TW201309786A - Process for producing glass product - Google Patents
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- TW201309786A TW201309786A TW101124997A TW101124997A TW201309786A TW 201309786 A TW201309786 A TW 201309786A TW 101124997 A TW101124997 A TW 101124997A TW 101124997 A TW101124997 A TW 101124997A TW 201309786 A TW201309786 A TW 201309786A
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- 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
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
- C03C23/0075—Cleaning of glass
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- Geochemistry & Mineralogy (AREA)
- Detergent Compositions (AREA)
- Mechanical Engineering (AREA)
- Surface Treatment Of Glass (AREA)
- Cleaning In General (AREA)
- Cleaning By Liquid Or Steam (AREA)
Abstract
Description
本發明係關於一種玻璃製品之製造方法。 The present invention relates to a method of making a glass article.
作為針對於玻璃研磨之研磨劑，一直廣泛地使用以氧化鈰為主成分之研磨粒(以下，稱為氧化鈰研磨粒)。然而，由於近年來稀土類氧化物之價格高漲，氧化鈰研磨粒亦變得無法以先前之成本獲得，故而業界正積極地研究其替代材料。作為替代材料，正在對氧化鋯或氧化鋁等各種氧化物展開研究。 As an abrasive for glass polishing, abrasive grains containing cerium oxide as a main component (hereinafter referred to as cerium oxide abrasive grains) have been widely used. However, due to the recent increase in the price of rare earth oxides, cerium oxide abrasive grains have also become impossible to obtain at the previous cost, and the industry is actively studying alternative materials. As an alternative material, various oxides such as zirconia or alumina are being studied.
近年來，作為加工玻璃基板所使用之研磨粒，已明確錳氧化物之三氧化二錳研磨粒於有限之特定條件下可表現出與氧化鈰研磨粒接近之研磨特性因而受到關注(非專利文獻1)。錳氧化物存在二氧化錳、三氧化二錳及四氧化三錳。 In recent years, as abrasive grains used for processing glass substrates, it has been clarified that manganese oxide trimanganese abrasive grains exhibit a polishing property close to that of cerium oxide abrasive grains under limited specific conditions (Non-Patent Literature) 1). Manganese oxide is present in manganese dioxide, dimanganese trioxide and trimanganese tetraoxide.
於上述錳氧化物中，先前以來作為研磨劑而眾所周知者為二氧化錳，使用二氧化錳研磨粒之研磨粒於半導體製程中之CMP(Chemical Mechanical Polishing，化學機械研磨)步驟中一直受到研究。於非專利文獻2中，揭示有於半導體製程中之CMP步驟中用作研磨劑的二氧化錳研磨粒及三氧化二錳研磨粒可利用包含過氧化氫水的洗淨液而洗淨。 Among the above manganese oxides, manganese dioxide has been known as an abrasive, and abrasive grains using manganese dioxide abrasive grains have been studied in the CMP (Chemical Mechanical Polishing) step in a semiconductor process. Non-Patent Document 2 discloses that manganese dioxide abrasive grains and trimanganese oxide abrasive grains used as an abrasive in a CMP step in a semiconductor process can be washed with a cleaning liquid containing hydrogen peroxide water.
非專利文獻1：2010精密工學會春季大會學術演講會論文 集p.723 Non-Patent Document 1: 2010 Precision Engineering Society Spring Conference Academic Lecture Paper Set p.723
非專利文獻2：砥粒加工學會志Vol. 43, No.12, 1999, p.20~23 Non-Patent Document 2: Society for Processing of Granules Vol. 43, No. 12, 1999, p. 20~23
然而，本發明者等人發現，非專利文獻2中所記載之利用包含過氧化氫之洗淨液所進行的二氧化錳研磨粒及三氧化二錳研磨粒之洗淨對於半導體CMP中所使用的平均粒徑通常為30~40 nm左右之二氧化錳研磨粒及三氧化二錳研磨粒較有效，與該等研磨粒相比平均粒徑較大且穩定的用於玻璃之研磨的三氧化二錳研磨粒若利用包含過氧化氫水之洗淨液，則洗淨效果較低。 However, the inventors of the present invention have found that the cleaning of manganese dioxide abrasive grains and dimanganese trioxide abrasive grains by a cleaning liquid containing hydrogen peroxide described in Non-Patent Document 2 is used for semiconductor CMP. The average particle size is usually about 30 to 40 nm, and the manganese dioxide abrasive grains and the manganese trioxide abrasive grains are more effective. Compared with the abrasive grains, the average particle size is larger and the stable trioxide is used for the grinding of the glass. When the di-manganese abrasive grain uses a washing liquid containing hydrogen peroxide water, the washing effect is low.
又，關於包含過氧化氫水之洗淨液，若洗淨液之pH值增大，則三氧化二錳研磨粒不易溶解，若洗淨液之pH值超過4，則三氧化二錳研磨粒幾乎不溶解，因此認為難以適用於耐酸性較弱之玻璃。 Further, in the cleaning liquid containing hydrogen peroxide water, if the pH of the cleaning liquid is increased, the dimanganese trioxide abrasive grains are not easily dissolved, and if the pH of the cleaning liquid exceeds 4, the dimanganese trioxide abrasive grains are not easily dissolved. It hardly dissolves, so it is considered to be difficult to apply to glass which is weak in acid resistance.
對於玻璃研磨後之洗淨的要求逐年提高，尤其是於磁碟玻璃基板或光罩之領域中，上述要求之提高較明顯，使用三氧化二錳研磨粒作為氧化鈰研磨粒之代替物之研磨後的洗淨亦期待較高之三氧化二錳研磨粒之去除效果。 The requirements for the cleaning after the glass polishing are increasing year by year, especially in the field of the disk glass substrate or the reticle, the above requirements are more obviously improved, and the trimanganese abrasive grains are used as the substitute for the cerium oxide abrasive grains. The subsequent cleaning also expects a higher removal effect of the dimanganese trioxide abrasive particles.
因此，本發明係鑒於上述問題而成者，其目的在於提供一種玻璃製品之製造方法，其於使用包含三氧化二錳研磨粒之研磨劑研磨玻璃的研磨步驟之後，包括使用洗淨液有效地洗淨附著於玻璃上的包含三氧化二錳研磨粒之研磨劑 的步驟。 Accordingly, the present invention has been made in view of the above problems, and an object thereof is to provide a method for producing a glass article, which comprises using a cleaning liquid after a grinding step of grinding a glass using an abrasive containing trimanganese abrasive grains. Washing the abrasive containing the manganese trioxide abrasive grains attached to the glass A step of.
本發明者對可溶解三氧化二錳研磨粒之水溶液進行研究，結果發現，包含抗壞血酸及異抗壞血酸之至少一者之水溶液對於玻璃之研磨中所使用之平均粒徑較大的三氧化二錳研磨粒之溶解力較高，並基於該見解完成了本發明。 The inventors of the present invention conducted an investigation on an aqueous solution of a dissolvable trimanganese abrasive grain, and as a result, found that an aqueous solution containing at least one of ascorbic acid and erythorbic acid is used to grind dimanganese oxide having a larger average particle diameter used for polishing the glass. The solvency of the granules is high, and the present invention has been completed based on this finding.
即，本發明之主旨如下所述。 That is, the gist of the present invention is as follows.
[1]一種玻璃製品之製造方法，其係包括：使用包含三氧化二錳研磨粒之研磨劑研磨玻璃的研磨步驟；及其後使用洗淨液洗淨該玻璃的洗淨步驟；且該洗淨液包含抗壞血酸及異抗壞血酸之至少一者。 [1] A method for producing a glass product, comprising: a grinding step of grinding a glass using an abrasive containing triammine abrasive grains; and a washing step of washing the glass with a cleaning liquid; and the washing The cleaning solution contains at least one of ascorbic acid and erythorbic acid.
[2]如上述[1]之玻璃製品之製造方法，其中三氧化二錳研磨粒之平均粒徑為0.3 μm以上、3 μm以下。 [2] The method for producing a glass product according to the above [1], wherein the average particle diameter of the dimanganese trioxide abrasive grains is 0.3 μm or more and 3 μm or less.
[3]如上述[1]或[2]之玻璃製品之製造方法，其中洗淨液之pH值為2以上、5以下。 [3] The method for producing a glass product according to the above [1] or [2] wherein the pH of the cleaning liquid is 2 or more and 5 or less.
根據本發明之玻璃製品之製造方法，在利用包含三氧化二錳研磨粒之研磨劑研磨玻璃之後，藉由使用包含抗壞血酸及異抗壞血酸之至少一者的洗淨液洗淨玻璃，可溶解且有效地洗淨附著於玻璃上之三氧化二錳研磨粒。 According to the method for producing a glass article of the present invention, after the glass is ground by the abrasive containing the trimanganese abrasive grains, the glass is washed by using a cleaning liquid containing at least one of ascorbic acid and erythorbic acid, and is soluble and effective. The dimanganese trioxide abrasive grains attached to the glass are washed.
由於包含抗壞血酸及異抗壞血酸之至少一者的洗淨液對於三氧化二錳研磨粒在較廣之pH值範圍內均具有一定程度以上之溶解度，因而本發明之玻璃製品之製造方法亦可適用於耐酸性較弱的玻璃。 Since the cleaning liquid containing at least one of ascorbic acid and erythorbic acid has a certain degree of solubility for the dimanganese trioxide abrasive grains in a wide pH range, the method for producing the glass article of the present invention can also be applied to A glass that is less resistant to acidity.
本發明之玻璃製品之製造方法包括使用包含三氧化二錳研磨粒之研磨劑研磨玻璃的研磨步驟。三氧化二錳研磨粒可作為氧化鈰研磨粒之替代材料而用於玻璃之研磨。 The method of producing a glass article of the present invention comprises the step of grinding a glass using an abrasive comprising trimanganese abrasive particles. The dimanganese trioxide abrasive particles can be used as a substitute for cerium oxide abrasive grains for the grinding of glass.
於本發明中，三氧化二錳研磨粒之平均粒徑較佳為0.3 μm以上、3 μm以下。三氧化二錳研磨粒之平均粒徑係使用雷射散射，藉由後文實施例中記述之方法進行測定。藉由將三氧化二錳研磨粒之平均粒徑設為0.3 μm以上，可獲得充分之研磨速率，藉由設為3 μm以下，可防止研磨粒造成磨痕。 In the present invention, the average particle diameter of the dimanganese trioxide abrasive grains is preferably 0.3 μm or more and 3 μm or less. The average particle diameter of the dimanganese trioxide abrasive grains was measured by laser scattering using the method described in the following examples. By setting the average particle diameter of the dimanganese trioxide abrasive grains to 0.3 μm or more, a sufficient polishing rate can be obtained, and by setting it to 3 μm or less, it is possible to prevent the abrasive grains from being scratched.
研磨劑中之三氧化二錳研磨粒之濃度通常較佳為1質量%以上、20質量%以下，更佳為3質量%以上、15質量%以下。藉由將研磨劑中之三氧化二錳研磨粒之濃度設為1質量%以上，可獲得充分之研磨速率。又，藉由設為20質量%以下，可防止因研磨過程中混入至漿料中之玻璃成分之影響而漿料黏度上升，可提高研磨速率。 The concentration of the dimanganese trioxide abrasive grains in the polishing agent is usually preferably 1% by mass or more and 20% by mass or less, more preferably 3% by mass or more and 15% by mass or less. A sufficient polishing rate can be obtained by setting the concentration of the dimanganese trioxide abrasive grains in the polishing agent to 1% by mass or more. Moreover, by setting it as 20 mass% or less, it can prevent that the viscosity of the slurry raises by the influence of the glass component mixed in the slurry in the grinding|polishing process, and can raise the polishing rate.
又，研磨劑中亦可包含界面活性劑及分散劑等。作為界面活性劑，例如可列舉以伸烷基二醇為代表之非泡沫性之界面活性劑。研磨劑中之界面活性劑之含量較佳為0.01~1質量%。 Further, a surfactant, a dispersant, or the like may be contained in the polishing agent. As the surfactant, for example, a non-foaming surfactant typified by an alkylene glycol is exemplified. The content of the surfactant in the abrasive is preferably from 0.01 to 1% by mass.
又，作為分散劑，例如可列舉：聚丙烯酸鈉、二磷酸鈉、膦酸鈉及檸檬酸鈉。研磨劑中之分散劑之含量較佳為0.5~2質量%。 Further, examples of the dispersant include sodium polyacrylate, sodium diphosphate, sodium phosphonate, and sodium citrate. The content of the dispersing agent in the abrasive is preferably from 0.5 to 2% by mass.
本發明中之研磨之方法並無特別限定，例如較佳為：使玻璃與研磨布接觸，一面供給包含三氧化二錳研磨粒之研磨劑，一面使研磨布與玻璃相對地移動，而將玻璃研磨成鏡面狀。作為研磨布，例如可使用胺基甲酸酯製研磨墊。 The method of polishing in the present invention is not particularly limited. For example, it is preferred that the glass be placed in contact with the polishing cloth while the polishing agent containing the manganese trioxide abrasive grains is supplied, and the polishing cloth is moved relative to the glass to move the glass. Grinded into a mirror shape. As the polishing cloth, for example, a urethane polishing pad can be used.
本發明之玻璃製品之製造方法包括使用包含抗壞血酸及異抗壞血酸之至少一者的洗淨液(以下，亦稱為本發明所使用之洗淨液)，將附著於玻璃上的包含三氧化二錳研磨粒之研磨劑洗淨的步驟。抗壞血酸及異抗壞血酸對於三氧化二錳研磨粒之溶解力較高，且擔負作為pH值調整劑之作用。 The method for producing a glass product of the present invention comprises using a cleaning liquid containing at least one of ascorbic acid and erythorbic acid (hereinafter also referred to as a cleaning liquid used in the present invention) to contain manganese dioxide adhered to the glass. The step of washing the abrasive grains. Ascorbic acid and erythorbic acid have a high solubility for the dimanganese trioxide abrasive grains and serve as a pH adjuster.
本發明所使用之洗淨液中抗壞血酸及異抗壞血酸之含量以合計值計較佳為0.1~1質量%，更佳為0.25~0.75質量%。藉由將洗淨液中抗壞血酸及異抗壞血酸之含量以合計值計設為0.1質量%以上，易於維持溶出量。又，藉由設為1質量%以下，易於維持包含三氧化二錳研磨粒之研磨劑之分散性。 The content of ascorbic acid and erythorbic acid in the cleaning liquid used in the present invention is preferably 0.1 to 1% by mass, and more preferably 0.25 to 0.75% by mass, based on the total value. By setting the content of ascorbic acid and erythorbic acid in the cleaning liquid to 0.1% by mass or more in total, it is easy to maintain the elution amount. Moreover, by setting it as 1 mass% or less, it is easy to maintain the dispersibility of the abrasive containing the trimanganese abrasive grain.
本發明所使用之洗淨液較佳為包含洗淨助劑。作為洗淨助劑，例如可列舉：用以降低表面張力之界面活性劑、及用以將pH值保持為穩定之具有緩衝效果之酸。作為界面活性劑，例如可列舉：乙炔二醇等非離子性界面活性劑、及聚丙烯酸鈉等陰離子界面活性劑等。 The cleaning solution used in the present invention preferably contains a cleaning aid. Examples of the detergent builder include a surfactant for lowering the surface tension and an acid having a buffering effect for maintaining a stable pH. Examples of the surfactant include nonionic surfactants such as acetylene glycol and anionic surfactants such as sodium polyacrylate.
又，作為用以將pH值保持為穩定之具有緩衝效果之酸，例如可列舉pKa處於2~5且具有一個以上之羧酸之酸。具體 而言，例如作為可期待緩衝效果之酸可列舉檸檬酸，除此以外亦有多種有機酸可使用。 Further, examples of the acid having a buffering effect for maintaining a stable pH value include an acid having a pKa of 2 to 5 and having one or more carboxylic acids. specific For example, citric acid can be mentioned as an acid which can be expected as a buffering effect, and various organic acids can also be used.
本發明所使用之洗淨液較佳為包含水作為溶劑。作為水，例如可列舉：去離子水、超純水、電荷離子水、氫水及臭氧水等。此外，由於水具有控制本發明所使用之洗淨液之流動性的功能，因此其含量可根據洗淨速度等目標之洗淨特性而適當地設定，通常較佳為設為55~98質量%。 The cleaning solution used in the present invention preferably contains water as a solvent. Examples of the water include deionized water, ultrapure water, charged ionized water, hydrogen water, and ozone water. Further, since water has a function of controlling the fluidity of the cleaning liquid used in the present invention, the content thereof can be appropriately set depending on the target washing performance such as the washing speed, and is usually preferably set to 55 to 98% by mass. .
本發明所使用之包含抗壞血酸及異抗壞血酸之至少一者的洗淨液雖於較廣之pH值範圍內對三氧化二錳研磨粒均具有一定程度以上之溶解度，但洗淨液之pH值較佳為2以上、5以下。藉由將洗淨液之pH值設為2以上，抗壞血酸或異抗壞血酸易於溶解，就操作及安全性之觀點而言亦較佳。又，藉由將洗淨液之pH值設為5以下，可提昇洗淨液對於三氧化二錳研磨粒之去除能力。此外，於對耐酸性較弱之玻璃應用本發明之情形時，洗淨液之pH值典型而言較佳為設為4以下。 The cleaning solution containing at least one of ascorbic acid and erythorbic acid used in the present invention has a certain degree of solubility to the dimanganese trioxide abrasive grains in a wide pH range, but the pH of the cleaning solution is higher than that of the cleaning solution. Good is 2 or more and 5 or less. By setting the pH of the cleaning liquid to 2 or more, ascorbic acid or erythorbic acid is easily dissolved, and it is also preferable from the viewpoint of handling and safety. Further, by setting the pH of the cleaning liquid to 5 or less, the removal ability of the cleaning liquid for the dimanganese trioxide abrasive grains can be improved. Further, in the case where the present invention is applied to a glass having weak acid resistance, the pH of the cleaning liquid is preferably set to 4 or less.
為防止因將玻璃浸漬於洗淨液中時生成之鹼/鹼土類而導致抗壞血酸或異抗壞血酸對於三氧化二錳研磨粒之溶解效果降低，可於本發明所使用之洗淨液中含有具有輔助劑效果(builder effect)之沸石等。 In order to prevent the alkali/alkaline earth which is formed when the glass is immersed in the cleaning liquid, the dissolution effect of ascorbic acid or erythorbic acid on the trimanganese abrasive grains is lowered, and the cleaning liquid used in the present invention may be contained in the cleaning liquid. Zeolite, etc. of the builder effect.
洗淨液中之沸石之含量並無特別限定，較佳為設為1質量%以下。 The content of the zeolite in the cleaning liquid is not particularly limited, but is preferably 1% by mass or less.
於洗淨步驟中，較佳為使上述洗淨液直接接觸玻璃而洗淨。作為使洗淨液直接接觸玻璃之方法，例如可列舉：於 洗淨槽中裝滿洗淨液，將玻璃放入至其中之浸漬式洗淨；自噴嘴向玻璃噴射洗淨液之方法；及使用聚乙烯醇製海綿之擦刷洗淨等。本發明所使用之洗淨液可適應上述任一種方法，但併用超音波洗淨之浸漬式洗淨由於可更高效率地洗淨因此較佳。 In the washing step, it is preferred that the washing liquid is directly contacted with the glass to be washed. As a method of directly contacting the washing liquid with the glass, for example, The washing tank is filled with the washing liquid, the glass is placed in the immersion type washing method; the washing liquid is sprayed from the nozzle to the glass; and the washing with a sponge made of polyvinyl alcohol is used. The cleaning solution used in the present invention can be adapted to any of the above methods, but the immersion cleaning using ultrasonic cleaning is preferred because it can be washed more efficiently.
於洗淨步驟中，使洗淨液與玻璃接觸之時間較佳為30秒以上。藉由設為30秒以上，可獲得充分之洗淨效果。 In the washing step, the time for bringing the cleaning liquid into contact with the glass is preferably 30 seconds or longer. By setting it to 30 second or more, sufficient washing effect can be obtained.
於洗淨步驟中，洗淨液之溫度可為室溫，亦可將其加熱至40~80℃左右而使用，較佳為設為80℃以下。藉由將洗淨液之溫度設為80℃以下，可防止抗壞血酸產生熱分解。又，於裝置之構成方面而言，若洗淨液達到接近100℃的溫度，則由於水之蒸發而pH值難以控制，故而較佳為設為80℃以下。 In the washing step, the temperature of the washing liquid may be room temperature, or it may be heated to about 40 to 80 ° C and used, preferably 80 ° C or less. By setting the temperature of the cleaning liquid to 80 ° C or lower, thermal decomposition of ascorbic acid can be prevented. Further, in terms of the configuration of the apparatus, when the cleaning liquid reaches a temperature close to 100 ° C, the pH value is difficult to control due to evaporation of water, and therefore it is preferably 80 ° C or lower.
於本發明之洗淨後，若進行使用水或鹼性洗劑的洗淨則更有效。 After the washing of the present invention, it is more effective if it is washed with water or an alkaline lotion.
又，亦可於本發明之洗淨之前組合使用水的洗淨。 Further, it is also possible to use a combination of water washing before the washing of the present invention.
本發明之製造方法中，於玻璃製品為磁碟用玻璃基板、高品質之液晶顯示器用玻璃基板之情形時等，較佳為於上述洗淨步驟之後，包括使用包含膠體二氧化矽研磨粒之漿料研磨玻璃之主表面的拋光研磨步驟作為其他步驟。 In the production method of the present invention, when the glass product is a glass substrate for a magnetic disk or a glass substrate for a high-quality liquid crystal display, it is preferable to use a colloidal cerium oxide abrasive grain after the cleaning step. The polishing and polishing step of the main surface of the slurry-polished glass is taken as another step.
作為藉由本發明之製造方法所製造之玻璃製品，例如可列舉：磁碟用玻璃基板、光罩基板及顯示器基板等玻璃基板，透鏡，以及用於CCD(Charge Coupled Device，電荷耦 合裝置)之藍色濾光玻璃及覆蓋玻璃等。藉由在利用本發明之製造方法製造之磁碟用玻璃基板的主表面形成磁記錄層，可製造磁碟。 Examples of the glass product produced by the production method of the present invention include a glass substrate for a disk, a glass substrate such as a mask substrate and a display substrate, a lens, and a CCD (Charge Coupled Device). Blue filter glass and cover glass, etc. A magnetic disk can be manufactured by forming a magnetic recording layer on the main surface of a glass substrate for a disk manufactured by the manufacturing method of the present invention.
以下對本發明之實施例具體地進行說明，但本發明並不限定於該等實施例。 The embodiments of the present invention are specifically described below, but the present invention is not limited to the embodiments.
認為可溶解三氧化二錳研磨粒之水溶液可作為包含三氧化二錳研磨粒之研磨劑的洗淨液而使用。因此，作為預調查，實施三氧化二錳研磨粒(平均粒徑1 μm )之溶解試驗。三氧化二錳研磨粒之平均粒徑係利用雷射繞射之粒度分佈測定器(日機裝製造之MT3300EX-II)進行測定。 It is considered that the aqueous solution in which the trimanganese abrasive grains are dissolved can be used as a cleaning liquid containing an abrasive of trimanganese oxide abrasive grains. Therefore, as a pre-survey, the operation of dimanganese trioxide abrasive grains (average particle size 1 μm) The dissolution test. The average particle diameter of the dimanganese trioxide abrasive grains was measured by a laser diffraction particle size analyzer (MT3300EX-II manufactured by Nikkiso Co., Ltd.).
於以成為表1所示之組成之方式添加酸後，製備pH值經調整之各種水溶液。向各水溶液40 ml中添加0.04 g之三氧化二錳研磨粒，並於25℃下振盪60分鐘。其後，使用離心分離機(日立工機製造之CF15-RXII)，於室溫下以10000 rpm處理30分鐘，去除上清液後，於70℃下乾燥2小時。乾燥後，測定三氧化二錳研磨粒之殘留量。由該值求出溶解於水溶液中之三氧化二錳研磨粒之比例(溶出量)。 After the acid was added in such a manner as to have the composition shown in Table 1, various aqueous solutions adjusted in pH were prepared. 0.04 g of dimanganese trioxide abrasive grains were added to 40 ml of each aqueous solution, and shaken at 25 ° C for 60 minutes. Thereafter, the mixture was centrifuged at 10,000 rpm for 30 minutes at room temperature using a centrifugal separator (CF15-RXII manufactured by Hitachi Plant), and the supernatant was removed, followed by drying at 70 ° C for 2 hours. After drying, the residual amount of the dimanganese trioxide abrasive grains was measured. From this value, the ratio (dissolution amount) of the dimanganese trioxide abrasive grains dissolved in the aqueous solution was determined.
即，將三氧化二錳研磨粒於各種水溶液中之溶出量設為自三氧化二錳研磨粒於各水溶液中之添加量減去殘留量所得之值，並以百分率(%)記載。將其結果示於表1中。 In other words, the amount of elution of the dimanganese trioxide abrasive grains in various aqueous solutions is a value obtained by subtracting the residual amount from the addition amount of the dimanganese trioxide abrasive grains in each aqueous solution, and is expressed as a percentage (%). The results are shown in Table 1.
如表1所示，若利用實施例1~10之包含抗壞血酸及異抗壞血酸之至少一者的水溶液，則於各pH值範圍內添加之三氧化二錳研磨粒之30%左右溶出。由該結果可知：包含抗壞血酸及異抗壞血酸之至少一者的水溶液於較廣之pH值範圍內對三氧化二錳研磨粒顯示出一定程度以上之溶解度。 As shown in Table 1, when the aqueous solution containing at least one of ascorbic acid and erythorbic acid of Examples 1 to 10 was used, about 30% of the dimanganese trioxide abrasive grains added in each pH range were eluted. From this result, it is understood that an aqueous solution containing at least one of ascorbic acid and erythorbic acid exhibits a certain degree or more of solubility to the dimanganese trioxide abrasive grains over a wide pH range.
又，由實施例1~3及6~8之結果可知：藉由將包含抗壞血酸及異抗壞血酸之至少一者的水溶液之pH值設為2~5，則溶解三氧化二錳研磨粒之能力進一步提昇。 Further, from the results of Examples 1 to 3 and 6 to 8, it is understood that the ability to dissolve the particles of dimanganese trioxide is further improved by setting the pH of the aqueous solution containing at least one of ascorbic acid and erythorbic acid to 2 to 5. Upgrade.
另一方面，比較例1~5之包含檸檬酸之水溶液中，於相同之pH值下進行比較時，結果僅為藉由包含抗壞血酸或異抗壞血酸之水溶液而溶出之三氧化二錳研磨粒的25%左右之研磨粒溶出。又，於比較例7之包含順丁烯二酸之溶液中，三氧化二錳研磨粒之溶出量顯著下降。進而，於比較例6、8~11之包含過氧化氫水之水溶液中，於pH值為4以上時，三氧化二錳研磨粒之溶出量顯著下降。認為係由於順丁烯二酸對於三氧化二錳研磨粒不具有還原能力，因而溶出量顯著下降。 On the other hand, in the aqueous solutions containing citric acid of Comparative Examples 1 to 5, when compared at the same pH value, the results were only 25 of the dimanganese trioxide abrasive grains which were eluted by the aqueous solution containing ascorbic acid or erythorbic acid. The abrasive grains of about % are dissolved. Further, in the solution containing maleic acid of Comparative Example 7, the elution amount of the dimanganese trioxide abrasive grains was remarkably lowered. Further, in the aqueous solution containing hydrogen peroxide water of Comparative Examples 6 and 8 to 11, when the pH was 4 or more, the elution amount of the dimanganese trioxide abrasive grains was remarkably lowered. It is considered that since the maleic acid does not have a reducing ability for the dimanganese trioxide abrasive grains, the amount of elution is remarkably lowered.
此外，亦關於含有抗壞血酸衍生物之水溶液中三氧化二錳研磨粒之溶出量進行評價，但未能觀察到促進三氧化二錳研磨粒溶出之效果。認為其原因在於：由於以磷酸抗壞血酸鎂、抗壞血酸葡糖苷為代表之抗壞血酸衍生物係形成為抑制抗壞血酸氧化之結構，故而無法還原三氧化二錳，無法促進三氧化二錳研磨粒之溶出。 Further, the amount of elution of the dimanganese trioxide abrasive grains in the aqueous solution containing the ascorbic acid derivative was also evaluated, but the effect of promoting the dissolution of the dimanganese trioxide abrasive grains was not observed. This is considered to be because the ascorbic acid derivative represented by magnesium ascorbyl phosphate and ascorbyl glucoside is formed to inhibit oxidation of ascorbic acid, so that manganese trioxide cannot be reduced, and dissolution of the dimanganese trioxide abrasive grains cannot be promoted.
利用包含平均粒徑1 μmφ之三氧化二錳研磨粒10質量%、及作為分散劑之丙烯酸-順丁烯二酸共聚物之鈉鹽0.1質量%的漿料與硬質胺基甲酸酯墊，使用單面研磨機(SpeedFam製造之FAM12B)對50 mm見方之鋁矽酸鹽玻璃板的單面進行研磨加工。研磨後，作為預洗淨，利用純水對玻璃板進行浸漬洗淨，且於表2所示之條件下進行超音波洗淨，其後利用純水進行浸漬洗淨。然後，利用純水沖洗玻璃板。之後，使玻璃板乾燥。 Using a slurry and a hard amine substrate pad containing 10% by mass of dimanganese trioxide abrasive grains having an average particle diameter of 1 μmφ and 0.1% by mass of a sodium salt of an acrylic acid-maleic acid copolymer as a dispersing agent, One side of a 50 mm square aluminosilicate glass plate was ground using a single-sided grinder (FAM12B manufactured by SpeedFam). After the polishing, the glass plate was immersed and washed with pure water as a pre-wash, and subjected to ultrasonic cleaning under the conditions shown in Table 2, and then immersed and washed with pure water. Then, rinse the glass plate with pure water. Thereafter, the glass plate is dried.
乾燥後，藉由以下之方法1或方法2檢查三氧化二錳研磨粒之殘留狀況。將其結果示於表2中。 After drying, the residual state of the dimanganese trioxide abrasive grains was examined by the following method 1 or method 2. The results are shown in Table 2.
(方法1)乾燥後，目視檢查殘留於玻璃板上之三氧化二錳研磨粒。將可確認到殘渣之情形評價為×，將未能確認到殘渣之情形評價為○。 (Method 1) After drying, the dimanganese trioxide abrasive grains remaining on the glass plate were visually inspected. The case where the residue was confirmed was evaluated as ×, and the case where the residue was not confirmed was evaluated as ○.
(方法2)乾燥後，一面對玻璃板照射高亮度光源，一面檢查殘留於玻璃板上之三氧化二錳研磨粒。將可確認到殘渣之情形評價為×，將未能確認到殘渣之情形評價為○。 (Method 2) After drying, the di-manganese trioxide abrasive grains remaining on the glass plate were inspected while irradiating the glass plate with a high-intensity light source. The case where the residue was confirmed was evaluated as ×, and the case where the residue was not confirmed was evaluated as ○.
如表2所示，關於利用包含抗壞血酸及異抗壞血酸之至少一者的洗淨液洗淨玻璃板的實施例11~14，可確認於超音波槽之底部不存在三氧化二錳研磨粒殘渣，三氧化二錳研磨粒溶解於洗淨液中。另一方面，關於利用不含抗壞血酸及異抗壞血酸之任一者的洗淨液洗淨玻璃板的比較例12~17，可確認到三氧化二錳研磨粒殘留於玻璃板上。 As shown in Table 2, in Examples 11 to 14 in which the glass plate was washed with a cleaning liquid containing at least one of ascorbic acid and erythorbic acid, it was confirmed that there was no di-manganese-containing abrasive grain residue at the bottom of the ultrasonic wave tank. The dimanganese trioxide abrasive particles are dissolved in the cleaning solution. On the other hand, in Comparative Examples 12 to 17 in which the glass plate was washed with a washing liquid containing no ascorbic acid or erythorbic acid, it was confirmed that the dimanganese trioxide abrasive grains remained on the glass plate.
由該結果可知，利用於使用包含三氧化二錳研磨粒之研磨劑研磨玻璃的步驟後，包括使用包含抗壞血酸及異抗壞 血酸之至少一者的洗淨液洗淨玻璃的洗淨步驟之本發明之方法，可自玻璃之表面有效地去除三氧化二錳研磨粒。 From the results, it is understood that the step of grinding the glass using the abrasive containing the trimanganese abrasive grains includes the use of ascorbic acid and the like The method of the present invention for washing the cleaning liquid of at least one of the blood acids, the manganese trioxide abrasive grains can be effectively removed from the surface of the glass.
以上使用特定之態樣詳細地說明了本發明，但業者清楚可於不偏離本發明之意圖與範圍之前提下作出各種變更及變形。此外，本申請案係基於2011年7月12日提出申請之日本專利申請案(日本專利特願2011-154312)，並藉由引用而援引其全部內容。 The present invention has been described in detail above with reference to the specific embodiments thereof. It is understood that various changes and modifications may be made without departing from the spirit and scope of the invention. In addition, the present application is based on Japanese Patent Application No. 2011-154312, filed on Jan.
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| JP4560278B2 (en) * | 2003-05-09 | 2010-10-13 | Ｊｓｒ株式会社 | Non-chemical mechanical polishing aqueous solution, polishing agent set, and manufacturing method for manufacturing semiconductor device |
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