ensures a sufficient amount of elution of the metal species, and from the viewpoint of increasing the density of the hydroxyl group, it is preferably 5 minutes or longer, more preferably 30 minutes. The above is more preferably 1 hour or longer, and from the viewpoint of productivity, it is preferably 72 hours or shorter.

如上所述，作為對矽藻土導入羥基之方法之一例，對利用酸所進行之處理進行了說明，但藉由如下方法亦可對矽藻土導入羥基，即於將市售之矽藻土與氫氧化鈉水溶液等鹼性水溶液加以混合後，將該混合液靜置特定時間，繼而進行脫鹼處理(利用鹼所進行之處理)之方 法。 As described above, as an example of a method of introducing a hydroxyl group into the diatomaceous earth, the treatment with an acid has been described, but a hydroxyl group may be introduced into the diatomaceous earth by the following method, that is, a commercially available diatomaceous earth After mixing with an alkaline aqueous solution such as an aqueous sodium hydroxide solution, the mixture is allowed to stand for a specific period of time, followed by a dealcoalization treatment (treatment by alkali) law.

於降低矽土之羥基密度之情形時，例如於焙燒爐內焙燒作為過濾助劑之一例之矽藻土。就更確實地焙燒體系整體之觀點而言，矽藻土之焙燒係藉由如下方式進行：於將矽藻土放入至焙燒爐內之狀態下，將焙燒爐內之溫度自室溫升溫至較佳為達到700℃、更佳為750℃、進而較佳為800℃，並保持該溫度較佳為3小時以上，更佳為5小時以上，進而較佳為10小時以上。就提高焙燒爐內之溫度之均勻性之觀點而言，焙燒爐內之環境溫度之升溫較佳為進行空氣流通，風速較佳為0.5~5L/min，更佳為2~3L/min。 In the case of reducing the density of the hydroxyl groups of the alumina, for example, calcined earth as an example of a filter aid is calcined in a baking furnace. From the viewpoint of the more accurate calcination system as a whole, the calcination of the diatomaceous earth is carried out by heating the temperature in the baking furnace from room temperature to the state in which the diatomaceous earth is placed in the baking furnace. It is preferably 700 ° C, more preferably 750 ° C, still more preferably 800 ° C, and the temperature is preferably 3 hours or longer, more preferably 5 hours or longer, and still more preferably 10 hours or longer. From the viewpoint of improving the uniformity of the temperature in the baking furnace, the temperature rise of the ambient temperature in the baking furnace is preferably such that the air is circulated, and the wind speed is preferably 0.5 to 5 L/min, more preferably 2 to 3 L/min.

[過濾助劑之粒徑分佈之CV值] [CV value of particle size distribution of filter aid]

於本揭示中，所謂「過濾助劑之粒徑分佈之CV值」係成為表示粒度分佈之範圍之指標之數值，係指根據CV值(%)=標準偏差/平均粒徑之式所求出之值。於一個或複數個實施形態中，CV值作為如下比率而求出，即，用利用雷射繞射/散射式粒度分佈計對過濾助劑進行測定而獲得之算術標準偏差除以作為體積基準之中值粒徑而獲得之值而得之值之比率(%)，於本揭示中，設為藉由利用檢測角90°之馬誇特(Marquardt)法所獲得之散射強度分佈之測定而算出之值。具體而言，可藉由實施例中記載之方法求出。 In the present disclosure, the "CV value of the particle size distribution of the filter aid" is a numerical value indicating an index of the range of the particle size distribution, and is obtained by the formula of CV value (%) = standard deviation / average particle diameter. The value. In one or more embodiments, the CV value is obtained as a ratio obtained by dividing the arithmetic standard deviation obtained by measuring the filter aid using a laser diffraction/scattering particle size distribution meter as a volume basis. The ratio (%) of the value obtained by the value obtained by the median diameter is calculated in the present disclosure by measurement of the scattering intensity distribution obtained by the Marquardt method having a detection angle of 90°. The value. Specifically, it can be obtained by the method described in the examples.

過濾助劑之粒徑分佈之CV值就減少粗大粒子及凝膠化物，及減少研磨後之基板表面之刮痕之觀點而言，較佳為70%以上，更佳為75%以上，進而較佳為80%以上，進而更佳為85%以上，就取得容易性之觀點而言，較佳為100%以下，更佳為99%以下。 The CV value of the particle size distribution of the filter aid is preferably 70% or more, more preferably 75% or more, from the viewpoint of reducing coarse particles and gelation, and reducing scratches on the surface of the substrate after polishing. It is preferably 80% or more, and more preferably 85% or more. From the viewpoint of easiness, it is preferably 100% or less, more preferably 99% or less.

[過濾助劑之雷射平均粒徑] [Laser average particle size of filter aids]

於本揭示中，所謂過濾助劑之「雷射平均粒徑」係利用雷射式粒度分佈測定裝置所測得之過濾助劑之平均粒徑，於本揭示中，設為藉由利用檢測角90°之馬誇特法獲得之散射強度分佈之測定而算出之 值。過濾助劑之雷射平均粒徑可藉由實施例中記載之方法而測定。 In the present disclosure, the "laser average particle diameter" of the filter aid is an average particle diameter of the filter aid measured by a laser particle size distribution analyzer, and is used in the present disclosure to utilize the detection angle. Calculated by measuring the scattering intensity distribution obtained by the Marquard method of 90° value. The laser average particle size of the filter aid can be determined by the method described in the examples.

過濾助劑之雷射平均粒徑就減少粗大粒子及凝膠化物及減少研磨後之基板表面之刮痕之觀點而言，較佳為0.5μm以上，更佳為1μm以上，進而較佳為4.5μm以上，進而更佳為8μm以上，進而更佳為10μm以上，就相同之觀點而言，較佳為100μm以下，更佳為60μm以下，進而較佳為50μm以下，進而更佳為40μm以下，進而更佳為20μm以下，進而更佳為13μm以下。 The laser average particle diameter of the filter aid is preferably 0.5 μm or more, more preferably 1 μm or more, and still more preferably 4.5, from the viewpoint of reducing coarse particles and gelation and reducing scratches on the surface of the substrate after polishing. It is more preferably 8 μm or more, and still more preferably 10 μm or more, and more preferably 100 μm or less, more preferably 60 μm or less, further preferably 50 μm or less, and still more preferably 40 μm or less. Further, it is more preferably 20 μm or less, and still more preferably 13 μm or less.

[過濾助劑之平均孔徑] [Average pore size of filter aid]

就減少刮痕及粒子之觀點以及提高研磨液組合物之生產性之觀點而言，上述過濾助劑之藉由水銀壓入法所獲得之平均孔徑較佳為0.1~3.5μm，更佳為0.1~3.0μm，進而較佳為0.1~2.7μm，進而更佳為0.1~2.6μm。再者，於本發明中，所謂「藉由水銀壓入法所獲得之平均孔徑」係過濾助劑粒子之體積基準之孔徑之平均值。 The average pore diameter of the filter aid obtained by the mercury intrusion method is preferably from 0.1 to 3.5 μm, more preferably from the viewpoint of reducing scratches and particles and improving the productivity of the polishing composition. It is preferably 3.0 to 2.7 μm, more preferably 0.1 to 2.6 μm. Further, in the present invention, the "average pore diameter obtained by the mercury intrusion method" is an average value of the pore diameters of the volume of the filter aid particles.

[膠體二氧化矽之一次粒子之平均粒徑/過濾助劑之雷射平均粒徑的比] [Average particle size of primary particles of colloidal cerium oxide / ratio of laser average particle size of filter aid]

就減少粗大粒子及凝膠化物，及減少研磨後之基板表面之刮痕之觀點而言，被處理二氧化矽分散液之膠體二氧化矽之藉由滴定法所求得之一次粒子之平均粒徑與過濾助劑之雷射平均粒徑的比(膠體二氧化矽之一次粒子之平均粒徑/過濾助劑之雷射平均粒徑)(以下亦稱為「二氧化矽/過濾助劑之平均粒徑比」)較佳為1.20×10-3以上，更佳為1.35×10-3以上，進而較佳為1.40×10-3以上，進而更佳為1.42×10-3以上。又，就相同之觀點而言，二氧化矽/過濾助劑之平均粒徑比較佳為4.20×10-3以下，更佳為3.80×10-3以下，進而較佳為3.00×10-3以下，進而更佳為2.50×10-3以下，進而更佳為2.00×10-3以下，進而更佳為1.50×10-3以下。 The average particle size of the primary particles obtained by titration of the colloidal cerium oxide of the treated cerium oxide dispersion from the viewpoint of reducing coarse particles and gelation, and reducing scratches on the surface of the substrate after polishing. Ratio of diameter to laser average particle size of filter aid (average particle size of colloidal ceria primary particles / laser average particle size of filter aid) (hereinafter also referred to as "cerium oxide / filter aid" The average particle diameter ratio ") is preferably 1.20 × 10 -3 or more, more preferably 1.35 × 10 -3 or more, still more preferably 1.40 × 10 -3 or more, still more preferably 1.42 × 10 -3 or more. Further, from the same viewpoint, the average particle diameter of the cerium oxide/filter aid is preferably 4.20 × 10 -3 or less, more preferably 3.80 × 10 -3 or less, still more preferably 3.00 × 10 -3 or less. Further, it is more preferably 2.50 × 10 -3 or less, still more preferably 2.00 × 10 -3 or less, still more preferably 1.50 × 10 -3 or less.

[過濾助劑之藉由氮吸附法所獲得之0.15μm以下之累計孔隙體 積] [Augmented pores of 0.15 μm or less obtained by nitrogen adsorption method for filter aids product]

就減少刮痕及粒子之觀點而言，過濾助劑之藉由氮吸附法所獲得之孔徑0.15μm以下之累計孔隙體積較佳為0.3mL/g以上，更佳為0.4mL/g以上，進而較佳為0.6mL/g以上。又，就提高研磨液組合物之生產性之觀點而言，上述累計孔隙體積較佳為100.0mL/g以下，更佳為50.0mL/g以下，進而較佳為10.0mL/g以下。再者，過濾助劑之0.15μm以下之累計孔隙體積可藉由實施例中記載之方法而測定。 The cumulative pore volume of the filter aid obtained by the nitrogen adsorption method and having a pore diameter of 0.15 μm or less is preferably 0.3 mL/g or more, more preferably 0.4 mL/g or more, from the viewpoint of reducing scratches and particles. It is preferably 0.6 mL/g or more. Moreover, from the viewpoint of improving the productivity of the polishing liquid composition, the cumulative pore volume is preferably 100.0 mL/g or less, more preferably 50.0 mL/g or less, and still more preferably 10.0 mL/g or less. Further, the cumulative pore volume of the filter aid of 0.15 μm or less can be measured by the method described in the examples.

[過濾助劑之藉由水銀壓入法所獲得之0.5μm以下之累計孔隙體積] [Cumulative pore volume of 0.5 μm or less obtained by mercury intrusion method of filter aid]

就減少刮痕及粒子之觀點而言，上述過濾助劑之藉由水銀壓入法所獲得之孔徑0.5μm以下之累計孔隙體積較佳為2.5mL/g以上，更佳為2.7mL/g以上，進而較佳為3.0mL/g以上，進而更佳為4.0mL/g以上，進而更佳為4.5mL/g以上。又，就提高研磨液組合物之生產性之觀點而言，上述過濾助劑之藉由水銀壓入法所獲得之孔徑0.5μm以下之累計孔隙體積較佳為1000mL/g以下，更佳為100mL/g以下，進而較佳為50mL/g以下，進而更佳為20mL/g以下，進而更佳為10mL/g以下。再者，所謂過濾助劑之「藉由水銀壓入法所獲得之0.5μm以下之累計孔隙體積」係藉由水銀壓入法所獲得之過濾助劑粒子之體積基準之孔分佈中之0.5μm以下之孔隙體積之總和，可藉由實施例中記載之方法而測定。 The cumulative pore volume of the filter aid obtained by the mercury intrusion method having a pore diameter of 0.5 μm or less is preferably 2.5 mL/g or more, and more preferably 2.7 mL/g or more, from the viewpoint of reducing scratches and particles. Further, it is preferably 3.0 mL/g or more, more preferably 4.0 mL/g or more, and still more preferably 4.5 mL/g or more. Further, from the viewpoint of improving the productivity of the polishing composition, the cumulative pore volume of the filter aid obtained by the mercury intrusion method having a pore diameter of 0.5 μm or less is preferably 1000 mL/g or less, more preferably 100 mL. The amount of /g or less is more preferably 50 mL/g or less, further preferably 20 mL/g or less, and still more preferably 10 mL/g or less. Further, the "accumulated pore volume of 0.5 μm or less obtained by the mercury intrusion method" of the filter aid is 0.5 μm in the pore volume distribution of the filter aid particles obtained by the mercury intrusion method. The sum of the following pore volumes can be measured by the method described in the examples.

[被處理二氧化矽分散液] [Processed cerium oxide dispersion]

於本揭示中，「被處理二氧化矽分散液」係指供於利用含過濾助劑之過濾器所進行之過濾處理前之二氧化矽漿料(二氧化矽分散液)。於一個或複數個實施形態中，被處理二氧化矽分散液可列舉包含膠體二氧化矽及水者、進而包含其他成分者、或通用膠體二氧化矽之漿料。於其他實施形態中，被處理二氧化矽分散液可列舉混合下述可調 配至研磨液組合物中之其他成分而製造者。作為被處理二氧化矽分散液之狀態，較佳為膠體二氧化矽分散之狀態。 In the present disclosure, the "treated cerium oxide dispersion" means a cerium oxide slurry (cerium oxide dispersion liquid) before being subjected to a filtration treatment by a filter containing a filter aid. In one or a plurality of embodiments, the treated ceria dispersion may be a slurry containing colloidal ceria and water, further containing other components, or a general-purpose colloidal ceria. In other embodiments, the treated cerium oxide dispersion can be exemplified by mixing as described below. Produced by other ingredients in the polishing composition. As a state of the treated cerium oxide dispersion, it is preferred that the colloidal cerium oxide is dispersed.

於本揭示之研磨液組合物之製造方法中，藉由將被處理二氧化矽分散液供於使用上述包含過濾助劑之過濾器(於本揭示中，亦稱為「含過濾助劑之過濾器」)之過濾，而可製造研磨液組合物。具體而言，將混合膠體二氧化矽、水及酸或氧化劑等其他成分而製造之被處理二氧化矽分散液供於上述過濾，或者於將含有膠體二氧化矽及水之被處理二氧化矽分散液供於上述過濾之後，於所獲得之過濾物(二氧化矽分散液)中混合其他成分，藉此可製造研磨液組合物。就於製造研磨液組合物時作業較容易之觀點而言，較佳為將含有膠體二氧化矽及水之被處理二氧化矽分散液供於上述過濾後，將所獲得之過濾物(二氧化矽分散液)與其他成分進行混合的研磨液組合物之製造方法。 In the method for producing a polishing composition according to the present disclosure, the treated cerium oxide dispersion is supplied to the filter using the above-mentioned filter aid (in the present disclosure, also referred to as "filtering aid-containing filtration". The slurry is filtered to produce a slurry composition. Specifically, the treated cerium oxide dispersion prepared by mixing colloidal cerium oxide, water, and other components such as an acid or an oxidizing agent is supplied to the above filtration, or the treated cerium oxide containing colloidal cerium oxide and water is used. After the dispersion is supplied to the above filtration, the other components are mixed with the obtained filtrate (cerium oxide dispersion), whereby a polishing liquid composition can be produced. From the viewpoint of facilitating the operation in the production of the polishing liquid composition, it is preferred to supply the treated cerium oxide dispersion containing colloidal cerium oxide and water to the above-mentioned filtration, and the obtained filtrate (2 oxidized) A method for producing a polishing liquid composition in which a hydrazine dispersion is mixed with other components.

[膠體二氧化矽之一次粒子之平均粒徑] [Average particle size of primary particles of colloidal cerium oxide]

於未特別提及之情形時，被處理二氧化矽分散液之膠體二氧化矽之一次粒子之平均粒徑係指藉由滴定法所求得之一次粒子之平均粒徑。具體而言，藉由滴定法所進行之一次粒子之平均粒徑之測定係如以下所記載。首先，於膠體二氧化矽漿料中添加水，而獲得混合液。 其次，使用電位差滴定裝置，利用鹽酸標準溶液等調整上述混合液之pH值(例如3.0)。其次，於pH值經調整之混合液中混合氯化鈉及水，使氯化鈉溶解，並使所獲得之試樣液充分地浸漬於恆溫水槽內。繼而，使用電位差滴定裝置，利用標準溶液(氫氧化鈉溶液等)進行滴定。讀取試樣液之pH值自4.0變為9.0時所使用之標準溶液之溶質量(g)(A)，亦讀取未於試樣液中添加膠體二氧化矽漿料之情形時之滴定所需之標準溶液之溶質量(g)(B)。然後，根據下述計算式而算出平均粒徑(nm)。 The average particle diameter of the primary particles of the colloidal ceria which is treated with the ceria dispersion is the average particle diameter of the primary particles obtained by the titration method, unless otherwise specified. Specifically, the measurement of the average particle diameter of the primary particles by the titration method is as follows. First, water is added to the colloidal cerium oxide slurry to obtain a mixed solution. Next, the pH of the mixed liquid (for example, 3.0) is adjusted using a potentiometric titration apparatus using a hydrochloric acid standard solution or the like. Next, sodium chloride and water were mixed in the pH-adjusted mixture to dissolve sodium chloride, and the obtained sample liquid was sufficiently immersed in a constant temperature water tank. Then, using a potentiometric titration apparatus, titration is performed using a standard solution (sodium hydroxide solution or the like). The dissolved mass (g) (A) of the standard solution used when the pH of the sample solution was changed from 4.0 to 9.0 was read, and the titration was also performed when the colloidal ceria slurry was not added to the sample solution. The dissolved mass of the standard solution required (g) (B). Then, the average particle diameter (nm) was calculated according to the following calculation formula.

平均粒徑(nm)=3100÷26.5×(A-B)÷試樣採取量(膠體二氧化矽固 形物成分量)(g) Average particle size (nm) = 3100 ÷ 26.5 × (A-B) ÷ sample taken amount (colloidal cerium oxide solid Shape component ()

被處理二氧化矽分散液之膠體二氧化矽之一次粒子之平均粒徑就減少粗大粒子及凝膠化物、及減少研磨後之基板表面之刮痕之觀點而言，為1.0nm以上且50nm以下，就相同之觀點而言，更佳為5.0nm以上，進而較佳為10.0nm以上，進而更佳為12.0nm以上，且較佳為45nm以下，更佳為42nm以下，進而較佳為40nm以下。於一個或複數個實施形態中，本揭示之被處理二氧化矽分散液、研磨液組合物係指含有上述範圍之一次粒子之平均粒徑之膠體二氧化矽者。 The average particle diameter of the primary particles of the colloidal cerium oxide of the treated cerium oxide dispersion is 1.0 nm or more and 50 nm or less from the viewpoint of reducing coarse particles and gelation and reducing scratches on the surface of the substrate after polishing. From the same viewpoint, it is more preferably 5.0 nm or more, further preferably 10.0 nm or more, further preferably 12.0 nm or more, and more preferably 45 nm or less, more preferably 42 nm or less, still more preferably 40 nm or less. . In one or more embodiments, the treated ceria dispersion and the polishing composition of the present invention are colloidal ceria having an average particle diameter of primary particles in the above range.

於本揭示中使用之膠體二氧化矽例如可藉由自矽酸水溶液生成之製法而獲得。又，亦可使用利用官能基對該等研磨粒子進行表面修飾或者表面改質而成者，利用界面活性劑或其他研磨材料將該等研磨粒子進行複合粒子化而成者等。 The colloidal cerium oxide used in the present disclosure can be obtained, for example, by a process for producing an aqueous solution of citric acid. Further, it is also possible to use a functional group to perform surface modification or surface modification of the abrasive particles, and to form a composite particle by using the surfactant or another polishing material.

就減少刮痕之觀點及提高生產性之觀點而言，上述被處理二氧化矽分散液中之膠體二氧化矽之含量較佳為1質量%以上，更佳為10質量%以上，進而較佳為20質量%以上，進而更佳為30質量%以上，又，較佳為50質量%以下，更佳為45質量%以下，進而較佳為43質量%以下，進而更佳為40質量%以下。 The content of the colloidal cerium oxide in the treated cerium oxide dispersion is preferably 1% by mass or more, more preferably 10% by mass or more, and further preferably from the viewpoint of reducing scratches and improving productivity. 20% by mass or more, more preferably 30% by mass or more, further preferably 50% by mass or less, more preferably 45% by mass or less, further preferably 43% by mass or less, and still more preferably 40% by mass or less. .

於一個或複數個實施形態中，就抑制粗大粒子之產生及提高膠體二氧化矽之穩定性之觀點而言，上述被處理二氧化矽分散液於25℃下之pH值較佳為8.5以上，更佳為8.8以上，進而較佳為9.0以上，又，較佳為11以下，更佳為10.8以下，進而較佳為10.5以下。上述被處理二氧化矽粒子分散液之pH值可利用公知之pH值調整劑進行調整。作為較佳之pH值調整劑，可列舉：氫氧化鈉、氫氧化鉀、氨、氫氧化四甲基銨。 In one or more embodiments, the pH of the treated ceria dispersion at 25 ° C is preferably 8.5 or more from the viewpoint of suppressing generation of coarse particles and improving stability of colloidal ceria. More preferably, it is 8.8 or more, further preferably 9.0 or more, further preferably 11 or less, more preferably 10.8 or less, still more preferably 10.5 or less. The pH of the above-mentioned treated cerium oxide particle dispersion can be adjusted by using a known pH adjusting agent. Preferred examples of the pH adjuster include sodium hydroxide, potassium hydroxide, ammonia, and tetramethylammonium hydroxide.

[含過濾助劑之過濾器] [Filter containing filter aid]

本揭示之研磨液組合物之製造方法所使用之含過濾助劑之過濾 器只要為於過濾器表面及/或過濾器內部含有上述過濾助劑者，則無特別限制。於本揭示之研磨液組合物之製造方法中，例如亦可對預塗覆進而組合主體加料而使用。就防止過濾助劑之洩漏之觀點而言，藉由JIS3801中規定之方法所測得之過濾器網眼較佳為15μm以下，更佳為12μm以下，進而較佳為10μm以下，進而更佳為8μm以下。又，就提高過濾器液體透過速度之觀點而言，過濾器網眼較佳為0.5μm以上，進而較佳為1.0μm以上，進而更佳為3.0μm以上，進而更佳為5.0μm以上。此處，所謂預塗覆係濾餅過濾過濾器之形成方法，係於下述過濾器材料(濾紙等基材)上形成厚度數mm左右之過濾助劑之較薄層。例如可列舉將過濾助劑粒子分散至水中，並利用濾材而濾取過濾助劑，形成過濾助劑層之方法。又，所謂主體加料係於過濾時一面於濾餅過濾之原液中投入一定量之過濾助劑一面進行過濾處理之方法，其目的為改善原液之過濾性。對於粒徑較細而濾餅阻力立刻極大化(變得無法過濾)之原液有效。 Filtration aid containing filtration agent used in the method for producing a polishing liquid composition of the present disclosure The device is not particularly limited as long as it contains the above-mentioned filter aid on the surface of the filter and/or inside the filter. In the method for producing a polishing liquid composition of the present invention, for example, it may be used by precoating and further combining the main body. The filter mesh measured by the method specified in JIS 3801 is preferably 15 μm or less, more preferably 12 μm or less, further preferably 10 μm or less, and more preferably from the viewpoint of preventing leakage of the filter aid. 8 μm or less. Further, from the viewpoint of increasing the liquid permeation rate of the filter, the filter mesh is preferably 0.5 μm or more, more preferably 1.0 μm or more, still more preferably 3.0 μm or more, and still more preferably 5.0 μm or more. Here, the method of forming the pre-coated filter cake filter is to form a thin layer of a filter aid having a thickness of about several mm on the filter material (base material such as filter paper) described below. For example, a method in which the filter aid particles are dispersed in water and the filter aid is filtered by a filter medium to form a filter aid layer is exemplified. Further, the main body feed is a method in which a predetermined amount of a filter aid is supplied to a filter solution-filtered stock solution for filtration while filtering, and the purpose thereof is to improve the filterability of the stock solution. It is effective for a stock solution having a fine particle size and immediately increasing the resistance of the filter cake (being unable to be filtered).

就減少刮痕之觀點而言，上述含過濾助劑之過濾器中之過濾助劑之含量(g/cm2)較佳為0.001g/cm2以上，更佳為0.005g/cm2以上，進而較佳為0.01g/cm2以上，進而更佳為0.02g/cm2以上，進而更佳為0.04g/cm2以上，進而更佳為0.1g/cm2以上。又，就提高過濾速度之觀點而言，較佳為1g/cm2以下，更佳為0.8g/cm2以下，進而較佳為0.6g/cm2以下，進而更佳為0.4g/cm2以下，進而更佳為0.3g/cm2以下，進而更佳為0.2g/cm2以下。 The content (g/cm 2 ) of the filter aid in the filter containing the filter aid is preferably 0.001 g/cm 2 or more, more preferably 0.005 g/cm 2 or more, from the viewpoint of reducing scratches. Further, it is preferably 0.01 g/cm 2 or more, more preferably 0.02 g/cm 2 or more, still more preferably 0.04 g/cm 2 or more, and still more preferably 0.1 g/cm 2 or more. Moreover, from the viewpoint of increasing the filtration rate, it is preferably 1 g/cm 2 or less, more preferably 0.8 g/cm 2 or less, still more preferably 0.6 g/cm 2 or less, and still more preferably 0.4 g/cm 2 . Hereinafter, it is more preferably 0.3 g/cm 2 or less, and still more preferably 0.2 g/cm 2 or less.

作為上述含過濾助劑之過濾器之過濾器材料，可列舉：濾紙、聚乙烯、聚丙烯、聚醚碸、乙酸纖維素、尼龍、聚碳酸酯、鐵氟龍(註冊商標)等塑膠，陶瓷、金屬網等，就減少刮痕之觀點而言，較佳為濾紙、聚乙烯、聚丙烯、聚醚碸、乙酸纖維素、尼龍、聚碳酸酯或鐵氟龍(註冊商標)製之塑膠網，更佳為濾紙、聚乙烯、聚丙烯、聚醚 碸、乙酸纖維素或尼龍製之塑膠網，進而較佳為濾紙、聚乙烯或聚丙烯製之塑膠網。 Examples of the filter material of the filter containing the filter aid include a filter paper, polyethylene, polypropylene, polyether oxime, cellulose acetate, nylon, polycarbonate, Teflon (registered trademark), and the like. , metal mesh, etc., from the viewpoint of reducing scratches, preferably a filter paper, polyethylene, polypropylene, polyether oxime, cellulose acetate, nylon, polycarbonate or Teflon (registered trademark) plastic mesh More preferably filter paper, polyethylene, polypropylene, polyether A plastic mesh made of enamel, cellulose acetate or nylon is preferably a filter paper, a plastic mesh made of polyethylene or polypropylene.

就防止過濾助劑之洩漏之觀點而言，過濾器材料(基材)之網眼較佳為15μm以下，更佳為12μm以下，進而較佳為10μm以下，進而更佳為8μm以下。又，就提高過濾器液體透過速度之觀點而言，過濾器材料(基材)之網眼較佳為0.5μm以上，進而較佳為1.0μm以上，進而更佳為3.0μm以上，進而更佳為5.0μm以上。 The mesh of the filter material (substrate) is preferably 15 μm or less, more preferably 12 μm or less, further preferably 10 μm or less, and still more preferably 8 μm or less from the viewpoint of preventing leakage of the filter aid. Further, from the viewpoint of increasing the liquid permeation rate of the filter, the mesh of the filter material (substrate) is preferably 0.5 μm or more, more preferably 1.0 μm or more, still more preferably 3.0 μm or more, and thus more preferably It is 5.0 μm or more.

上述含過濾助劑之過濾器之形狀並無特別限定，就操作容易性、刮痕減少之觀點而言，較佳為片型、圓筒型、圓盤型、***型，更佳為片型、圓盤型、***型，進而較佳為圓盤型、***型。 The shape of the filter containing the filter aid is not particularly limited, and from the viewpoint of ease of handling and reduction of scratches, a sheet type, a cylinder type, a disk type, an insert type, and more preferably a sheet type are preferable. The disc type and the insert type are further preferably a disc type or an insert type.

[過濾處理步驟] [Filtering process steps]

於本揭示之研磨液組合物或二氧化矽分散液之製造方法中，利用含過濾助劑之過濾器進行過濾處理之步驟之條件中之過濾壓就減少粗大粒子及凝膠化物、及減少研磨後之基板表面之刮痕之觀點而言，較佳為0.16MPa以上，更佳為0.18MPa以上，進而較佳為0.20MPa以上。就相同之觀點而言，過濾處理步驟之過濾壓力較佳為0.49MPa以下，更佳為0.45MPa以下，進而較佳為0.40MPa以下，進而更佳為0.30MPa以下。再者，於本揭示中，所謂「過濾壓力」係對過濾助劑所施加之每單位面積之壓力，於一個或複數個實施形態中，可藉由利用調節器調整輸出壓力而進行調節。 In the method for producing a polishing liquid composition or a cerium oxide dispersion according to the present disclosure, the filtration pressure in the conditions of the filtration treatment step using a filter containing a filter aid reduces coarse particles and gelation, and reduces grinding. From the viewpoint of scratches on the surface of the substrate, it is preferably 0.16 MPa or more, more preferably 0.18 MPa or more, still more preferably 0.20 MPa or more. From the same viewpoint, the filtration pressure in the filtration treatment step is preferably 0.49 MPa or less, more preferably 0.45 MPa or less, further preferably 0.40 MPa or less, and still more preferably 0.30 MPa or less. Further, in the present disclosure, the "filter pressure" is a pressure per unit area applied to the filter aid, and can be adjusted by adjusting the output pressure by a regulator in one or a plurality of embodiments.

於本揭示之研磨液組合物或二氧化矽分散液之製造方法中，利用含過濾助劑之過濾器進行過濾處理之步驟之條件中之過濾流量就減少粗大粒子及凝膠化物、及減少研磨後之基板表面之刮痕之觀點而言，較佳為10.0g/(分鐘．m2)以上，更佳為12.0g/(分鐘．m2)以上，進而較佳為14.0g/(分鐘．m2)以上。就相同之觀點而言，過濾處理步驟之過濾流量較佳為40.0g/(分鐘．m2)以下，更佳為38.0g/(分鐘． m2)以下，進而較佳為36.0g/(分鐘．m2)以下。再者，於本揭示中，所謂「過濾流量」係每單位面積所過濾之每單位時間之重量，於一個或複數個實施形態中，可藉由調整作為過濾器出口之二次側之閥而進行調節。 In the method for producing a polishing liquid composition or a cerium oxide dispersion according to the present disclosure, the filtration flow rate under the conditions of the filtration treatment step using a filter containing a filter aid reduces coarse particles and gelation, and reduces grinding. From the viewpoint of scratches on the surface of the substrate, it is preferably 10.0 g/(min. m 2 ) or more, more preferably 12.0 g/(min. m 2 ) or more, and still more preferably 14.0 g/(min. m 2 ) or more. From the same viewpoint, the filtration flow rate in the filtration treatment step is preferably 40.0 g/(min.m 2 ) or less, more preferably 38.0 g/(min. m 2 ) or less, and still more preferably 36.0 g/(minute. .m 2 ) below. Furthermore, in the present disclosure, the "filter flow rate" is the weight per unit time filtered per unit area, and in one or more embodiments, the valve acting as the secondary side of the filter outlet can be adjusted. Make adjustments.

就同時實現過濾精度提高與生產性提高之觀點而言，含過濾助劑之過濾器之段數較佳為1~5段，更佳為1~3段，進而較佳為1~2段。 The number of the filter containing the filter aid is preferably from 1 to 5, more preferably from 1 to 3, and still more preferably from 1 to 2, from the viewpoint of achieving both improvement in filtration accuracy and improvement in productivity.

就減少粗大粒子及凝膠化物、及減少研磨後之基板表面之刮痕之觀點而言，較佳為於本揭示之研磨液組合物或二氧化矽分散液之製造方法中，進而組合先前以來用於製造研磨液組合物之深度型過濾器或摺疊型過濾器而使用。 From the viewpoint of reducing coarse particles and gelation, and reducing scratches on the surface of the substrate after polishing, it is preferably used in the method for producing a polishing liquid composition or a cerium oxide dispersion according to the present disclosure, and further combining It is used for a depth type filter or a folding type filter for manufacturing a polishing liquid composition.

於一個或複數個實施形態中，就減少粗大粒子及凝膠化物、及減少研磨後之基板表面之刮痕之觀點而言，本揭示之研磨液組合物之製造方法較佳為利用深度型過濾器過濾被處理二氧化矽分散液後，利用含過濾助劑之過濾器進行過濾處理，更佳為利用含過濾助劑之過濾器進行過濾後，進而利用摺疊型過濾器進行過濾。推測藉由利用深度型過濾器而去除特別大之粗大粒子，而更顯著地發揮出含過濾助劑之過濾器之優異性能，從而可有效率地去除粗大粒子及沈澱物。 In one or more embodiments, the method for producing the polishing liquid composition of the present disclosure preferably utilizes depth filtration in terms of reducing coarse particles and gelation, and reducing scratches on the surface of the substrate after polishing. After filtering the treated cerium oxide dispersion, it is filtered by a filter containing a filter aid, more preferably filtered by a filter containing a filter aid, and then filtered by a folding filter. It is presumed that the use of the deep type filter removes particularly large coarse particles, and the excellent performance of the filter containing the filter aid is more prominently exhibited, so that the coarse particles and the precipitate can be efficiently removed.

作為本揭示之研磨液組合物或二氧化矽分散液之製造方法所使用之深度型過濾器之具體例，除袋式(Sumitomo 3M公司等)以外，可列舉筒式(Advantec Toyo公司、Nihon Pall公司、CUNO公司、Daiwabo公司等)之過濾器。 Specific examples of the depth type filter used in the method for producing a polishing liquid composition or a cerium oxide dispersion according to the present invention include a cartridge type (Advantec Toyo Co., Ltd., Nihon Pall), in addition to a bag type (Sumitomo 3M Co., Ltd., etc.). Filters of the company, CUNO, Daiwabo, etc.).

所謂深度型過濾器，具有如下特徵：過濾材料之孔構造於入口側較粗，於出口側較細，且隨著自入口側朝向出口側，連續地或階段性地變細。即，於入口側附近捕獲粗大粒子中較大之粒子，於出口側附近捕獲較小之粒子，因此可進行有效之過濾。深度型過濾器之形狀 可為袋狀之袋式，又，亦可為中空圓筒形狀之筒式。又，僅將具有上述特徵之過濾材料成形加工為褶狀者由於具有深度型過濾器之功能，故而分類為深度型過濾器。深度型過濾器可以1段使用，亦可以多段組合(例如以串聯配置)使用，就提高生產性之觀點而言，較佳為將孔之直徑不同之過濾器以孔由大到小之順序設為多段。又，亦可將袋式與筒式組合而使用。 The depth type filter has a feature that the pore structure of the filter material is thicker on the inlet side, thinner on the outlet side, and is tapered continuously or stepwise from the inlet side toward the outlet side. That is, larger particles of the coarse particles are trapped near the inlet side, and smaller particles are trapped near the outlet side, so that effective filtration can be performed. Depth filter shape It can be a bag-shaped bag or a hollow cylindrical tube. Further, only the filter material having the above characteristics is formed into a pleat shape, and since it has a function of a depth filter, it is classified into a depth filter. The depth type filter can be used in one stage or in multiple stages (for example, in a series configuration). From the viewpoint of improving productivity, it is preferable to set the filters having different diameters of the holes in order from large to small. For multiple segments. Further, it is also possible to use a combination of a bag type and a drum type.

作為本揭示之研磨液組合物或二氧化矽分散液之製造方法所使用之摺疊型過濾器，通常可使用將過濾材料成形加工為褶狀(褶裙狀)，設為中空圓筒形狀之筒式者(Advantec Toyo公司、Nihon Pall公司、CUNO公司、Daiwabo公司等)。據稱摺疊型過濾器與於厚度方向之各部分進行捕獲之深度型過濾器不同，過濾材料之厚度較薄，於過濾器表面之捕獲為主體，一般而言特徵為過濾精度較高。摺疊型過濾器可以1段使用，亦可以多段組合(例如以串聯配置)使用。 As the folding type filter used in the polishing liquid composition or the method for producing a cerium oxide dispersion of the present invention, a filter material is usually formed into a pleated shape (pleated skirt shape), and a hollow cylindrical shape can be used. (Advantec Toyo, Nihon Pall, CUNO, Daiwabo, etc.). It is said that the folding type filter is different from the depth type filter which captures each part in the thickness direction, the thickness of the filter material is thin, and the capture on the surface of the filter is the main body, and generally the characteristic is high filtration precision. The folding filter can be used in one stage or in multiple stages (for example, in a series configuration).

於整個過濾處理步驟中，若依序進行利用深度型過濾器所進行之過濾、利用含過濾助劑之過濾器所進行之過濾、利用摺疊型過濾器所進行之過濾，則可整體地延長過濾器之壽命，可經濟性地生產本揭示之研磨液組合物或二氧化矽分散液，故而較佳。 In the entire filtration treatment step, if the filtration by the depth filter is performed in sequence, the filtration by the filter containing the filter aid, and the filtration by the folding filter, the filtration can be extended as a whole. The life of the apparatus is economical to produce the polishing liquid composition or the cerium oxide dispersion of the present invention, which is preferable.

作為過濾處理方法，可為反覆進行過濾之循環式，亦可為單程處理方式。又，亦可使用反覆進行單程處理方式之分批式。液體透過方法由於進行加壓，故而循環式較佳為使用泵，單程處理方式除使用泵以外，亦可使用藉由向槽內導入氣壓等而過濾器入口壓力之變動幅度較小之加壓過濾法。 As the filtration treatment method, it may be a cyclic type in which filtration is repeated, or a single-pass treatment method. Further, it is also possible to use a batch type in which the one-way processing method is repeated. Since the liquid permeation method is pressurized, the circulation type is preferably a pump, and the one-way treatment method may use a pressure filtration method in which the fluctuation of the inlet pressure of the filter is small by introducing a gas pressure or the like into the tank. law.

於本揭示之研磨液組合物或二氧化矽分散液之製造方法中，除使用上述深度型過濾器或摺疊型過濾器以外，亦可設置一般粒子之分散步驟或者粒子去除步驟。例如亦可利用使用高速分散裝置或高壓均質機等高壓分散裝置之分散步驟、或利用離心分離裝置等所進行之粗 大粒子之沈澱步驟。於使用該等進行處理之情形時，可分別單獨進行處理，亦可組合2種以上進行處理，組合之處理順序亦無任何限制。 又，其處理條件或處理次數亦可適當地選擇使用。 In the method for producing a polishing liquid composition or a cerium oxide dispersion according to the present disclosure, in addition to the above-described depth type filter or folding type filter, a general particle dispersion step or a particle removal step may be provided. For example, it is also possible to use a dispersion step using a high-pressure dispersing device such as a high-speed dispersing device or a high-pressure homogenizer, or a coarsening device using a centrifugal separating device or the like. The precipitation step of large particles. When the treatment is carried out using these, the treatment may be carried out separately or in combination of two or more kinds, and the order of the combination is not limited. Further, the processing conditions or the number of times of processing may be appropriately selected and used.

[0.45μm過濾器液體透過量] [0.45μm filter liquid permeation amount]

使粗大粒子或凝膠化物較多之研磨液組合物或二氧化矽分散液(經過濾處理之被處理二氧化矽分散液)透過過濾器時，會引起堵塞，導致液體透過量減少。因此，研磨液組合物/二氧化矽分散液之0.45μm過濾器液體透過量(對孔徑0.45μm之過濾器之液體透過量)成為粗大粒子或凝膠化物之存在量之尺度。再者，於二氧化矽粒子之一次粒子之平均粒徑較大之情形時，亦容易引起堵塞，導致0.45μm過濾器液體透過量減少，因此「0.45μm過濾器液體透過量」適合作為用以比較二氧化矽粒子之一次粒子之平均粒徑為相同程度之研磨液組合物/二氧化矽分散液之參數。 When the polishing liquid composition or the ceria dispersion (filtered treated ceria dispersion) having a large amount of coarse particles or a gelation is passed through the filter, clogging is caused, and the amount of liquid permeation is reduced. Therefore, the 0.45 μm filter liquid permeation amount (liquid permeation amount of the filter having a pore diameter of 0.45 μm) of the polishing liquid composition/cerium oxide dispersion is a measure of the amount of coarse particles or gelation present. Further, when the average particle diameter of the primary particles of the cerium oxide particles is large, clogging is likely to occur, and the liquid permeation amount of the 0.45 μm filter is reduced. Therefore, the "0.45 μm filter liquid permeation amount" is suitable for use. The parameters of the slurry composition/cerium dioxide dispersion having the same average particle diameter of the primary particles of the ceria particles are compared.

就減少刮痕之觀點而言，本揭示之研磨液組合物或二氧化矽分散液(經過濾處理之被處理二氧化矽分散液)之0.45μm過濾器液體透過量較佳為100mL以上，更佳為120mL以上，進而較佳為140mL以上，進而更佳為150ml以上，進而更佳為180ml以上。此處，研磨液組合物或二氧化矽分散液之0.45μm過濾器液體透過量可藉由實施例中記載之方法進行測定。 The 0.45 μm filter liquid permeation amount of the polishing liquid composition or the cerium oxide dispersion (filtered treated cerium oxide dispersion) of the present disclosure is preferably 100 mL or more, from the viewpoint of reducing scratches, and more preferably It is preferably 120 mL or more, more preferably 140 mL or more, still more preferably 150 ml or more, and still more preferably 180 ml or more. Here, the 0.45 μm filter liquid permeation amount of the polishing liquid composition or the ceria dispersion can be measured by the method described in the examples.

[二氧化矽分散液之製造方法] [Method for producing cerium oxide dispersion]

藉由上述過濾處理方法，可獲得粗大粒子及凝膠化物減少之二氧化矽分散液。因此，本揭示於另一態樣中係關於一種二氧化矽分散液之製造方法，其包括利用包含過濾助劑之過濾器對含有膠體二氧化矽之被處理二氧化矽分散液進行過濾處理之步驟，並且上述膠體二氧化矽之藉由滴定法所求得之一次粒子之平均粒徑為1nm以上且50nm以下，上述過濾助劑之羥基密度為0.40×10-5mol/m2以上。於一個或 複數個實施形態中，藉由該製造方法所獲得之二氧化矽分散液可製造下述本揭示之過濾精度較高之研磨液組合物，又，可製造研磨後之基板表面之刮痕減少之基板。 By the above filtration treatment method, a coarse particle and a gelation-reduced cerium oxide dispersion can be obtained. Therefore, the present disclosure relates to another aspect of a method for producing a cerium oxide dispersion, which comprises filtering a treated cerium oxide dispersion containing colloidal cerium oxide by using a filter comprising a filter aid. In the step, the average particle diameter of the primary particles obtained by the titration method of the colloidal ceria is 1 nm or more and 50 nm or less, and the hydroxyl concentration of the filter aid is 0.40×10 -5 mol/m 2 or more. In one or more embodiments, the cerium oxide dispersion obtained by the production method can produce the polishing liquid composition having the higher filtration precision as disclosed in the following disclosure, and can also be used to manufacture the surface of the substrate after polishing. A substrate with reduced marks.

[研磨液組合物] [grinding liquid composition]

本揭示於另一態樣中係關於一種利用或可利用研磨液組合物之製造方法而製造之研磨液組合物(以下亦稱為「本揭示之研磨液組合物」)。於一個或複數個實施形態中，本揭示之研磨液組合物可列舉除膠體二氧化矽及水以外，亦包含下述酸或者其鹽或鹼、及/或氧化劑之形態。但是，本揭示之研磨液組合物並不限定於該等組成，亦可包含其他成分。於一個或複數個實施形態中，本揭示之研磨液組合物係藉由於利用本揭示之二氧化矽分散液之製造方法所獲得之二氧化矽分散液中視需要混合其他成分而獲得之研磨液組合物。 In another aspect, the present disclosure relates to a polishing composition (hereinafter also referred to as "the polishing composition of the present invention") which is produced by using the method for producing a polishing composition. In one or a plurality of embodiments, the polishing liquid composition of the present invention may be in the form of an acid or a salt or a base thereof and/or an oxidizing agent in addition to colloidal cerium oxide and water. However, the polishing liquid composition of the present disclosure is not limited to the compositions, and may contain other components. In one or more embodiments, the polishing composition of the present disclosure is a slurry composition obtained by mixing other components as needed in the cerium oxide dispersion obtained by the method for producing a cerium oxide dispersion of the present disclosure. Things.

[膠體二氧化矽之含量] [Content of colloidal cerium oxide]

對被研磨物進行研磨時之本揭示之研磨液組合物中之膠體二氧化矽之含量就提高研磨速度之觀點而言，較佳為0.5質量%以上，更佳為1質量%以上，進而較佳為2質量%以上，進而較佳為4質量%以上，又，就經濟性地提高表面品質之觀點而言，較佳為20質量%以下，更佳為15質量%以下，進而較佳為13質量%以下，進而更佳為10質量%以下，進而更佳為8質量%以下。 The content of the colloidal cerium oxide in the polishing liquid composition of the present invention when the object to be polished is polished is preferably 0.5% by mass or more, more preferably 1% by mass or more, and more preferably from the viewpoint of increasing the polishing rate. It is preferably 2% by mass or more, and more preferably 4% by mass or more, and is preferably 20% by mass or less, more preferably 15% by mass or less, and more preferably from the viewpoint of economically improving the surface quality. 13% by mass or less, more preferably 10% by mass or less, still more preferably 8% by mass or less.

[水] [water]

作為本揭示之研磨液組合物所使用之水，可列舉離子交換水、蒸餾水、超純水等。本揭示之研磨液組合物中之水之含量相當於自100質量%去除研磨材料及其他成分後之剩餘部分，較佳為60~99質量%，更佳為80~97質量%。 Examples of the water used in the polishing liquid composition of the present invention include ion-exchanged water, distilled water, ultrapure water, and the like. The content of water in the polishing liquid composition of the present invention corresponds to the remainder after removing the abrasive and other components from 100% by mass, preferably 60 to 99% by mass, more preferably 80 to 97% by mass.

[pH值] [pH]

本揭示之研磨液組合物於25℃下之pH值只要根據研磨對象而適 當地進行調節即可，較佳為0.1以上且7.0以下。於為鹼性時，與酸性相比，有容易產生刮痕之傾向。其產生機制尚不明確，推測於研磨粒子彼此因表面電荷而強烈地相互排斥之鹼性環境下，研磨液組合物中所含有之研磨材料之一次粒子之凝集物或者粗大粒子會妨礙研磨材料緊密地填充至被研磨物與研磨墊之間，因此荷重會不均勻地被施加於整個研磨面。pH值較佳為根據被研磨物之種類或要求特性而決定，於被研磨物之材質為金屬材料時，就提高研磨速度之觀點而言，更佳為6.0以下，進而較佳為5.0以下，進而更佳為4.0以下，進而更佳為3.0以下，進而更佳為2.0以下。又，就減少對人體之影響之觀點及防止研磨裝置之腐蝕之觀點而言，pH值更佳為0.5以上，進而較佳為0.7以上，進而更佳為0.9以上，進而更佳為1.0以上，進而更佳為1.2以上。尤其是於如鍍鎳-磷(Ni-P)之鋁合金基板般，被研磨物之材質為金屬材料，被研磨物為精密零件用基板之情形時，就提高研磨速度之觀點、減少對人體之影響之觀點、及防止研磨裝置之腐蝕之觀點而言，pH值更佳為0.5以上且6.0以下，進而較佳為0.7以上且5.0以下，進而更佳為0.9以上且4.0以下，進而更佳為1.0以上且3.0以下，進而更佳為1.0以上且2.0以下。 The pH of the polishing composition of the present disclosure at 25 ° C is suitable according to the object to be polished. The adjustment may be performed locally, preferably 0.1 or more and 7.0 or less. When it is alkaline, it tends to cause scratches as compared with acidity. The mechanism of the production is not clear. It is presumed that under the alkaline environment in which the abrasive particles are strongly mutually repelled by the surface charge, the agglomerates or coarse particles of the primary particles of the abrasive material contained in the polishing liquid composition may hinder the abrasive material from being tight. The ground is filled between the object to be polished and the polishing pad, so that the load is unevenly applied to the entire polishing surface. The pH is preferably determined according to the type of the object to be polished or the required characteristics. When the material of the object to be polished is a metal material, the polishing rate is preferably 6.0 or less, and more preferably 5.0 or less. Further, it is more preferably 4.0 or less, still more preferably 3.0 or less, and still more preferably 2.0 or less. Further, from the viewpoint of reducing the influence on the human body and preventing corrosion of the polishing apparatus, the pH is more preferably 0.5 or more, further preferably 0.7 or more, still more preferably 0.9 or more, and still more preferably 1.0 or more. More preferably, it is 1.2 or more. In particular, in the case of a nickel-plated-phosphorus (Ni-P)-based aluminum alloy substrate, when the material to be polished is a metal material and the object to be polished is a substrate for a precision component, the polishing speed is improved and the human body is reduced. From the viewpoint of the influence and the corrosion prevention of the polishing apparatus, the pH is more preferably 0.5 or more and 6.0 or less, still more preferably 0.7 or more and 5.0 or less, still more preferably 0.9 or more and 4.0 or less, and still more preferably It is 1.0 or more and 3.0 or less, and more preferably 1.0 or more and 2.0 or less.

[酸] [acid]

就提高研磨速度之觀點而言，本揭示之研磨液組合物亦可包含酸或其鹽。作為上述酸及其鹽，具體而言，可列舉：硝酸、硫酸、亞硝酸、過硫酸、鹽酸、過氯酸、磷酸、膦酸、次膦酸、焦磷酸、三聚磷酸、胺基磺酸等無機酸或該等之鹽、2-胺基乙基膦酸、1-羥基亞乙基-1,1-二膦酸、羥基膦酸基乙酸(PHAA)、胺基三(亞甲基膦酸)、乙二胺四(亞甲基膦酸)、二乙三胺五(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-1,1-二膦酸、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-膦酸基丁烷-1,2- 二羧酸、2-膦酸基-1,2,4-丁烷三羧酸(PBTC)、1-膦酸基丁烷-2,3,4-三羧酸、α-甲基膦酸基琥珀酸等有機膦酸或該等之鹽、麩胺酸、吡啶甲酸、天冬胺酸等胺基羧酸或該等之鹽、草酸、硝乙酸、順丁烯二酸、草醯乙酸等羧酸或該等之鹽等。該等可單獨或混合2種以上而使用。 其中，就減少刮痕之觀點而言，本揭示之研磨液組合物較佳為包含無機酸或有機膦酸及該等之鹽。 The polishing liquid composition of the present invention may also contain an acid or a salt thereof from the viewpoint of increasing the polishing rate. Specific examples of the acid and the salt thereof include nitric acid, sulfuric acid, nitrous acid, persulfuric acid, hydrochloric acid, perchloric acid, phosphoric acid, phosphonic acid, phosphinic acid, pyrophosphoric acid, tripolyphosphoric acid, and aminosulfonic acid. Or an inorganic acid or such a salt, 2-aminoethylphosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, hydroxyphosphonic acid acetic acid (PHAA), aminotris (methylenephosphine) Acid), ethylenediaminetetrakis (methylene phosphonic acid), diethylenetriamine penta (methylene phosphonic acid), ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphine Acid, ethane-1-hydroxy-1,1-diphosphonic acid, ethane-1-hydroxy-1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphine Acid, methane hydroxyphosphonic acid, 2-phosphonylbutane-1,2- Dicarboxylic acid, 2-phosphono-1,2,4-butanetricarboxylic acid (PBTC), 1-phosphonic acid butane-2,3,4-tricarboxylic acid, α-methylphosphonic acid group An organic phosphonic acid such as succinic acid or a salt of the same, an aminocarboxylic acid such as glutamic acid, picolinic acid or aspartic acid or a salt thereof, a carboxylic acid such as oxalic acid, nitric acid, maleic acid or oxalic acid; Acid or such salt and the like. These may be used alone or in combination of two or more. Among them, the polishing liquid composition of the present invention preferably contains a mineral acid or an organic phosphonic acid and the salts thereof from the viewpoint of reducing scratches.

上述無機酸或該等之鹽中，更佳為硝酸、硫酸、鹽酸、過氯酸或該等之鹽，上述有機膦酸或該等之鹽中，更佳為1-羥基亞乙基-1,1-二膦酸、羥基膦酸基乙酸、胺基三(亞甲基膦酸)、乙二胺四(亞甲基膦酸)、二乙三胺五(亞甲基膦酸)、2-膦酸基-1,2,4-丁烷三羧酸或該等之鹽，進而較佳為1-羥基亞乙基-1,1-二膦酸。該等可單獨或混合2種以上而使用。 More preferably, the above inorganic acid or the salt is nitric acid, sulfuric acid, hydrochloric acid, perchloric acid or the like, and the above organic phosphonic acid or the above salts is more preferably 1-hydroxyethylidene-1. , 1-diphosphonic acid, hydroxyphosphonic acid acetic acid, amine tris (methylene phosphonic acid), ethylene diamine tetra (methylene phosphonic acid), diethylene triamine penta (methylene phosphonic acid), 2 - phosphonic acid-1,2,4-butanetricarboxylic acid or a salt thereof, and more preferably 1-hydroxyethylidene-1,1-diphosphonic acid. These may be used alone or in combination of two or more.

作為上述酸之鹽，並無特別限定，具體而言，可列舉與金屬、氨、烷基胺之鹽。作為金屬之具體例，可列舉屬於週期表(長週期型)之1A、1B、2A、2B、3A、3B、4A、6A、7A或8族之金屬。就減少刮痕之觀點而言，較佳為氨或屬於1A族之金屬。 The salt of the above acid is not particularly limited, and specific examples thereof include a salt of a metal, ammonia, and an alkylamine. Specific examples of the metal include metals belonging to Groups 1A, 1B, 2A, 2B, 3A, 3B, 4A, 6A, 7A or 8 of the periodic table (long-period type). From the viewpoint of reducing scratches, ammonia or a metal belonging to Group 1A is preferred.

就提高研磨速度及減少研磨後之基板表面之刮痕之觀點而言，本揭示之研磨液組合物中之上述酸及其鹽之含量較佳為0.001質量%以上且5質量%以下，更佳為0.01質量%以上且4質量%以下，進而較佳為0.05質量%以上且3質量%以下，進而更佳為0.1質量%以上且2.0質量%以下，進而更佳為0.1質量%以上且1.0質量%以下。 The content of the acid and the salt thereof in the polishing liquid composition of the present invention is preferably 0.001% by mass or more and 5% by mass or less, more preferably from the viewpoint of increasing the polishing rate and reducing the scratch on the surface of the substrate after polishing. It is 0.01% by mass or more and 4% by mass or less, more preferably 0.05% by mass or more and 3% by mass or less, still more preferably 0.1% by mass or more and 2.0% by mass or less, and still more preferably 0.1% by mass or more and 1.0% by mass. %the following.

[氧化劑] [oxidant]

就研磨速度提高之觀點而言，本揭示之研磨液組合物較佳為含有氧化劑。作為可用於本揭示之研磨液組合物的氧化劑，就提高研磨速度之觀點而言，可列舉：過氧化物、過錳酸或其鹽、鉻酸或其鹽、過氧酸或其鹽、含氧酸或其鹽、金屬鹽類、硝酸類、硫酸類等。 The polishing liquid composition of the present invention preferably contains an oxidizing agent from the viewpoint of an increase in the polishing rate. Examples of the oxidizing agent which can be used in the polishing liquid composition of the present invention include a peroxide, permanganic acid or a salt thereof, chromic acid or a salt thereof, peroxy acid or a salt thereof, and the like, from the viewpoint of increasing the polishing rate. Oxyacid or a salt thereof, a metal salt, a nitric acid, a sulfuric acid or the like.

作為上述過氧化物，可列舉過氧化氫、過氧化鈉、過氧化鋇等，作為過錳酸或其鹽，可列舉過錳酸鉀等，作為鉻酸或其鹽，可列舉鉻酸金屬鹽、重鉻酸金屬鹽等，作為過氧酸或其鹽，可列舉：過氧二硫酸、過氧二硫酸銨、過氧二硫酸金屬鹽、過氧磷酸、過氧硫酸、過氧硼酸鈉、過氧甲酸、過氧乙酸、過氧苯甲酸、過氧鄰苯二甲酸等，作為含氧酸或其鹽，可列舉：次氯酸、次溴酸、次碘酸、氯酸、溴酸、碘酸、次氯酸鈉、次氯酸鈣等，作為金屬鹽類，可列舉氯化鐵(III)、硫酸鐵(III)、硝酸鐵(III)、檸檬酸鐵(III)、硫酸銨鐵(III)等。 Examples of the peroxide include hydrogen peroxide, sodium peroxide, and ruthenium peroxide. Examples of the permanganic acid or a salt thereof include potassium permanganate. Examples of the chromic acid or a salt thereof include a metal chromate salt. And a dichromate metal salt, etc., as peroxy acid or its salt, a peroxy disulfate, ammonium peroxydisulfate, a metal salt of peroxy disulfate, a peroxy phosphoric acid, a peroxy sulfuric acid, sodium peroxyborate, etc. Peroxyformic acid, peracetic acid, peroxybenzoic acid, peroxyphthalic acid, etc., as an oxoacid or a salt thereof, hypochlorous acid, hypobromous acid, hypoiodous acid, chloric acid, bromic acid, Examples of metal salts include iodic acid, sodium hypochlorite, calcium hypochlorite, and the like, and iron chloride (III), iron (III) sulfate, iron (III) nitrate, iron (III) citrate, and iron (III) sulfate. Wait.

作為較佳之氧化劑，可列舉過氧化氫、硝酸鐵(III)、過氧乙酸、過氧二硫酸銨、硫酸鐵(III)及硫酸銨鐵(III)等。作為更佳之氧化劑，就金屬離子不附著於表面、通用地使用且廉價之觀點而言，可列舉過氧化氫。該等氧化劑可單獨或混合2種以上而使用。 Preferred examples of the oxidizing agent include hydrogen peroxide, iron (III) nitrate, peracetic acid, ammonium peroxodisulfate, iron (III) sulfate, and iron (III) sulfate. As a more preferable oxidizing agent, hydrogen peroxide is mentioned from the viewpoint that metal ions do not adhere to the surface, are generally used, and are inexpensive. These oxidizing agents can be used singly or in combination of two or more.

上述研磨液組合物中之上述氧化劑之含量就提高研磨速度之觀點而言，較佳為0.01質量%以上，更佳為0.05質量%以上，進而較佳為0.1質量%以上，就降低基板之表面粗糙度之觀點而言，較佳為4質量%以下，更佳為2質量%以下，進而較佳為1質量%以下。 The content of the oxidizing agent in the polishing liquid composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and still more preferably 0.1% by mass or more, from the viewpoint of increasing the polishing rate, thereby lowering the surface of the substrate. From the viewpoint of roughness, it is preferably 4% by mass or less, more preferably 2% by mass or less, and still more preferably 1% by mass or less.

[其他成分] [Other ingredients]

又，上述研磨液組合物可視需要調配其他成分。於一個或複數個實施形態中，作為其他成分，可列舉雜環芳香族化合物、具有陰離子性基之水溶性高分子(亦稱為「陰離子性水溶性高分子」)、脂肪族胺化合物、脂環式胺化合物等。又，於一個或複數個實施形態中，進而作為其他成分，可列舉增黏劑、分散劑、防銹劑、鹼性物質、界面活性劑等。 Further, the above-mentioned polishing liquid composition may be blended with other components as needed. In one or a plurality of embodiments, examples of the other component include a heterocyclic aromatic compound, a water-soluble polymer having an anionic group (also referred to as "anionic water-soluble polymer"), an aliphatic amine compound, and a fat. Cyclic amine compounds and the like. Further, in one or a plurality of embodiments, examples of the other component include a tackifier, a dispersant, a rust preventive, a basic substance, and a surfactant.

[雜環芳香族化合物] [Heterocyclic aromatic compound]

對被研磨物進行研磨時之研磨液組合物較佳為含有雜環芳香族化合物(亦包括其鹽)。就減少研磨後之基板之刮痕及粒子之觀點而 言，本揭示之研磨液組合物中所含有之雜環芳香族化合物較佳為於雜環內包含2個以上氮原子之雜環芳香族化合物，更佳為於雜環內具有3個以上氮原子，進而較佳為3個以上且9個以下，進而更佳為3個以上且5個以下，進而更佳為3或4個。 The polishing composition for polishing the object to be polished preferably contains a heterocyclic aromatic compound (including a salt thereof). In terms of reducing the scratches and particles of the polished substrate The heterocyclic aromatic compound contained in the polishing liquid composition of the present invention is preferably a heterocyclic aromatic compound containing two or more nitrogen atoms in the hetero ring, and more preferably having three or more nitrogens in the heterocyclic ring. The atom is further preferably 3 or more and 9 or less, more preferably 3 or more and 5 or less, and still more preferably 3 or 4.

就減少研磨後之基板之刮痕之觀點而言，上述雜環芳香族化合物較佳為嘧啶、吡、嗒、1,2,3-三、1,2,4-三、1,2,5-三、1,3,5-三、1,2,4-二唑、1,2,5-二唑、1,3,4-二唑、1,2,5-噻二唑、1,3,4-噻二唑、3-胺基吡唑、4-胺基吡唑、3,5-二甲基吡唑、吡唑、2-胺基咪唑、4-胺基咪唑、5-胺基咪唑、2-甲基咪唑、2-乙基咪唑、咪唑、苯并咪唑、1,2,3-***、4-胺基-1,2,3-***、5-胺基-1,2,3-***、1,2,4-***、3-胺基-1,2,4-***、5-胺基-1,2,4-***、3-巰基-1,2,4-***、1H-四唑、5-胺基四唑、1H-苯并***、1H-甲苯***、2-胺基苯并***、3-胺基苯并***、或該等之烷基取代體或者胺取代體，更佳為1H-苯并***、1H-甲苯***，進而較佳為1H-苯并***。 作為上述烷基取代體之烷基，例如可列舉碳數1~4之低級烷基，更具體而言，可列舉甲基、乙基。又，作為上述胺取代體，可列舉1-[N,N-雙(羥基伸乙基)胺基甲基]苯并***、1-[N,N-雙(羥基伸乙基)胺基甲基]甲苯***。 The above heterocyclic aromatic compound is preferably pyrimidine or pyridinium from the viewpoint of reducing scratches of the substrate after polishing. ,despair 1,2,3-three 1,2,4-three 1,2,5-three 1,3,5-three 1,2,4- Diazole, 1,2,5- Diazole, 1,3,4- Diazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 3-aminopyrazole, 4-aminopyrazole, 3,5-dimethylpyrazole, pyrazole, 2-Aminoimidazole, 4-Aminoimidazole, 5-Aminoimidazole, 2-Methylimidazole, 2-Ethylimidazole, Imidazole, Benzimidazole, 1,2,3-Triazole, 4-Amino- 1,2,3-triazole, 5-amino-1,2,3-triazole, 1,2,4-triazole, 3-amino-1,2,4-triazole, 5-amino group -1,2,4-triazole, 3-mercapto-1,2,4-triazole, 1H-tetrazole, 5-aminotetrazole, 1H-benzotriazole, 1H-tolutriazole, 2- Aminobenzotriazole, 3-aminobenzotriazole, or such alkyl substituent or amine substituent, more preferably 1H-benzotriazole, 1H-tolutriazole, and further preferably 1H - benzotriazole. Examples of the alkyl group of the alkyl group-substituted ones include a lower alkyl group having 1 to 4 carbon atoms, and more specifically, a methyl group or an ethyl group. Further, examples of the amine substituent include 1-[N,N-bis(hydroxyethyl)aminomethyl]benzotriazole and 1-[N,N-bis(hydroxyethyl)amino group. Methyl]toluene triazole.

作為上述雜環芳香族化合物之鹽，並無特別限定，具體而言，可列舉與金屬、氨、烷基胺之鹽。作為金屬之具體之例，可列舉屬於週期表(長週期型)之1A、1B、2A、2B、3A、3B、4A、6A、7A或8族之金屬。就減少刮痕之觀點而言，較佳為氨或屬於1A族之金屬。 The salt of the above heterocyclic aromatic compound is not particularly limited, and specific examples thereof include salts with metals, ammonia, and alkylamines. Specific examples of the metal include metals belonging to Groups 1A, 1B, 2A, 2B, 3A, 3B, 4A, 6A, 7A or 8 of the periodic table (long-period type). From the viewpoint of reducing scratches, ammonia or a metal belonging to Group 1A is preferred.

就減少研磨後之基板之刮痕及粒子之觀點而言，研磨液組合物中之雜環芳香族化合物之含量相對於研磨液組合物整體之質量，較佳為0.01質量%以上，更佳為0.02質量%以上，進而較佳為0.05質量%以上，進而更佳為0.06質量%以上，進而更佳為0.07質量%以上，進而 更佳為0.08質量%以上，又，較佳為10質量%以下，更佳為5質量%以下，進而較佳為2質量%以下，進而更佳為1質量%以下，進而更佳為0.5質量%以下，進而更佳為0.3質量%以下。再者，研磨液組合物中之雜環芳香族化合物可為1種，亦可為2種以上。 The content of the heterocyclic aromatic compound in the polishing liquid composition is preferably 0.01% by mass or more, more preferably 0.01% by mass or more based on the total mass of the polishing liquid composition, from the viewpoint of reducing scratches and particles of the substrate after polishing. 0.02% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.06% by mass or more, still more preferably 0.07% by mass or more, and further It is more preferably 0.08% by mass or more, further preferably 10% by mass or less, more preferably 5% by mass or less, further preferably 2% by mass or less, further preferably 1% by mass or less, and further preferably 0.5% by mass. % or less, more preferably 0.3% by mass or less. In addition, the heterocyclic aromatic compound in the polishing liquid composition may be one type or two or more types.

[陰離子性水溶性高分子] [Anionic water-soluble polymer]

就研磨後之基板之刮痕、粒子及表面粗糙度之最大值(AFM-Rmax)減少之觀點而言，對被研磨物進行研磨時之研磨液組合物較佳為含有陰離子性水溶性高分子。推測該高分子係減少研磨時之摩擦振動，防止二氧化矽凝集體自研磨墊之開孔部脫落，而減少研磨後之基板之刮痕及降低表面粗糙度之最大值(AFM-Rmax)者。 The polishing liquid composition for polishing the object to be polished preferably contains an anionic water-soluble polymer from the viewpoint of reducing the scratch of the substrate after polishing, the maximum value of the particles and the surface roughness (AFM-Rmax). . It is presumed that the polymer reduces the frictional vibration during polishing, prevents the cerium oxide aggregate from falling off from the opening portion of the polishing pad, and reduces the scratch of the substrate after polishing and the maximum surface roughness (AFM-Rmax). .

作為陰離子性水溶性高分子之陰離子性基，可列舉羧酸基、磺酸基、硫酸酯基、磷酸酯基、膦酸基等，就減少刮痕、粒子及降低表面粗糙度之最大值(AFM-Rmax)之觀點而言，更佳為具有羧酸基及/或磺酸基者，進而較佳為具有磺酸基者。再者，該等陰離子性基亦可採用經中和之鹽之形態。 Examples of the anionic group of the anionic water-soluble polymer include a carboxylic acid group, a sulfonic acid group, a sulfate group, a phosphate group, and a phosphonic acid group, thereby reducing scratches, particles, and reducing the maximum value of surface roughness ( From the viewpoint of AFM-Rmax), it is more preferred to have a carboxylic acid group and/or a sulfonic acid group, and more preferably a sulfonic acid group. Further, the anionic groups may also be in the form of a neutralized salt.

作為具有羧酸基及/或磺酸基之水溶性高分子，可列舉具有選自由源自具有羧酸基之單體之結構單元及源自具有磺酸基之單體之結構單元所組成之群中之至少1種結構單元的(共)聚合物或其鹽。作為具有羧酸基之單體，例如可列舉伊康酸、(甲基)丙烯酸、順丁烯二酸等。作為具有磺酸基之單體，例如可列舉：異戊二烯磺酸、2-(甲基)丙烯醯胺-2-甲基丙磺酸、苯乙烯磺酸、甲基烯丙基磺酸、乙烯基磺酸、烯丙基磺酸、異戊烯磺酸、萘磺酸等。陰離子性水溶性高分子中亦可分別包含2種以上之源自具有羧酸基之單體之結構單元及源自具有磺酸基之單體之結構單元。 The water-soluble polymer having a carboxylic acid group and/or a sulfonic acid group may be one having a structural unit selected from a structural unit derived from a monomer having a carboxylic acid group and a monomer derived from a monomer having a sulfonic acid group. a (co)polymer of at least one structural unit of the group or a salt thereof. Examples of the monomer having a carboxylic acid group include itaconic acid, (meth)acrylic acid, maleic acid, and the like. Examples of the monomer having a sulfonic acid group include isoprenesulfonic acid, 2-(methyl)acrylamido-2-methylpropanesulfonic acid, styrenesulfonic acid, and methallylsulfonic acid. , vinyl sulfonic acid, allyl sulfonic acid, isopentenyl sulfonic acid, naphthalene sulfonic acid and the like. The anionic water-soluble polymer may each contain two or more kinds of structural units derived from a monomer having a carboxylic acid group and a structural unit derived from a monomer having a sulfonic acid group.

該等之中，作為陰離子性水溶性高分子，於一個或複數個實施形態中，較佳為包含源自(甲基)丙烯酸之結構單元及源自含磺酸基之 單體之結構單元之共聚物(以下亦稱為「(甲基)丙烯酸/磺酸共聚物」)。 Among these, as an anionic water-soluble polymer, in one or a plurality of embodiments, it is preferred to include a structural unit derived from (meth)acrylic acid and derived from a sulfonic acid group. A copolymer of a structural unit of a monomer (hereinafter also referred to as "(meth)acrylic acid/sulfonic acid copolymer").

上述(甲基)丙烯酸/磺酸共聚物亦可於發揮出本發明之效果之範圍內，含有源自含磺酸基之單體及(甲基)丙烯酸單體以外之單體之結構單元成分。 The (meth)acrylic acid/sulfonic acid copolymer may contain a structural unit component derived from a monomer other than the sulfonic acid group-containing monomer and the (meth)acrylic monomer, within the range in which the effects of the present invention are exerted. .

就減少刮痕之觀點而言，源自含磺酸基之單體之結構單元於構成(甲基)丙烯酸/磺酸共聚物或其鹽各者之全部結構單元中所占之含有率較佳為3莫耳%以上，更佳為5莫耳%以上，進而較佳為8莫耳%以上，又，較佳為97莫耳%以下，更佳為50莫耳%以下，進而較佳為30莫耳%以下。再者，此處，包含磺酸基之(甲基)丙烯酸單體算作含磺酸基之單體。 From the viewpoint of reducing scratches, the structural unit derived from the sulfonic acid group-containing monomer preferably has a content ratio in all structural units constituting each of the (meth)acrylic acid/sulfonic acid copolymer or its salt. It is 3 mol% or more, more preferably 5 mol% or more, further preferably 8 mol% or more, and further preferably 97 mol% or less, more preferably 50 mol% or less, further preferably 30% or less. Here, the (meth)acrylic acid monomer containing a sulfonic acid group is counted as a monomer containing a sulfonic acid group.

於(甲基)丙烯酸/磺酸共聚物為(甲基)丙烯酸/2-(甲基)丙烯醯胺-2-甲基丙磺酸共聚物之情形時，就減少研磨後之基板表面之刮痕及粒子之觀點而言，(甲基)丙烯酸與2-(甲基)丙烯醯胺-2-甲基丙磺酸之聚合莫耳比((甲基)丙烯酸/2-(甲基)丙烯醯胺-2-甲基丙磺酸)較佳為95/5~40/60，更佳為95/5~50/50，進而較佳為95/5~60/40，進而更佳為95/5~70/30，進而更佳為95/5~75/25，進而更佳為95/5~80/20，進而更佳為95/5~85/15。 In the case where the (meth)acrylic acid/sulfonic acid copolymer is a (meth)acrylic acid/2-(meth)acrylamide amine-2-methylpropanesulfonic acid copolymer, the scraping of the surface of the substrate after grinding is reduced. From the viewpoint of traces and particles, a polymerized molar ratio of (meth)acrylic acid to 2-(meth)acrylamidoxime-2-methylpropanesulfonic acid ((meth)acrylic acid/2-(methyl)acrylic acid) The indoleamine-2-methylpropanesulfonic acid) is preferably 95/5 to 40/60, more preferably 95/5 to 50/50, still more preferably 95/5 to 60/40, and still more preferably 95. /5~70/30, and further preferably 95/5~75/25, and further preferably 95/5~80/20, and more preferably 95/5~85/15.

就減少刮痕之觀點而言，作為較佳之(甲基)丙烯酸/磺酸共聚物，可列舉：(甲基)丙烯酸/異戊二烯磺酸共聚物、(甲基)丙烯酸/2-(甲基)丙烯醯胺-2-甲基丙磺酸共聚物、(甲基)丙烯酸/異戊二烯磺酸/2-(甲基)丙烯醯胺-2-甲基丙磺酸共聚物，更佳為(甲基)丙烯酸/2-(甲基)丙烯醯胺-2-甲基丙磺酸共聚物。 From the viewpoint of reducing scratches, preferred (meth)acrylic acid/sulfonic acid copolymers include (meth)acrylic acid/isoprenesulfonic acid copolymer and (meth)acrylic acid/2-( Methyl) acrylamide-2-methylpropanesulfonic acid copolymer, (meth)acrylic acid/isoprenesulfonic acid/2-(meth)acrylamide amine-2-methylpropanesulfonic acid copolymer, More preferably, it is a (meth)acrylic acid / 2 - (meth) acrylamide - 2 - methyl propane sulfonic acid copolymer.

作為具有陰離子性基之水溶性高分子之抗衡離子，並無特別限定，具體而言，可列舉金屬、銨、烷基銨等之離子。作為金屬之具體例，可列舉屬於週期表(長週期型)1A、1B、2A、2B、3A、3B、4A、 6A、7A或8族之金屬。該等金屬中，就表面粗糙度及減少刮痕之觀點而言，較佳為屬於1A、3B、或8族之金屬，更佳為屬於1A族之鈉及鉀。作為烷基銨之具體例，可列舉四甲基銨、四乙基銨、四丁基銨等。該等之鹽中，更佳為銨鹽、鈉鹽及鉀鹽。 The counter ion of the water-soluble polymer having an anionic group is not particularly limited, and specific examples thereof include ions such as metal, ammonium, and alkylammonium. Specific examples of the metal include a periodic table (long-period type) 1A, 1B, 2A, 2B, 3A, 3B, and 4A. Metal of Group 6A, 7A or 8. Among these metals, from the viewpoint of surface roughness and scratch reduction, a metal belonging to Group 1A, 3B, or 8 is preferable, and sodium and potassium belonging to Group 1A are more preferable. Specific examples of the alkylammonium include tetramethylammonium, tetraethylammonium, and tetrabutylammonium. Among these salts, ammonium salts, sodium salts and potassium salts are more preferred.

就減少刮痕及粒子以及維持生產性之觀點而言，陰離子性水溶性高分子之重量平均分子量較佳為500以上且10萬以下，更佳為500以上且5萬以下，進而較佳為500以上且2萬以下，進而更佳為1000以上且1萬以下，進而更佳為1000以上且8000以下，進而更佳為1000以上且5000以下，進而更佳為1000以上且4000以下，進而更佳為1000以上且3000以下。具體而言，該重量平均分子量係藉由實施例中記載之測定方法而測定。 The weight average molecular weight of the anionic water-soluble polymer is preferably 500 or more and 100,000 or less, more preferably 500 or more and 50,000 or less, and further preferably 500, from the viewpoint of reducing scratches and particles and maintaining productivity. More preferably, it is 20,000 or less, more preferably 1,000 or more and 10,000 or less, still more preferably 1,000 or more and 8,000 or less, still more preferably 1,000 or more and 5,000 or less, still more preferably 1,000 or more and 4,000 or less, and still more preferably 1,000 or more. It is 1000 or more and 3000 or less. Specifically, the weight average molecular weight is measured by the measurement method described in the examples.

就同時實現刮痕及粒子之減少與生產性之觀點而言，研磨液組合物中之陰離子性水溶性高分子之含量較佳為0.001~1質量%，更佳為0.005~0.5質量%，進而較佳為0.08~0.2質量%，進而更佳為0.01~0.1質量%，進而更佳為0.01~0.075質量%。 The content of the anionic water-soluble polymer in the polishing composition is preferably from 0.001 to 1% by mass, more preferably from 0.005 to 0.5% by mass, from the viewpoint of simultaneously achieving reduction of scratches and particles and productivity. It is preferably 0.08 to 0.2% by mass, more preferably 0.01 to 0.1% by mass, still more preferably 0.01 to 0.075% by mass.

[脂肪族胺化合物或脂環式胺化合物] [aliphatic amine compound or alicyclic amine compound]

就減少研磨後之基板表面之刮痕及粒子之觀點而言，較佳為對被研磨物進行研磨時之研磨液組合物含有脂肪族胺化合物或脂環式胺化合物。關於上述脂肪族胺化合物或脂環式胺化合物，就減少研磨後之基板表面之刮痕及粒子之觀點而言，較佳為分子內之氮原子數為2個以上。又，就維持研磨速度之觀點而言，上述脂肪族胺化合物或脂環式胺化合物之分子內之氮原子數較佳為4個以下，更佳為3個以下，進而較佳為2個以下。因此，就維持研磨速度、以及減少刮痕及粒子之觀點而言，上述脂肪族胺化合物或脂環式胺化合物之分子內之氮原子數較佳為2~4個，更佳為2~3個，進而較佳為2個。 From the viewpoint of reducing scratches and particles on the surface of the substrate after polishing, it is preferred that the polishing composition for polishing the object to be polished contains an aliphatic amine compound or an alicyclic amine compound. The aliphatic amine compound or the alicyclic amine compound preferably has two or more nitrogen atoms in the molecule from the viewpoint of reducing scratches and particles on the surface of the substrate after polishing. In addition, the number of nitrogen atoms in the molecule of the aliphatic amine compound or the alicyclic amine compound is preferably 4 or less, more preferably 3 or less, still more preferably 2 or less, from the viewpoint of maintaining the polishing rate. . Therefore, the number of nitrogen atoms in the molecule of the aliphatic amine compound or the alicyclic amine compound is preferably 2 to 4, more preferably 2 to 3, from the viewpoint of maintaining the polishing rate and reducing scratches and particles. Further, it is preferably two.

作為上述脂肪族胺化合物，就減少研磨後之基板表面之刮痕及 粒子之觀點而言，較佳為選自由乙二胺、N,N,N',N'-四甲基乙二胺、1,2-二胺基丙烷、1,3-二胺基丙烷、1,4-二胺基丁烷、六亞甲基二胺、3-(二乙基胺基)丙基胺、3-(二丁基胺基)丙基胺、3-(甲基胺基)丙基胺、3-(二甲基胺基)丙基胺、N-胺基乙基乙醇胺、N-胺基乙基異丙醇胺、N-胺基乙基-N-甲基乙醇胺、二乙三胺、及三乙四胺所組成之群，更佳為選自由乙二胺、N,N,N',N'-四甲基乙二胺、1,2-二胺基丙烷、1,3-二胺基丙烷、1,4-二胺基丁烷、六亞甲基二胺、3-(二乙基胺基)丙基胺、3-(二丁基胺基)丙基胺、3-(甲基胺基)丙基胺、3-(二甲基胺基)丙基胺、N-胺基乙基乙醇胺、N-胺基乙基異丙醇胺、及N-胺基乙基-N-甲基乙醇胺所組成之群，進而就減少胺臭、提高於水中之溶解性之觀點而言，進而較佳為選自由N-胺基乙基乙醇胺、N-胺基乙基異丙醇胺、N-胺基乙基-N-甲基乙醇胺所組成之群，進而更佳為N-胺基乙基乙醇胺。 As the above aliphatic amine compound, the scratch on the surface of the substrate after polishing is reduced and From the viewpoint of particles, it is preferably selected from the group consisting of ethylenediamine, N,N,N',N'-tetramethylethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-Diaminobutane, hexamethylenediamine, 3-(diethylamino)propylamine, 3-(dibutylamino)propylamine, 3-(methylamino group Propylamine, 3-(dimethylamino)propylamine, N-aminoethylethanolamine, N-aminoethylisopropanolamine, N-aminoethyl-N-methylethanolamine, More preferably, the group consisting of diethylenetriamine and triethylenetetramine is selected from the group consisting of ethylenediamine, N,N,N',N'-tetramethylethylenediamine, 1,2-diaminopropane, 1,3-Diaminopropane, 1,4-diaminobutane, hexamethylenediamine, 3-(diethylamino)propylamine, 3-(dibutylamino)propyl Amine, 3-(methylamino)propylamine, 3-(dimethylamino)propylamine, N-aminoethylethanolamine, N-aminoethylisopropanolamine, and N-amine The group consisting of ethyl ethyl-N-methylethanolamine further preferably is selected from the group consisting of N-aminoethylethanolamine and N-amino group B from the viewpoint of reducing amine odor and improving solubility in water. Isopropanolamine, N-aminoethyl-N-methylethanolamine The group, and more preferably the N-aminoethylethanolamine.

作為上述脂環式胺化合物，就減少研磨後之基板表面之刮痕及粒子之觀點而言，較佳為選自由哌、2-甲基哌、2,5-二甲基哌、1-胺基-4-甲基哌、N-甲基哌、1-(2-胺基乙基)哌及羥基乙基哌所組成之群，更佳為選自由哌、2-甲基哌、2,5-二甲基哌、N-甲基哌及羥基乙基哌所組成之群，進而較佳為選自由哌、N-(2-胺基乙基)哌及羥基乙基哌所組成之群，進而更佳為選自由N-(2-胺基乙基)哌及羥基乙基哌所組成之群。 The alicyclic amine compound is preferably selected from the viewpoint of reducing scratches and particles on the surface of the substrate after polishing. 2-methylperazine 2,5-Dimethyl pipe 1-amino-4-methylper N-methylperazine 1-(2-aminoethyl)per Hydroxyethylpipe More preferably selected from the group 2-methylperazine 2,5-Dimethyl pipe N-methylperazine Hydroxyethylpipe The group consisting of, preferably, selected from the group N-(2-Aminoethyl) piperidine Hydroxyethylpipe The group formed, and more preferably selected from N-(2-aminoethyl)peri Hydroxyethylpipe The group formed.

因此，就減少研磨後之基板表面之刮痕及粒子、減少胺臭、提高於水中之溶解性之觀點而言，研磨液組合物所使用之脂肪族胺化合物或脂環式胺化合物進而更佳為選自由N-胺基乙基乙醇胺、N-胺基乙基異丙醇胺、N-胺基乙基-N-甲基乙醇胺、哌、N-(2-胺基乙基)哌及羥基乙基哌所組成之群，進而更佳為選自由N-胺基乙基乙醇胺、N-(2-胺基乙基)哌及羥基乙基哌所組成之群，進而更佳為N-胺基 乙基乙醇胺。 Therefore, the aliphatic amine compound or the alicyclic amine compound used in the polishing composition is further improved from the viewpoint of reducing scratches and particles on the surface of the substrate after polishing, reducing amine odor, and improving solubility in water. Is selected from N-aminoethylethanolamine, N-aminoethylisopropanolamine, N-aminoethyl-N-methylethanolamine, piperazine N-(2-Aminoethyl) piperidine Hydroxyethylpipe The group formed, and more preferably selected from the group consisting of N-aminoethylethanolamine, N-(2-aminoethyl)perazine Hydroxyethylpipe The group formed is more preferably N-aminoethylethanolamine.

就減少研磨後之基板表面之刮痕及粒子之觀點而言，上述研磨液組合物中之脂肪族胺化合物或脂環式胺化合物之含量相對於研磨液組合物整體之質量，較佳為0.001~10質量%，更佳為0.005~5質量%，進而較佳為0.008~2質量%，進而更佳為0.01~1質量%，進而更佳為0.01~0.5質量%，進而更佳為0.01~0.1質量%。再者，研磨液組合物中之脂肪族胺化合物或脂環式胺化合物可為1種，亦可為2種以上。 The content of the aliphatic amine compound or the alicyclic amine compound in the polishing liquid composition is preferably 0.001 based on the mass of the entire polishing liquid composition, from the viewpoint of reducing scratches and particles on the surface of the substrate after polishing. ~10% by mass, more preferably 0.005 to 5% by mass, still more preferably 0.008 to 2% by mass, still more preferably 0.01 to 1% by mass, still more preferably 0.01 to 0.5% by mass, still more preferably 0.01% 0.1% by mass. In addition, the aliphatic amine compound or the alicyclic amine compound in the polishing composition may be one type or two or more types.

[研磨方法] [grinding method]

藉由本揭示之研磨液組合物之製造方法所獲得之研磨液組合物例如被供給至不織布之有機高分子系研磨布等(研磨墊)與被研磨基板之間、即研磨液組合物被供給至被貼附有研磨墊之研磨盤所夾入之基板研磨面，於特定壓力下移動研磨盤及/或基板，藉此一面與基板接觸一面用於研磨步驟。藉由該研磨可顯著抑制刮痕及粒子之產生。因此，本揭示於另一態樣中係關於一種基板之研磨方法，其係基板之研磨方法，並且包括將本揭示之研磨液組合物供給至被研磨基板之研磨對象面，使研磨墊與上述研磨對象面接觸，移動上述研磨墊及/或上述被研磨基板而進行研磨。 The polishing liquid composition obtained by the method for producing a polishing liquid composition of the present invention is supplied, for example, to a non-woven organic polymer-based polishing cloth or the like (polishing pad) and a substrate to be polished, that is, a polishing liquid composition is supplied thereto. The polishing surface of the substrate sandwiched by the polishing pad to which the polishing pad is attached moves the polishing disk and/or the substrate under a specific pressure, thereby being used for the polishing step while being in contact with the substrate. The scratching and the generation of particles can be remarkably suppressed by the grinding. Therefore, in another aspect, the present disclosure relates to a method of polishing a substrate, which is a method for polishing a substrate, and includes supplying the polishing composition of the present disclosure to a polishing target surface of the substrate to be polished, and the polishing pad and the above The polishing target is in surface contact, and the polishing pad and/or the substrate to be polished are moved to be polished.

上述研磨液組合物尤其適合於精密零件用基板之製造。例如適合於磁碟、磁光碟等磁性記錄媒體之基板、光碟、光罩基板、光學透鏡、光學反射鏡、光學稜鏡、半導體基板等精密零件基板之研磨。於半導體基板之製造中，於矽晶圓(裸晶圓)之拋光步驟、嵌入元件隔離膜之形成步驟、層間絕緣膜之平坦化步驟、埋入金屬配線之形成步驟、嵌入電容器形成步驟等中，可使用利用本揭示之研磨液組合物之製造方法所獲得之研磨液組合物。 The above polishing liquid composition is particularly suitable for the production of a substrate for precision parts. For example, it is suitable for polishing a substrate of a magnetic recording medium such as a magnetic disk or a magneto-optical disk, a precision component substrate such as an optical disk, a photomask substrate, an optical lens, an optical mirror, an optical ray, or a semiconductor substrate. In the manufacture of a semiconductor substrate, a polishing step of a germanium wafer (bare wafer), a step of forming an embedded element isolation film, a planarization step of an interlayer insulating film, a step of forming a buried metal wiring, an insertion capacitor forming step, and the like A polishing liquid composition obtained by the production method of the polishing liquid composition of the present disclosure can be used.

本揭示之研磨液組合物於拋光步驟中尤其有效，但亦可同樣地 應用於其以外之研磨步驟、例如磨削步驟等。 The polishing liquid composition of the present disclosure is particularly effective in the polishing step, but can be similarly It is applied to a grinding step other than the grinding step, such as a grinding step.

作為使用本揭示之研磨液組合物的適宜之被研磨物之材質，例如可列舉：矽、鋁、鎳、鎢、銅、鉭、鈦等金屬或者半金屬、或該等之合金、玻璃、玻璃狀碳、非晶形碳等玻璃狀物質、氧化鋁、二氧化矽、氮化矽、氮化鉭、碳化鈦等陶瓷材料、聚醯亞胺樹脂等樹脂等。該等之中，適宜為含有鋁、鎳、鎢、銅等金屬及以該等金屬為主成分之合金之被研磨物。例如更適合為鍍Ni-P之鋁合金基板或結晶化玻璃、強化玻璃等玻璃基板，進而適合為鍍Ni-P之鋁合金基板。 Examples of a material of the workpiece to be polished using the polishing composition of the present invention include metals such as ruthenium, aluminum, nickel, tungsten, copper, rhenium, and titanium, or semimetals, or alloys thereof, glass, and glass. A glassy substance such as carbon or amorphous carbon, a ceramic material such as alumina, ceria, tantalum nitride, tantalum nitride or titanium carbide, or a resin such as a polyimide resin. Among these, a material to be polished containing a metal such as aluminum, nickel, tungsten or copper and an alloy containing the metal as a main component is suitable. For example, it is more suitably a Ni-P-plated aluminum alloy substrate, a glass substrate such as crystallized glass or tempered glass, and further preferably a Ni-P-plated aluminum alloy substrate.

被研磨物之形狀並無特別限制，例如對碟狀、板狀、塊狀、角柱狀等具有平面部之形狀、或透鏡等具有曲面部之形狀者使用本揭示之研磨液組合物。其中，對碟狀之被研磨物之研磨優異。 The shape of the object to be polished is not particularly limited. For example, the polishing liquid composition of the present disclosure is used for a shape having a flat portion such as a disk shape, a plate shape, a block shape, or a prismatic shape, or a shape having a curved surface portion such as a lens. Among them, the polishing of the dish-shaped object to be polished is excellent.

[磁碟基板之製造方法] [Method of Manufacturing Disk Substrate]

因此，本揭示於另一態樣中係關於一種磁碟基板之製造方法，其包括將藉由本揭示之研磨液組合物之製造方法所獲得之研磨液組合物供給至被研磨基板之研磨對象面，藉此對上述研磨對象面進行研磨之步驟。又，本揭示於另一態樣中係關於一種磁碟基板之製造方法，其包括藉由本揭示之研磨液組合物之製造方法而製造研磨液組合物，及將上述研磨液組合物供給至被研磨基板之研磨對象面，並使研磨墊與上述研磨對象面接觸，移動上述研磨墊及/或上述被研磨基板，而對上述研磨對象面進行研磨。 Therefore, the present disclosure relates to a method of manufacturing a magnetic disk substrate, which comprises supplying a polishing liquid composition obtained by the method for producing a polishing liquid composition of the present invention to a polishing target surface of a substrate to be polished. Thereby, the step of polishing the surface of the polishing target is performed. Further, in another aspect, the present invention relates to a method for producing a magnetic disk substrate, comprising: manufacturing a polishing liquid composition by the method for producing a polishing liquid composition of the present invention, and supplying the polishing liquid composition to a The polishing target surface of the substrate is polished, and the polishing pad is brought into surface contact with the polishing target surface to move the polishing pad and/or the substrate to be polished, and the polishing target surface is polished.

關於上述實施形態，本揭示進而揭示以下之組合物、製造方法、或者用途。 In the above embodiment, the present disclosure further discloses the following composition, production method, or use.

<1>一種研磨液組合物之製造方法，其包括利用包含過濾助劑之過濾器對含有膠體二氧化矽之被處理二氧化矽分散液進行過濾處理之步驟，上述膠體二氧化矽之藉由滴定法所求得之一次粒子之平均粒徑 為1nm以上且50nm以下，上述過濾助劑之羥基密度為0.40×10-5mol/m2以上。 <1> A method for producing a polishing composition comprising the step of filtering a treated ceria dispersion containing colloidal cerium oxide by a filter comprising a filter aid, wherein the colloidal cerium oxide is used The average particle diameter of the primary particles obtained by the titration method is 1 nm or more and 50 nm or less, and the hydroxyl density of the above filter aid is 0.40 × 10 -5 mol/m 2 or more.

<2>如<1>之研磨液組合物之製造方法，其中上述膠體二氧化矽之藉由滴定法所求得之一次粒子之平均粒徑較佳為5.0nm以上，更佳為10.0nm以上，進而較佳為12.0nm以上，且較佳為45nm以下，更佳為42nm以下，進而較佳為40nm以下。 <2> The method for producing a polishing composition according to <1>, wherein the average particle diameter of the primary particles obtained by the titration method of the colloidal ceria is preferably 5.0 nm or more, more preferably 10.0 nm or more. Further, it is preferably 12.0 nm or more, and is preferably 45 nm or less, more preferably 42 nm or less, still more preferably 40 nm or less.

<3>如<1>或<2>之研磨液組合物之製造方法，其中上述過濾助劑較佳為矽藻土之羥基密度較佳為0.41×10-5mol/m2以上，更佳為0.43×10-5mol/m2以上，且較佳為2.0×10-5mol/m2以下，更佳為1.5×10-5mol/m2以下。 <3> The method for producing a polishing composition according to <1> or <2>, wherein the filter aid is preferably a diatomaceous earth having a hydroxyl group density of preferably 0.41 × 10 -5 mol/m 2 or more, more preferably It is 0.43 × 10 -5 mol/m 2 or more, and preferably 2.0 × 10 -5 mol / m 2 or less, more preferably 1.5 × 10 -5 mol / m 2 or less.

<4>如<1>至<3>中任一項記載之研磨液組合物之製造方法，其中上述過濾助劑係藉由將上述羥基密度未達0.40×10-5mol/m2之矽藻土與酸水溶液進行混合後，對上述矽藻土進行脫酸處理而獲得。 The method for producing a polishing composition according to any one of the above aspects, wherein the filter aid is obtained by using the hydroxyl group having a density of less than 0.40 × 10 -5 mol/m 2 After the algae soil is mixed with the aqueous acid solution, the diatomaceous earth is subjected to deacidification treatment.

<5>如<4>記載之研磨液組合物之製造方法，其中上述酸水溶液中所含之酸較佳為選自由鹽酸、硝酸、磷酸、1-羥基亞乙基-1,1-二膦酸等膦酸、次膦酸、pKa未達4之有機酸所組成之群中之至少1種，更佳為選自由鹽酸、硝酸、磷酸、膦酸、次膦酸、及pKa未達3.5之有機酸所組成之群中之至少1種，進而較佳為選自由硝酸、磷酸、膦酸、次膦酸、及pKa 3.1以下之有機酸所組成之群中之至少1種，進而更佳為選自由膦酸、及次膦酸所組成之群中之至少1種。 <5> The method for producing a polishing composition according to <4>, wherein the acid contained in the aqueous acid solution is preferably selected from the group consisting of hydrochloric acid, nitric acid, phosphoric acid, and 1-hydroxyethylidene-1,1-diphosphine. At least one of a group consisting of a phosphonic acid such as an acid, a phosphinic acid, and an organic acid having a pKa of less than 4, more preferably selected from the group consisting of hydrochloric acid, nitric acid, phosphoric acid, phosphonic acid, phosphinic acid, and pKa not up to 3.5. At least one selected from the group consisting of organic acids, more preferably at least one selected from the group consisting of nitric acid, phosphoric acid, phosphonic acid, phosphinic acid, and an organic acid having a pKa of 3.1 or less, and more preferably At least one selected from the group consisting of phosphonic acid and phosphinic acid is selected.

<6>如<1>至<5>中任一項記載之研磨液組合物之製造方法，其中上述膠體二氧化矽之藉由滴定法所求得之一次粒子之平均粒徑與上述過濾助劑之藉由雷射式粒度分佈測定裝置所測得之平均粒徑的比(膠體二氧化矽之藉由滴定法所測得之一次粒子之平均粒徑/過濾助劑之藉由雷射式粒度分佈測定裝置所測得之平均粒徑)較佳為 1.20×10-3以上，更佳為1.35×10-3以上，進而較佳為1.40×10-3以上，進而更佳為1.42×10-3以上，且較佳為4.20×10-3以下，更佳為3.80×10-3以下，進而較佳為3.00×10-3以下，進而更佳為2.50×10-3以下，進而更佳為2.00×10-3以下，進而更佳為1.50×10-3以下。 The method for producing a polishing liquid composition according to any one of the above aspects, wherein the average particle diameter of the primary particles obtained by the titration method of the colloidal cerium oxide and the filtration aid are as described above. Ratio of average particle size measured by a laser particle size distribution analyzer (average particle size of primary particles measured by titration of colloidal ceria/laser aid by laser type) The average particle diameter measured by the particle size distribution measuring device is preferably 1.20 × 10 -3 or more, more preferably 1.35 × 10 -3 or more, still more preferably 1.40 × 10 -3 or more, and still more preferably 1.42 × 10 -3 or more, and preferably 4.20 × 10 -3 or less, more preferably 3.80 × 10 -3 or less, still more preferably 3.00 × 10 -3 or less, still more preferably 2.50 × 10 -3 or less, and still more preferably It is 2.00 × 10 -3 or less, and more preferably 1.50 × 10 -3 or less.

<7>如<1>至<6>中任一項記載之研磨液組合物之製造方法，其中上述過濾助劑CV值較佳為70%以上，更佳為75%以上，進而較佳為80%以上，進而更佳為85%以上，且較佳為100%以下，更佳為99%以下。 The method for producing a polishing composition according to any one of the above aspects, wherein the filter aid CV value is preferably 70% or more, more preferably 75% or more, and still more preferably It is 80% or more, more preferably 85% or more, and is preferably 100% or less, more preferably 99% or less.

<8>如<1>至<7>中任一項記載之研磨液組合物之製造方法，其中上述過濾助劑之藉由雷射式粒度分佈測定裝置所測得之平均粒徑較佳為0.5μm以上，更佳為1μm以上，進而較佳為4.5μm以上，進而更佳為8μm以上，進而更佳為10μm以上，且較佳為100μm以下，更佳為60μm以下，進而較佳為50μm以下，進而更佳為40μm以下，進而更佳為20μm以下，進而更佳為13μm以下。 The method for producing a polishing composition according to any one of the above aspects, wherein the average particle diameter of the filter aid measured by a laser particle size distribution analyzer is preferably 0.5 μm or more, more preferably 1 μm or more, further preferably 4.5 μm or more, further preferably 8 μm or more, further preferably 10 μm or more, and more preferably 100 μm or less, more preferably 60 μm or less, further preferably 50 μm. Hereinafter, it is more preferably 40 μm or less, further preferably 20 μm or less, and still more preferably 13 μm or less.

<9>如<1>至<8>中任一項記載之研磨液組合物之製造方法，其中上述過濾助劑之藉由水銀壓入法所獲得之平均孔徑較佳為0.1~3.5μm，更佳為0.1~3.0μm，進而較佳為0.1~2.7μm，進而更佳為0.1~2.6μm。 The method for producing a polishing composition according to any one of the above aspects, wherein the filter aid has an average pore diameter of from 0.1 to 3.5 μm obtained by a mercury intrusion method. More preferably, it is 0.1 to 3.0 μm, further preferably 0.1 to 2.7 μm, and still more preferably 0.1 to 2.6 μm.

<10>如<1>至<9>中任一項記載之研磨液組合物之製造方法，其中上述過濾助劑之藉由氮吸附法所獲得之孔徑0.15μm以下之累計孔隙體積較佳為0.3mL/g以上，更佳為0.4mL/g以上，進而較佳為0.6mL/g以上，且較佳為100.0mL/g以下，更佳為50.0mL/g以下，進而較佳為10.0mL/g以下。 The method for producing a polishing composition according to any one of the above aspects, wherein the cumulative pore volume of the filter aid obtained by a nitrogen adsorption method having a pore diameter of 0.15 μm or less is preferably 0.3 mL / g or more, more preferably 0.4 mL / g or more, further preferably 0.6 mL / g or more, and preferably 100.0 mL / g or less, more preferably 50.0 mL / g or less, further preferably 10.0 mL /g below.

<11>如<1>至<10>中任一項記載之研磨液組合物之製造方法，其中上述過濾助劑之藉由水銀壓入法所獲得之孔徑0.5μm以下之累計孔隙體積較佳為2.5mL/g以上，更佳為2.7mL/g以上，進而較佳 為3.0mL/g以上，進而更佳為4.0mL/g以上，進而更佳為4.5mL/g以上，且較佳為1000mL/g以下，更佳為100mL/g以下，進而較佳為50mL/g以下，進而更佳為20mL/g以下，進而更佳為10mL/g以下。 The method for producing a polishing composition according to any one of the above aspects, wherein the cumulative pore volume of the filter aid obtained by the mercury intrusion method having a pore diameter of 0.5 μm or less is preferably. It is preferably 2.5 mL/g or more, more preferably 2.7 mL/g or more, and further preferably It is 3.0 mL/g or more, more preferably 4.0 mL/g or more, further preferably 4.5 mL/g or more, and more preferably 1000 mL/g or less, more preferably 100 mL/g or less, further preferably 50 mL/ The amount of g or less is more preferably 20 mL/g or less, and still more preferably 10 mL/g or less.

<12>如<1>至<11>中任一項記載之研磨液組合物之製造方法，其中上述被處理二氧化矽分散液中之膠體二氧化矽之含量較佳為1質量%以上，更佳為10質量%以上，進而較佳為20質量%以上，進而更佳為30質量%以上，且較佳為50質量%以下，更佳為45質量%以下，進而較佳為43質量%以下，進而更佳為40質量%以下。 The method for producing a polishing liquid composition according to any one of the above aspects, wherein the content of the colloidal cerium oxide in the treated cerium oxide dispersion is preferably 1% by mass or more. It is more preferably 10% by mass or more, further preferably 20% by mass or more, further preferably 30% by mass or more, more preferably 50% by mass or less, still more preferably 45% by mass or less, and still more preferably 43% by mass. Hereinafter, it is more preferably 40% by mass or less.

<13>如<1>至<12>中任一項記載之研磨液組合物之製造方法，其中上述被處理二氧化矽分散液於25℃下之pH值較佳為8.5以上，更佳為8.8以上，進而較佳為9.0以上，且較佳為11以下，更佳為10.8以下，進而較佳為10.5以下。 The method for producing a polishing composition according to any one of the above aspects, wherein the pH of the treated ceria dispersion at 25 ° C is preferably 8.5 or more, more preferably 8.8 or more is further preferably 9.0 or more, and is preferably 11 or less, more preferably 10.8 or less, still more preferably 10.5 or less.

<14>如<1>至<13>中任一項記載之研磨液組合物之製造方法，其包括於包含酸、氧化劑及水之混合液中混合藉由對上述被處理二氧化矽分散液實施上述過濾處理而獲得之二氧化矽分散液之步驟。 The method for producing a polishing composition according to any one of the above aspects, comprising the mixing of the acid, the oxidizing agent and the water, and the mixing of the treated cerium oxide dispersion The step of carrying out the above-described filtration treatment to obtain a cerium oxide dispersion.

<15>一種研磨液組合物，其係藉由如<1>至<14>中任一項記載之研磨液組合物之製造方法而製造。 <15> A polishing liquid composition produced by the method for producing a polishing composition according to any one of <1> to <14>.

<16>如<15>記載之研磨液組合物，其進而含有具有陰離子性基之水溶性高分子、雜環芳香族化合物、及脂肪族胺化合物或脂環式胺化合物。 <16> The polishing liquid composition according to <15>, which further comprises a water-soluble polymer having an anionic group, a heterocyclic aromatic compound, an aliphatic amine compound or an alicyclic amine compound.

<17>一種磁碟基板之製造方法，其包括將藉由如<1>至<14>中任一項記載之研磨液組合物之製造方法所獲得之研磨液組合物供給至被研磨基板之研磨對象面，藉此對上述研磨對象面進行研磨之步驟。 <17> A method of producing a disk substrate, comprising: supplying the polishing liquid composition obtained by the method for producing a polishing composition according to any one of <1> to <14> to a substrate to be polished The step of polishing the surface of the object to be polished by polishing the surface of the object to be polished.

<18>如上述<17>記載之磁碟基板之製造方法，其包括藉由上述研磨液組合物之製造方法而製造研磨液組合物，及將上述研磨液 組合物供給至被研磨基板之研磨對象面，並使研磨墊與上述研磨對象面接觸，移動上述研磨墊及/或上述被研磨基板，而對上述研磨對象面進行研磨。 <18> The method for producing a magnetic disk substrate according to the above <17>, comprising: the polishing liquid composition produced by the method for producing the polishing liquid composition, and the polishing liquid The composition is supplied to the polishing target surface of the substrate to be polished, and the polishing pad is brought into surface contact with the polishing target surface to move the polishing pad and/or the substrate to be polished, and the polishing target surface is polished.

<19>一種過濾助劑，其係用於如<1>至<14>中任一項記載之研磨液組合物之製造方法者，並且包含羥基密度為0.40×10-5mol/m2以上、較佳為0.41×10-5mol/m2以上、更佳為0.43×10-5mol/m2以上，且較佳為2.0×10-5mol/m2以下，更佳為1.5×10-5mol/m2以下之矽藻土。 <19> A filter aid for use in a method for producing a polishing composition according to any one of <1> to <14>, which comprises a hydroxyl group having a density of 0.40×10 -5 mol/m 2 or more. Preferably, it is 0.41 × 10 -5 mol / m 2 or more, more preferably 0.43 × 10 -5 mol / m 2 or more, and preferably 2.0 × 10 -5 mol / m 2 or less, more preferably 1.5 × 10 - 5 mol/m 2 or less of diatomaceous earth.

<20>一種過濾助劑之製造方法，其係上述<19>記載之過濾助劑之製造方法，並且包括將羥基密度未達0.40×10-5mol/m2之矽藻土與酸水溶液進行混合後，對上述矽藻土進行脫酸處理之步驟。 <20> A method for producing a filter aid according to the above <19>, which comprises the method of producing a diatomaceous earth having a hydroxyl group density of less than 0.40 × 10 -5 mol/m 2 and an aqueous acid solution; After mixing, the above-mentioned diatomaceous earth is subjected to a step of deacidification treatment.

[實施例] [Examples]

以下，藉由實施例更詳細地說明本揭示，但該等係例示，本揭示不受該等實施例所限制。 In the following, the present disclosure will be described in more detail by way of examples, but these are exemplified, and the present disclosure is not limited by the embodiments.

[被處理二氧化矽分散液] [Processed cerium oxide dispersion]

作為被處理二氧化矽分散液，使用膠體二氧化矽漿料a(pH值9.0，日揮觸媒化成公司製造，一次粒子之平均粒徑18.0nm，二氧化矽粒子濃度40質量%)、膠體二氧化矽漿料b(pH值10.0，日揮觸媒化成公司製造，一次粒子之平均粒徑50.0nm，二氧化矽粒子濃度40質量%)、及膠體二氧化矽漿料c(pH值10.0，日揮觸媒化成公司製造，一次粒子之平均粒徑100.0nm，二氧化矽粒子濃度40質量%)(表1)。被處理二氧化矽分散液及研磨液組合物中之膠體二氧化矽之一次粒子之平均粒徑、0.45μm過濾器液體透過量係藉由以下方式測定。 As the treated cerium oxide dispersion, a colloidal cerium oxide slurry a (pH 9.0, manufactured by Nissin Chemical Co., Ltd., average particle diameter of primary particles of 18.0 nm, concentration of cerium oxide particles of 40% by mass), colloidal Cerium oxide slurry b (pH 10.0, manufactured by Nissan Catalyst Co., Ltd., average particle size of primary particles 50.0 nm, concentration of ceria particles 40% by mass), and colloidal ceria slurry c (pH 10.0, daily wave) It was manufactured by Catalyst Chemical Co., Ltd., and the average particle diameter of primary particles was 100.0 nm, and the concentration of cerium oxide particles was 40% by mass) (Table 1). The average particle diameter of the primary particles of the colloidal cerium oxide and the 0.45 μm filter liquid permeation amount in the treated cerium oxide dispersion liquid and the polishing liquid composition were measured by the following methods.

[膠體二氧化矽之一次粒子之平均粒徑之測定方法] [Method for determination of average particle size of primary particles of colloidal cerium oxide]

首先，採取以固形物成分計為1.5g份之膠體二氧化矽漿料置於 200mL燒杯內，並添加離子交換水100mL，利用攪拌器混合該等，而獲得混合液。其次，使用電位差滴定裝置，利用0.1mol/L之鹽酸標準溶液將混合液之pH值調整為3.0。於pH值經調整之混合液中，添加氯化鈉30.0g，利用攪拌器將其溶解，進而添加離子交換水，直至達到燒杯之150mL之標線，利用攪拌器混合。將所獲得之試樣液浸漬於恆溫水槽(20±2℃)內約30分鐘。使用電位差滴定裝置，利用0.1mol/L之氫氧化鈉標準溶液進行滴定，讀取試樣液之pH值自4.0變為9.0時所使用之氫氧化鈉標準溶液之量(g)(A)。另一方面，不將膠體二氧化矽漿料放入至200mL燒杯內，進行空白試驗，讀取空白試驗之滴定所需要之氫氧化鈉標準溶液之量(g)(B)。然後，根據下述計算式而算出平均粒徑(nm)。 First, a 1.5 g portion of a colloidal cerium oxide slurry in a solid content is placed. In a 200 mL beaker, 100 mL of ion-exchanged water was added, and the mixture was mixed with a stirrer to obtain a mixed solution. Next, the pH of the mixture was adjusted to 3.0 using a potential difference titration apparatus using a 0.1 mol/L hydrochloric acid standard solution. To the pH-adjusted mixture, 30.0 g of sodium chloride was added, and the mixture was dissolved by a stirrer, and ion-exchanged water was further added until a 150 mL mark of the beaker was reached, and the mixture was mixed by a stirrer. The obtained sample liquid was immersed in a constant temperature water bath (20 ± 2 ° C) for about 30 minutes. The potentiometric titration apparatus was used to titrate with a 0.1 mol/L sodium hydroxide standard solution, and the amount (g) (A) of the sodium hydroxide standard solution used when the pH of the sample liquid was changed from 4.0 to 9.0 was read. On the other hand, the colloidal cerium oxide slurry was not placed in a 200 mL beaker, and a blank test was performed to read the amount (g) (B) of the sodium hydroxide standard solution required for the titration of the blank test. Then, the average particle diameter (nm) was calculated according to the following calculation formula.

平均粒徑(nm)=3100÷26.5×(A-B)÷試樣採取量(g) Average particle size (nm) = 3100 ÷ 26.5 × (A-B) ÷ sample taken amount (g)

試樣採取量：膠體二氧化矽漿料固形物成分1.5g Sample taken amount: colloidal cerium oxide slurry solid content 1.5g

[含過濾助劑之過濾器] [Filter containing filter aid]

使用下述市售之過濾助劑A~C(參照下述表2)，如下所述製作含過濾助劑之過濾器。藉由下述方法，求出過濾助劑A~C及對過濾助劑A~C進行熱處理或酸處理而獲得之過濾助劑1~16之雷射平均粒徑、CV值、累計孔隙體積、過濾助劑之羥基密度。將過濾助劑A~C之上述參數示於表2。過濾助劑1~16之上述參數中，雷射平均粒徑、CV值、累計孔隙體積、平均孔徑分別與藉由酸水溶液等進行處理前 之過濾助劑之值相同。將過濾助劑A~C、及過濾助劑1~16之羥基密度分別示於表2、表4~表7。表2中之平均孔徑為目錄值。 A filter containing a filter aid was prepared as follows using the following commercially available filter aids A to C (see Table 2 below). The laser averaging particle size, CV value, cumulative pore volume of the filter aids 1 to 16 obtained by heat treatment or acid treatment of the filter aids A to C and the filter aids A to C are determined by the following methods. The hydroxyl density of the filter aid. The above parameters of the filter aids A to C are shown in Table 2. Among the above parameters of the filter aids 1 to 16, the laser average particle diameter, the CV value, the cumulative pore volume, and the average pore diameter are respectively treated with an aqueous acid solution or the like. The value of the filter aid is the same. The hydroxyl densities of the filter aids A to C and the filter aids 1 to 16 are shown in Table 2 and Table 4 to Table 7, respectively. The average pore diameter in Table 2 is the catalog value.

[過濾助劑之雷射平均粒徑之測定方法] [Method for Measuring Laser Average Particle Diameter of Filtration Aid]

針對各過濾助劑，將利用雷射繞射/散射式粒度分佈計(商品名LA-920，堀場製作所製造)所測得之體積基準之中值粒徑之值設為雷射平均粒徑。 For each of the filter aids, the value of the volume-based median diameter measured by a laser diffraction/scattering particle size distribution meter (trade name: LA-920, manufactured by Horiba, Ltd.) was used as the laser average particle diameter.

[過濾助劑之CV值之測定方法] [Method for measuring CV value of filter aid]

將利用雷射繞射/散射式粒度分佈計(商品名LA-920，堀場製作所製造)對各過濾助劑進行測定而獲得之算術標準偏差除以體積基準之中值粒徑之值而獲得之值之比率設為CV值(%)。 The arithmetic standard deviation obtained by measuring each filter aid by a laser diffraction/scattering particle size distribution meter (trade name: LA-920, manufactured by Horiba, Ltd.) is divided by the value of the volume-based median diameter. The ratio of values is set to the CV value (%).

[0.15μm以下之累計孔隙體積之測定方法] [Method for measuring cumulative pore volume below 0.15 μm]

過濾助劑之孔徑0.15μm以下之累計孔隙體積係藉由氮吸附法進行測定。具體而言，將精確稱量之約1g之各過濾助劑置於ASAP2020(島津製作所股份有限公司製造，比表面積、孔分佈測定裝置)中，將根據氮吸附等溫線藉由BJH(Barrett-Joyner-Halenda)法之Halsey式所求得之孔徑為0.15μm以下之孔隙體積之總和設為0.15μm以下之累計孔隙體積。再者，試樣之預處理係藉由如下方式進行：將試樣放入至焙燒爐(MOTOYAMA股份有限公司製造，商品名：SK-2535E)內，使焙燒爐之溫度以10℃/分鐘升溫至100℃，其後於100℃下保持2小時。又，於60℃之時間點，於焙燒爐內，以其壓力成為500μmHg之方式進行脫氣。 The cumulative pore volume of the filter aid having a pore diameter of 0.15 μm or less is measured by a nitrogen adsorption method. Specifically, about 1 g of each of the filter aids accurately weighed is placed in ASAP2020 (manufactured by Shimadzu Corporation, specific surface area, pore distribution measuring device), and will be based on nitrogen adsorption isotherms by BJH (Barrett- The sum of the pore volumes having a pore diameter of 0.15 μm or less as determined by the Halsey formula of the Joyner-Halenda method is set to a cumulative pore volume of 0.15 μm or less. Further, the pretreatment of the sample was carried out by placing the sample in a baking furnace (manufactured by MOTOYAMA Co., Ltd., trade name: SK-2535E) to raise the temperature of the baking furnace at 10 ° C / min. It was kept at 100 ° C for 2 hours at 100 ° C. Further, at 60 ° C, degassing was carried out in a calciner so that the pressure became 500 μmHg.

[0.5μm以下之累計孔隙體積之測定方法] [Method for measuring cumulative pore volume below 0.5 μm]

利用天秤精確稱量約0.1~0.3g之各過濾助劑，以不附著於管內或印刷部之方式將其放入至利用己烷充分清洗之5cc粉末用測定單元，將單元置於AutoPoreIV-9500(島津製作所公司製造水銀壓入法孔分佈測定裝置)中。其次，利用個人電腦啟動應用程式(AutoPoreIV- 9500 ver1.07)，對樣品資訊(先前測定之過濾助劑之重量)、分析條件(選擇標準)、穿透計特性(單元重量)、報告條件(選擇標準)輸入必要事項，進行測定。按照低壓部、高壓部之順序進行測定，自動獲得針對中值孔徑(體積)(μm)與各孔徑(μm)之Log差分孔隙體積(mL/g)之結果。 Weigh accurately about 0.1 to 0.3 g of each filter aid using Libra, and put it into the measuring unit of 5 cc powder which is sufficiently washed with hexane without attaching it to the inside of the tube or the printing part, and place the unit in AutoPoreIV- 9500 (made by Shimadzu Corporation, a mercury intrusion method). Second, use the PC to launch the application (AutoPoreIV- 9500 ver1.07), the sample information (weight of the previously determined filter aid), analysis conditions (selection criteria), penetrometer characteristics (unit weight), and report conditions (selection criteria) are input and necessary for measurement. The measurement was performed in the order of the low pressure portion and the high pressure portion, and the results of the Log differential pore volume (mL/g) for the median pore diameter (volume) (μm) and each pore diameter (μm) were automatically obtained.

(1)測定條件 (1) Measurement conditions

測定單元：Micromeritics公司製造之5cc-Powder(08-0444)) Measuring unit: 5cc-Powder (08-0444) manufactured by Micromeritics

測定方式：壓力控制方式(壓力錶模式) Measuring method: pressure control mode (pressure gauge mode)

低壓平衡時間5秒， Low pressure balance time 5 seconds,

高壓平衡時間5秒， High pressure balance time 5 seconds,

Hg之參數：接觸角為130°，表面張力為485dynes/cm Hg parameters: contact angle is 130°, surface tension is 485dynes/cm

管體積使用率：將樣品量調整為100%以下之約50% Tube volume usage: Adjust the sample volume to approximately 50% of 100% or less

(2)0.5μm以下之累計孔隙體積之計算方法 (2) Calculation method of cumulative pore volume below 0.5 μm

累計0.5μm以下之Log差分孔隙體積(mL/g)之值，設為孔徑為0.5μm以下之累計孔隙體積。 The value of the Log differential pore volume (mL/g) of 0.5 μm or less is accumulated, and the cumulative pore volume having a pore diameter of 0.5 μm or less is set.

[過濾助劑之羥基密度之測定方法] [Method for determination of hydroxyl density of filter aids]

將藉由下述測定法所獲得之每1g羥基數量除以藉由下述測定法所獲得之每1g過濾助劑之表面積而獲得之值設為過濾助劑之羥基密度。 The value obtained by dividing the number of hydroxyl groups per gram obtained by the following measurement by the surface area per gram of the filter aid obtained by the following measurement method was taken as the hydroxyl density of the filter aid.

(1)過濾助劑之羥基數量之測定方法 (1) Method for determining the amount of hydroxyl groups of filter aids

‧電位差測定裝置：京都電子公司製造，電位差自動滴定裝置「AT-310J」 ‧Potential difference measuring device: manufactured by Kyoto Electronics Co., Ltd., potentiometer automatic titrator "AT-310J"

‧滴定試劑：0.01N鹽酸水溶液 ‧Titration reagent: 0.01N hydrochloric acid aqueous solution

‧滴定試劑之滴加速度：0.03ml/分鐘 ‧ titration acceleration of titration reagent: 0.03ml/min

‧測定試樣：使用以成為0.2重量%之過濾助劑濃度之方式利用NaOH水溶液稀釋而成者作為測定試樣。 ‧ Measurement sample: A sample was prepared by diluting with an aqueous NaOH solution so as to have a concentration of a filter aid of 0.2% by weight.

(2)過濾助劑之表面積之測定方法 (2) Method for measuring surface area of filter aid

過濾助劑之表面積係藉由氮吸附法進行測定。具體而言，將精確稱量之約1g之各過濾助劑置於ASAP2020(島津製作所股份有限公司製造，比表面積、孔分佈測定裝置)中，將根據氮吸附等溫線藉由BJH法之Halsey式所獲得之值設為表面積。 The surface area of the filter aid was determined by a nitrogen adsorption method. Specifically, about 1 g of each of the filter aids accurately weighed is placed in ASAP2020 (manufactured by Shimadzu Corporation, specific surface area, pore distribution measuring device), and will be based on the nitrogen adsorption isotherm by the BJH method of Halsey. The value obtained by the formula is set as the surface area.

[OH基密度之控制方法] [How to control the density of OH groups]

藉由對上述記載之上述A~C之各過濾助劑進行下述所示之熱處理、或酸處理，而進行OH基密度之控制。 The OH group density is controlled by performing the heat treatment or the acid treatment described below for each of the filter aids A to C described above.

(1)熱處理 (1) Heat treatment

將過濾助劑放入至焙燒盤內，使用焙燒爐(MOTOYAMA股份有限公司製造，商品名：SK-2535E)焙燒過濾助劑。具體而言，將放有過濾助劑之焙燒盤放入至爐內之溫度設定為25℃之焙燒爐內，一面進行空氣流通(3L/min)一面以10小時將焙燒爐內之溫度升溫至800℃，進而於800℃之環境下進行5小時或10小時過濾助劑之焙燒。 The filter aid was placed in a calcination tray, and a filter aid was calcined using a calciner (manufactured by MOTOYAMA Co., Ltd., trade name: SK-2535E). Specifically, the calcination tray containing the filter aid was placed in a baking furnace having a temperature set at 25 ° C, and the temperature in the calciner was raised to 10 hours while air circulation (3 L/min) was performed. The calcination of the filter aid was carried out at 800 ° C for 5 hours or 10 hours in an environment of 800 ° C.

(2)利用酸所進行之處理 (2) Treatment with acid

於各過濾助劑50g中，添加下述表3所示之酸水溶液(a~t)150ml，充分地進行攪拌、混合。停止攪拌，靜置表3中記載之時間(處理時間)後，去除上清液。於去除上清液之混合液中添加離子交換水， 並利用攪拌器攪拌5分鐘，靜置直至上清液變透明，之後去除上清液，清洗過濾助劑。重複該操作，直至上清液變為中性(pH值=5~8)。最後，將過濾助劑過濾於濾紙上，使之自然乾燥，獲得經酸處理之過濾助劑。 To 50 g of each of the filtration aids, 150 ml of an aqueous acid solution (a to t) shown in the following Table 3 was added, and the mixture was sufficiently stirred and mixed. Stirring was stopped, and the time (treatment time) described in Table 3 was allowed to stand, and then the supernatant was removed. Adding ion-exchanged water to the mixture of the supernatant removed, The mixture was stirred for 5 minutes with a stirrer, and allowed to stand until the supernatant became transparent, after which the supernatant was removed and the filter aid was washed. Repeat this operation until the supernatant becomes neutral (pH = 5~8). Finally, the filter aid is filtered on the filter paper to be naturally dried to obtain an acid-treated filter aid.

[含有過濾助劑之過濾器之製作] [Production of filter containing filter aid]

於上述經酸處理之過濾助劑10g中添加100mL之離子交換水，並進行攪拌、混合，而獲得過濾助劑分散水溶液。其次，將濾紙(No.5A(網眼7μm)：Advantech公司製造)置於90mmφ之平板型SUS製殼體(住友3M公司製造之INLET90-TL)中，於0.1MPa以下之壓力下對 過濾助劑分散水溶液進行過濾，而於濾紙上形成過濾助劑均勻之濾餅層後，利用1~2L之離子交換水清洗濾餅層，而獲得含有過濾助劑之過濾器。再者，含過濾助劑之過濾器中之過濾助劑之含量為0.18g/cm2。 100 mL of ion-exchanged water was added to 10 g of the above-mentioned acid-treated filter aid, and the mixture was stirred and mixed to obtain a filter aid dispersion aqueous solution. Next, a filter paper (No. 5A (mesh 7 μm): manufactured by Advantech Co., Ltd.) was placed in a 90 mmφ flat-type SUS case (INLET90-TL manufactured by Sumitomo 3M Co., Ltd.), and filtered under a pressure of 0.1 MPa or less. After dispersing the aqueous solution to filter, and forming a filter cake layer having a uniform filter aid on the filter paper, the filter cake layer is washed with 1 to 2 L of ion-exchanged water to obtain a filter containing a filter aid. Further, the content of the filter aid in the filter containing the filter aid was 0.18 g/cm 2 .

[過濾處理] [Filtering]

[被處理二氧化矽分散液之過濾條件：實施例1~18及比較例1~17] [Filtering conditions of the treated cerium oxide dispersion: Examples 1 to 18 and Comparative Examples 1 to 17]

不使所製作之含過濾助劑之過濾器乾燥，於經清洗水潤濕之狀態下，以過濾壓0.30MPa、過濾流量34.6g/(分鐘．m2)，過濾被處理二氧化矽分散液(膠體二氧化矽漿料a~c)，而獲得用於研磨液組合物之二氧化矽分散液。再者，將二氧化矽分散液於25℃下之pH值示於表4~表7。 The filter containing the filter aid is not dried, and the treated cerium oxide dispersion is filtered at a filtration pressure of 0.30 MPa and a filtration flow rate of 34.6 g/(min.m 2 ) in a state of being wetted by the washing water. (Colloidal cerium oxide slurry a to c), and a cerium oxide dispersion for a polishing liquid composition is obtained. Further, the pH values of the cerium oxide dispersion at 25 ° C are shown in Tables 4 to 7.

[0.45μm過濾器液體透過量之測定方法] [Method for Measuring Liquid Permeation Amount of 0.45 μm Filter]

利用特定之過濾器(Advantech公司製造之親水性PTFE0.45(孔徑)μm過濾器，型號：25HP045AN)，於氣壓0.25MPa之固定壓力下，使藉由上述過濾獲得之二氧化矽分散液液體透過過濾器，求出直至過濾器阻塞之液體透過量(ml)作為MF值，示於表4~表7。再者，可將本條件之0.45μm過濾器液體透過量設為於將該二氧化矽分散液用於研磨液組合物之製備之情形時可減少刮痕之指標。即，MF值越高，可評價為越可減少刮痕之二氧化矽分散液或研磨液組合物。 The cerium oxide dispersion liquid obtained by the above filtration was permeated by a specific filter (a hydrophilic PTFE 0.45 (pore size) μm filter manufactured by Advantech Co., Ltd., model: 25HP045AN) at a fixed pressure of 0.25 MPa. The filter was used to determine the liquid permeation amount (ml) until the filter was clogged as the MF value, which is shown in Tables 4 to 7. Further, the 0.45 μm filter liquid permeation amount of the present conditions can be set as an index for reducing the scratch when the ceria dispersion is used for the preparation of the polishing composition. That is, the higher the MF value, the more the cerium oxide dispersion or the polishing liquid composition which can reduce the scratches.

[完工研磨液組合物之製備方法] [Preparation method of finished polishing liquid composition]

於在離子交換水中添加1H-苯并***鈉鹽0.1質量%、N-胺基乙基乙醇胺0.03質量%、丙烯酸/丙烯醯胺-2-甲基丙磺酸共聚物鈉鹽(陰離子性高分子，莫耳比90/10，重量平均分子量2000，東亞合成公司製造)0.02質量%、硫酸0.4質量%、1-羥基亞乙基-1,1-二膦酸0.05質量%、過氧化氫0.4質量%，並進行混合而獲得之水溶液之攪拌下，以研 磨液組合物中之二氧化矽濃度成為5質量%之方式添加利用上述含有過濾助劑之過濾器進行過濾之過濾結束之二氧化矽分散液，而製備實施例1~18及比較例1~17之研磨液組合物(pH值1.0~2.0(25℃))。 0.1% by mass of 1H-benzotriazole sodium salt, 0.03% by mass of N-aminoethylethanolamine, and sodium salt of acrylic acid/acrylamide-methylaminesulfonate copolymer (high anionicity) in ion-exchanged water Molecule, molar ratio 90/10, weight average molecular weight 2000, manufactured by Toagosei Co., Ltd.) 0.02% by mass, 0.4% by mass of sulfuric acid, 0.05% by mass of 1-hydroxyethylidene-1,1-diphosphonic acid, 0.4 hydrogen peroxide % by mass, and mixing with the aqueous solution obtained by mixing The cerium oxide dispersion liquid which was filtered by the above filter containing the filter aid was added to the pulverized cerium concentration in the pulverization composition, and the cerium oxide dispersion liquid which was filtered by the filter containing the filter aid was added to prepare Examples 1 to 18 and Comparative Example 1 17 polishing liquid composition (pH 1.0~2.0 (25 ° C)).

[陰離子性高分子之重量平均分子量之測定方法] [Method for Measuring Weight Average Molecular Weight of Anionic Polymer]

陰離子性高分子之重量平均分子量係藉由下述測定條件下之凝膠滲透層析法(GPC)法進行測定。 The weight average molecular weight of the anionic polymer was measured by a gel permeation chromatography (GPC) method under the following measurement conditions.

(GPC條件) (GPC condition)

管柱：TSKgel G4000PWXL+TSKgel G2500PWXL(Tosoh製造) Column: TSKgel G4000PWXL+TSKgel G2500PWXL (manufactured by Tosoh)

保護管柱：TSKguardcolumn PWXL(Tosoh製造) Protection column: TSKguardcolumn PWXL (manufactured by Tosoh)

溶離液：0.2M磷酸緩衝液/CH3CN=9/1(體積比) Dissolution: 0.2M phosphate buffer / CH3CN = 9 / 1 (volume ratio)

溫度：40℃ Temperature: 40 ° C

流速：1.0mL/分鐘 Flow rate: 1.0 mL/min

試樣尺寸：5mg/mL Sample size: 5mg/mL

檢測器：RI Detector: RI

換算標準：聚丙烯酸鈉(分子量(Mp)：11.5萬、2.8萬、4100、1250(創和科學及American Polymer Standards Corp.製造)) Conversion standard: sodium polyacrylate (molecular weight (Mp): 115,000, 28,000, 4100, 1250 (Chuanghe Science and American Polymer Standards Corp.))

[使用研磨液組合物之基板之研磨] [Grinding of substrate using polishing composition]

使用藉由上述方式製備之實施例1~18及比較例1~17之研磨液組合物，於下述條件下進行精研磨。對各個研磨後之基板之刮痕數量進行評價，將其結果示於下述表4~表7。作為被研磨基板，使用利用含有氧化鋁研磨材料之研磨液預先進行粗研磨，AFM-Ra為5~15Å、厚度1.27mm之外徑95mmφ且內徑25mmφ之鍍Ni-P之鋁合金基板。 The polishing liquid compositions of Examples 1 to 18 and Comparative Examples 1 to 17 prepared by the above-described methods were subjected to finish polishing under the following conditions. The number of scratches on each of the polished substrates was evaluated, and the results are shown in Tables 4 to 7 below. As the substrate to be polished, a Ni-P plated aluminum alloy substrate having an AFM-Ra of 5 to 15 Å, a thickness of 1.27 mm, an outer diameter of 95 mmφ, and an inner diameter of 25 mmφ was used as a substrate to be polished.

[精研磨條件] [fine grinding conditions]

‧研磨試驗機：SpeedFam公司製造，雙面9B研磨機 ‧ Grinding test machine: Made by SpeedFam, double-sided 9B grinder

‧研磨墊：Fujibo公司製造，胺基甲酸酯製精研磨用墊 ‧ polishing pad: manufactured by Fujibo, urethane polishing pad

‧上壓盤轉數：32.5rpm/分鐘 ‧Upper platen rotation: 32.5rpm/min

‧研磨液組合物供給量：100mL/分鐘 ‧Sales composition supply: 100mL / min

‧正式研磨時間：4分鐘 ‧ Official grinding time: 4 minutes

‧正式研磨荷重：7.8kPa ‧ Official grinding load: 7.8kPa

‧所投入之基板之片數：10片 ‧ The number of substrates invested: 10

[刮痕之測定條件] [Measurement conditions for scratches]

‧測定設備：光學式全面缺陷檢查機(KLA-Tencor公司製造之Candela OSA6100) ‧Measuring equipment: Optical comprehensive defect inspection machine (Candela OSA6100 manufactured by KLA-Tencor)

：原子力顯微鏡(Veco社公司製造，DI Nano-Scope III) : Atomic Force Microscope (DI Nano-Scope III, manufactured by Veco Corporation)

‧測定方法：將進行過研磨之基板浸漬於離子交換水中5分鐘後，利用離子交換水沖洗20秒鐘。其後，於投入至研磨試驗機之基板中，隨機選擇4片，使用光學式全面缺陷檢查機，對以10000rpm進行旋轉中之各基板照射雷射，檢測長度為100μm以上之基板表面之損傷。又，該等刮痕中，使用原子力顯微鏡，將深度為1nm以上且未達100nm，寬度為5nm以上且未達500nm之損傷作為刮痕而計數。將位於4片基板各自之兩面之刮痕數量(條)之合計除以8，算出每個基板面之刮痕數量，並示於表4~表7。 ‧ Measurement method: The polished substrate was immersed in ion-exchanged water for 5 minutes, and then rinsed with ion-exchanged water for 20 seconds. Thereafter, four substrates were randomly selected and placed on a substrate of a polishing tester, and each of the substrates rotated at 10,000 rpm was irradiated with a laser using an optical full-scale defect inspection machine to detect damage of the surface of the substrate having a length of 100 μm or more. Further, among the scratches, an atomic force microscope was used to count the damage having a depth of 1 nm or more and less than 100 nm, and a width of 5 nm or more and less than 500 nm as scratches. The total number of scratches (bars) on each of the four substrates was divided by 8, and the number of scratches on each substrate surface was calculated and shown in Tables 4 to 7.

如上述表4~表7所示，關於矽藻土之羥基密度為0.40×10-5mol/m2以上，膠體二氧化矽之一次粒子之平均粒徑為1nm以上且50nm以下之實施例1~18，與比較例1~17相比，MF值更高，刮痕數量更少。 As shown in the above Tables 4 to 7, the hydroxyl group density of the diatomite is 0.40 × 10 -5 mol/m 2 or more, and the average particle diameter of the primary particles of the colloidal cerium oxide is 1 nm or more and 50 nm or less. ~18, compared with Comparative Examples 1 to 17, the MF value was higher and the number of scratches was smaller.

[產業上之可利用性] [Industrial availability]

如以上所說明，根據本揭示，可製造一種研磨液組合物，其可有效地去除含有膠體二氧化矽之被處理二氧化矽分散液中之粗大粒子或凝膠化物，藉此過濾精度較高，可減少研磨後之基板表面之刮痕數量。因此，若使用本發明之研磨液組合物之製造方法，則磁碟基板等基板之生產性提高。 As explained above, according to the present disclosure, it is possible to manufacture a polishing liquid composition which can effectively remove coarse particles or gelled substances in a treated cerium oxide dispersion containing colloidal cerium oxide, whereby filtration precision is high It can reduce the number of scratches on the surface of the substrate after grinding. Therefore, when the method for producing a polishing liquid composition of the present invention is used, the productivity of a substrate such as a disk substrate is improved.

Claims (10)

一種研磨液組合物之製造方法，其包括利用包含過濾助劑之過濾器對含有膠體二氧化矽之被處理二氧化矽分散液進行過濾處理之步驟，上述膠體二氧化矽之藉由滴定法所求得之一次粒子之平均粒徑為1nm以上且50nm以下，上述過濾助劑之羥基密度為0.40×10-5mol/m2以上。 A method for producing a polishing liquid composition, comprising the step of filtering a treated ceria dispersion containing colloidal ceria by a filter comprising a filter aid, wherein the colloidal ceria is titrated The primary particle obtained has an average particle diameter of 1 nm or more and 50 nm or less, and the filter aid has a hydroxyl group density of 0.40 × 10 -5 mol/m 2 or more. 如請求項1之研磨液組合物之製造方法，其中上述過濾助劑係藉由將羥基密度未達0.40×10-5mol/m2之矽藻土與酸水溶液進行混合後，對上述矽藻土進行脫酸處理而獲得。 The method for producing a polishing composition according to claim 1, wherein the filter aid is obtained by mixing diatomaceous earth having a hydroxyl group density of less than 0.40 × 10 -5 mol/m 2 with an aqueous acid solution; The soil is obtained by deacidification treatment. 如請求項1或2之研磨液組合物之製造方法，其中上述膠體二氧化矽之藉由滴定法所求得之一次粒子之平均粒徑與上述過濾助劑之藉由雷射式粒度分佈測定裝置所測得之平均粒徑的比(膠體二氧化矽之藉由滴定法所測得之一次粒子之平均粒徑/過濾助劑之利用雷射式粒度分佈測定裝置所測得之平均粒徑)為1.20×10-3以上且4.20×10-3以下。 The method for producing a polishing composition according to claim 1 or 2, wherein the average particle diameter of the primary particles obtained by titration of the colloidal ceria and the above-mentioned filter aid are determined by a laser particle size distribution Ratio of average particle diameter measured by the apparatus (average particle diameter of primary particles measured by titration of colloidal cerium oxide / average particle diameter measured by a laser particle size distribution analyzer using a filter aid) ) is 1.20 × 10 -3 or more and 4.20 × 10 -3 or less. 如請求項1或2之研磨液組合物之製造方法，其包括於包含酸、氧化劑及水之混合液中，混合藉由對上述被處理二氧化矽分散液實施上述過濾處理而獲得之二氧化矽分散液之步驟。 A method for producing a polishing composition according to claim 1 or 2, which comprises mixing in a mixture comprising an acid, an oxidizing agent and water, and mixing the second oxidation obtained by subjecting the above-mentioned treated ceria dispersion to the above filtration treatment. The step of 矽 dispersion. 一種研磨液組合物，其係藉由如請求項1至4中任一項之研磨液組合物之製造方法而製造。 A polishing liquid composition produced by the method for producing a polishing liquid composition according to any one of claims 1 to 4. 如請求項5之研磨液組合物，其進而含有具有陰離子性基之水溶性高分子、雜環芳香族化合物、及脂肪族胺化合物或脂環式胺化合物。 The polishing composition of claim 5, which further comprises a water-soluble polymer having an anionic group, a heterocyclic aromatic compound, and an aliphatic amine compound or an alicyclic amine compound. 一種磁碟基板之製造方法，其包括將藉由如請求項1至4中任一 項之研磨液組合物之製造方法所獲得之研磨液組合物供給至被研磨基板之研磨對象面，藉此對上述研磨對象面進行研磨之步驟。 A method of manufacturing a disk substrate, comprising: by any one of claims 1 to 4 The polishing liquid composition obtained by the method for producing a polishing composition of the present invention is supplied to the polishing target surface of the substrate to be polished, thereby polishing the surface to be polished. 如請求項7之磁碟基板之製造方法，其包括：藉由上述研磨液組合物之製造方法而製造研磨液組合物，及將上述研磨液組合物供給至上述被研磨基板之上述研磨對象面，並使研磨墊與上述研磨對象面接觸，移動上述研磨墊及/或上述被研磨基板，而對上述研磨對象面進行研磨。 The method for producing a magnetic disk substrate according to claim 7, comprising: producing a polishing liquid composition by the method for producing the polishing liquid composition; and supplying the polishing liquid composition to the polishing target surface of the substrate to be polished And the polishing pad is brought into surface contact with the polishing target, and the polishing pad and/or the substrate to be polished is moved to polish the polishing target surface. 一種過濾助劑，其係用於如請求項1至4中任一項之研磨液組合物之製造方法者，並且包含羥基密度為0.40×10-5mol/m2以上之矽藻土。 A filter aid for use in a method for producing a polishing composition according to any one of claims 1 to 4, and comprising diatomaceous earth having a hydroxyl group density of 0.40 × 10 -5 mol/m 2 or more. 一種過濾助劑之製造方法，其係如請求項9之過濾助劑之製造方法，並且包括將羥基密度未達0.40×10-5mol/m2之矽藻土與酸水溶液進行混合後，對上述矽藻土進行脫酸處理之步驟。 A method for producing a filter aid, which is the method for producing a filter aid according to claim 9, and comprising mixing the diatomaceous earth having a hydroxyl group density of less than 0.40×10 -5 mol/m 2 with an aqueous acid solution, The above diatomaceous earth is subjected to a step of deacidification treatment.
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