JP5627108B2 - Abrasive - Google Patents

Description

  The present invention relates to an abrasive.

Conventionally, various types of abrasives having inorganic oxide fine particles dispersed in a dispersion medium have been proposed.
For example, Patent Document 1 discloses a composite oxide having a core-shell structure in which the average particle diameter and the thickness of the shell part are within a specific range, and the core part is made of SiO ₂ , Al ₂ O ₃ , CeO _2, or the like. A dispersion of fine particles for polishing is described, wherein the shell portion is made of silica / alumina or silica / zirconia, and the content of silica in the composite oxide is a specific amount. And it is described that according to such an abrasive | polishing agent, the abrasive | polishing agent which set the grinding | polishing speed, the grinding | polishing precision, and the grinding | polishing characteristic to the appropriate value is obtained.

Japanese Patent No. 4190198

  The abrasive described in Patent Document 1 has excellent polishing characteristics, but development of an abrasive having more excellent polishing characteristics is desired.

An object of the present invention is to solve the above problems.
That is, the present invention has an object to provide an abrasive having excellent polishing characteristics, specifically, an abrasive having a high polishing rate and less scratches (linear traces) when an object to be polished is polished using the same. And

The inventor has intensively studied to solve the above-mentioned problems, and has completed the present invention.
The present invention includes the following (1) to (4) .
(1) Inorganic oxide fine particles having a solid acid amount or a solid base amount of 0.01 mmol / g or more and an average particle diameter of 2 μm or less are dispersed in a dispersion medium, and the pH is 8.0 to 11.5. A certain abrasive.
(2) The oxide-based mass molar concentration (mol / kg) of an element having a relatively high valence is smaller than the oxide-based mass molar concentration (mol / kg) of an element having a relatively low valence. The polishing agent according to (1) above, which is the inorganic oxide fine particle mainly composed of an oxide containing two elements at the same or large ratio.
(3) The inorganic oxide fine particles are selected from the group consisting of Si, Al, B, Mg, Ca, Ba, Mo, Zr, Ga, Be, Sr, Y, La, Ce, Sn, Fe, Zn, and Ti. The abrasive | polishing agent as described in said (1) or (2) which has as a main component the oxide containing the said at least 2 element.
(4) the inorganic oxide fine particles are at least one element selected from the group consisting of B, Ba, Mo, Ga, Be, Sr, Y, La, Fe, Ti, Al, Zr, Ce, Sn, and Zn; An oxide containing at least one element selected from the group consisting of Si, Mg and Ca as a main component, an oxide containing Ti and Zr as a main component, or an oxide containing Mg and Si The abrasive | polishing agent in any one of said (1)-(3) which makes a main component .

  ADVANTAGE OF THE INVENTION According to this invention, when a grinding | polishing target object is grind | polished using it, an abrasive | polishing agent with a quick grinding | polishing speed | rate and few scratches (linear trace) can be provided.

The present invention will be described.
In the present invention, inorganic oxide fine particles having a solid acid amount or a solid base amount of 0.01 mmol / g or more and an average particle size of 2 μm or less are dispersed in a dispersion medium, and the pH is 8.0 to 11.5. Is an abrasive.
Hereinafter, such an abrasive is also referred to as “the abrasive of the present invention”.

The amount of solid acid and the amount of solid base will be described.
The inorganic oxide fine particles contained in the abrasive of the present invention have a solid acid amount of 0.01 mmol / g or more, or a solid base amount of 0.01 mmol / g or more. Of course, the solid acid amount may be 0.01 mmol / g or more, and the solid base amount may be 0.01 mmol / g or more.
The abrasive of the present invention in which the inorganic oxide fine particles having such a solid acid amount or solid base amount are dispersed in a dispersion medium is more polished than a conventional one when a polishing object is polished using this. Speed is high and scratches (linear traces) are reduced. The present inventor has intensively studied, considering that the polishing characteristics of an abrasive may depend on the amount of solid acid or solid base rather than the hardness of particles contained in the abrasive. A polishing agent having a specific solid acid amount or solid base amount, in which inorganic oxide fine particles having a specific average particle size are dispersed in a dispersion medium, and having a specific range of pH has excellent polishing characteristics (polishing And the present invention was completed.

Here, the amount of solid acid means a value obtained by measurement by the following temperature programmed desorption method (NH ₃ -TPD).
First, inorganic oxide fine particles are separated from the abrasive of the present invention. Specifically, after filtering the abrasive of the present invention to separate the solid content, the solid content is placed in a sealed container and kept at 400 ° C. and 1 × 10 ⁻⁴ Torr for 4 hours to remove the dispersion medium. Evaporate to obtain only inorganic oxide fine particles. Next, 1 g of the obtained inorganic oxide fine particles are put in a reaction tube, pretreated by holding 2 hours while flowing 500 ° C. He, and then allowed to cool, so that the temperature of the inorganic oxide fine particles is 60 ° C. Next, ammonia is adsorbed on the surface of the inorganic oxide fine particles by flowing ammonia gas at 60 ° C. into the reaction tube for 30 minutes. Next, the temperature in the reaction tube is raised to 600 ° C. at 10 ° C./min, and ammonia desorbed in the process is detected by Q-MASS to obtain a diagram showing a spectrum. Then, by obtaining the total area (total acid amount) of the ammonia temperature-programmed desorption spectrum obtained, the solid acid amount (mol / g) per 1 g of the inorganic oxide fine particles is obtained. Here, the total area of the spectrum is an integrated value from 60 ° C to 600 ° C.

Also, solid amount of base, Atsushi Nobori spectroscopy for obtaining the solid acid amount of the ammonia gas used in (NH ₃ -TPD) as CO ₂ gas, the other are all the same as the Atsushi Nobori spectroscopy (CO ₂ -A value obtained by measurement by (TPD).

In the abrasive of the present invention, the inorganic oxide fine particles have an average particle size of 2 μm or less, preferably 1 μm or less, more preferably 500 nm or less, more preferably 300 nm or less, and more preferably 150 nm or less. More preferably, it is more preferably 100 nm or less, and even more preferably 50 nm or less. The average particle diameter is preferably 5 nm or more, more preferably 10 nm or more, and further preferably 15 nm or more.
In the present invention, the average particle diameter means the median diameter.

In the abrasive of the present invention, the inorganic oxide fine particles preferably have a standard deviation (SD) of particle size distribution of 10 nm or more, preferably 15 nm or more, and preferably 20 nm or more. More preferably, it is 30 nm or more, more preferably 35 nm or more. Further, it is preferably 100 nm or less, more preferably 80 nm or less, more preferably 70 nm or less, and further preferably 60 nm or less.
The present inventor has found that the polishing rate is increased when the standard deviation is large, that is, when particles of various sizes are included and the particle size is not biased. The present inventor has found that the standard deviation is small even with the same average particle size, that is, if the particle size is uniform, the polishing rate is low and the sustainability of polishing is also poor.

In the abrasive of the present invention, the maximum value of the particle size distribution of the inorganic oxide fine particles is preferably 3,000 nm, more preferably 2,000 nm, more preferably 1,000 nm, and 700 nm. Is more preferable, 500 nm is more preferable, and 300 nm is still more preferable. Further, the minimum value is preferably 1 nm, more preferably 2 nm, and further preferably 5 nm.
When the maximum value and the minimum value in the particle size distribution are as described above, the polishing rate of the abrasive of the present invention tends to increase.

  In the present invention, the average particle diameter, the standard deviation (SD), the maximum value and the minimum value in the particle size distribution are obtained based on the particle size distribution obtained by the dynamic light scattering method.

In the abrasive of the present invention, the inorganic oxide fine particles are made of Si, Al, B, Mg, Ca, Ba, Mo, Zr, Ga, Be, Sr, Y, La, Ce, Sn, Fe, Zn, and Ti. It is preferable that the main component is an oxide containing at least two elements selected from. The inorganic oxide fine particles are more preferably substantially composed of such an oxide. Note that “substantially” means that impurities mixed from the raw materials and the manufacturing process can be included.
The inorganic oxide fine particles include at least one element selected from the group consisting of B, Ba, Mo, Ga, Be, Sr, Y, La, Fe, Ti, Al, Zr, Ce, Sn, and Zn, and Si. An oxide containing at least one element selected from the group consisting of Mg and Ca , containing Ti and Zr, or containing Mg and Si, and containing two or more elements. Is preferred. The inorganic oxide fine particles are more preferably substantially composed of such an oxide.
Furthermore, the inorganic oxide fine particles may be a mixture of two or more kinds of oxides or a complex oxide containing two or more kinds of elements.

The inorganic oxide fine particles are selected from the group consisting of Si, Al, B, Mg, Ca, Ba, Mo, Zr, Ga, Be, Sr, Y, La, Ce, Sn, Fe, Zn, and Ti. The main component is an oxide containing at least two elements having different valences. The inorganic oxide fine particles are more preferably substantially composed of such an oxide.
In addition, when two elements having different valences are included, the oxide molar mass (mol / kg) of an element having a relatively high valence is an oxide equivalent mass of an element having a relatively low valence. It is preferable that the oxide contains two elements at the same or larger ratio with respect to the molar concentration (mol / kg). For example, an oxide containing Si and Al at a ratio such that the molar molar concentration of tetravalent Si in terms of SiO ₂ is the same as or larger than the molar molar concentration of trivalent Al in terms of Al ₂ O ₃ . It is preferable that
The present inventors have found that when two elements having different valences are contained, the amount of solid acid or solid base of the inorganic oxide fine particles tends to be 0.01 mmol / g or more.
In addition, when two elements having the same valence are included, if the abundance ratio of these elements (ratio by mass molar concentration (mol / kg)) is different, similarly, the solid acid amount or solid base of the inorganic oxide fine particles The present inventor has found that the amount tends to be 0.01 mmol / g or more.

  The inorganic oxide fine particles may contain cerium but may not contain cerium. In recent years, the price of cerium (Ce) has risen with a decrease in reserves, and therefore development of an abrasive that does not contain cerium is desired. The abrasive of the present invention has excellent polishing characteristics even when it does not contain cerium.

  In the abrasive of the present invention, the shape of the inorganic oxide fine particles is not particularly limited, and may be, for example, spherical.

The dispersion medium in the abrasive | polishing agent of this invention is not specifically limited, It is preferable that it is aqueous system and it is more preferable that it is water.
The solid content concentration in the abrasive of the present invention is not particularly limited, but is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, and further preferably 20 to 40% by mass.

The abrasive of the present invention has a pH of 8.0 to 11.5, preferably 8.7 to 11.3, and more preferably 9.2 to 11.0.
With such a pH, it is easy to maintain a state in which the inorganic oxide fine particles are stably dispersed. If the pH is too low, the inorganic oxide fine particles tend to aggregate. If the pH is too high, the inorganic oxide fine particles may be dissolved.
In order to obtain such a pH, the abrasive of the present invention can contain a conventionally known stabilizer such as NaOH.

  Such a polishing agent of the present invention is excellent in polishing characteristics (specifically, polishing rate and scratch) and can be preferably used as a polishing agent for finish polishing of the surface of a silicon wafer, a semiconductor device substrate or the like. Further, it can be preferably used as an abrasive for primary or secondary polishing of a glass hard disk substrate.

Moreover, it is preferable that the polishing agent of the present invention has a polishing rate of 160 nm / min or more and a scratch number of 8 pieces / cm ² or less.
The polishing rate is preferably 170 nm / min or more, more preferably 175 nm / min or more, and further preferably 180 nm / min or more.
The number of scratches is preferably 7 pieces / cm ² or less, more preferably 6 pieces / cm ² or less, and further preferably 5 pieces / cm ² or less.

In the present invention, the polishing rate means that when the SiO ₂ film is polished by the following method.
As a test substrate, a 29 mm square substrate made of silicon having a 1 μm thick SiO ₂ film formed on the main surface by a vapor deposition method is prepared. Then, the SiO ₂ film on the test substrate is polished with the polishing agent of the present invention using a polishing machine (for example, NF300 manufactured by Nano Factor). Here, the polishing conditions are polishing load: 350 g / cm ² , polishing time: 30 seconds, slurry flow rate: 70 ml / min, and the polishing pad has a compressibility of 1%, Asker C hardness 95, Shore D hardness 60 (For example, IC1000 manufactured by Rodel Nitta Co., Ltd.) is used, and the polishing pad rotation speed is 30 rpm.
Then, the polishing rate (nm / min) is obtained from the change in thickness (nm) of the SiO ₂ film calculated from the change in mass of the test substrate before and after polishing and the polishing time (30 seconds).

In the present invention, the number of scratches means that when the metal copper film is polished by the following method.
A 30 mm square substrate made of silica / alumina is prepared as a test substrate. Then, as in the case of the above-described measurement of the polishing rate, the test substrate is polished with the polishing agent of the present invention using a polishing machine (for example, NF300, manufactured by Nano Factor). Here, the polishing conditions and the polishing pad to be used are the same as those in the measurement of the polishing rate.
Then, the 10 mm square near the center of the surface of the test substrate after polishing is divided into 30 fields of view with a metal microscope, observed at a magnification of 200 times, and the total number of scratches (linear marks) is counted as the number of scratches. .

The manufacturing method of the abrasive | polishing agent of this invention is not specifically limited, For example, it can manufacture by the following methods.
First, an aqueous solution in which a salt containing at least one element selected from the group consisting of B, Ba, Mo, Ga, Be, Sr, Y, La, Fe, Ti, Al, Zr, Ce, Sn, and Zn is dissolved. And an aqueous solution in which a salt containing at least one element selected from the group consisting of Si, Mg and Ca is dissolved, and these are mixed to obtain a composite salt containing two kinds of elements. Or two different valences selected from the group consisting of Si, Al, B, Mg, Ca, Ba, Mo, Zr, Ga, Be, Sr, Y, La, Ce, Sn, Fe, Zn, and Ti. Two types of aqueous solutions in which each of the element salts are dissolved are prepared and mixed to obtain a composite salt containing the two types of elements. Here, the molar concentration (mol / L) in terms of oxide of the element having a high valence is the same or larger than the molar concentration in terms of oxide (mol / L) of the element having a low valence, It is preferable to adjust the concentrations and amounts of the two types of aqueous solutions. For example, the molar concentration (mol / L) of tetravalent Si in terms of SiO ₂ is relatively large, and the molar concentration (mol / L) of trivalent Al in terms of Al ₂ O ₃ is relatively small. It is preferable to prepare the same amount of aqueous solution and mix them to obtain an oxide containing Si and Al. In this case, the present inventor has found that the amount of the solid acid and / or the amount of the solid base of the obtained inorganic oxide fine particles tends to be 0.01 mmol / g or more.
In addition, examples of water-soluble salts containing the above elements include sulfates, nitrates, hydrochlorides, and organic acid salts. Moreover, when mixing, it is preferable to maintain the pH of the mixed solution at about 6 while adding other acidic aqueous solution or alkaline aqueous solution as necessary. Further, the mixing is performed with stirring, and after the mixing is completed, the mixture is preferably left for about 1 hour while being maintained at a temperature of about room temperature (about 25 ° C.).
The composite salt thus obtained is preferably washed with water, and then dried at about 120 ° C. for about 10 to 20 hours. And after grind | pulverizing as needed, it bakes by hold | maintaining at about 400 degreeC for several hours. Here, if the calcination temperature is too high, the solid acid amount and / or the solid base amount of the inorganic oxide fine particles tends to be difficult to be 0.01 mmol / g or more.
And the abrasive | polishing agent of this invention is obtained by disperse | distributing the obtained inorganic oxide microparticles | fine-particles in dispersion media, such as water. Here, NaOH or the like may be added so that the pH becomes a desired value. Moreover, after adding the obtained inorganic oxide fine particles to a dispersion medium, it is preferable to mix and grind using a sand mill or the like.

<Example 1>
1800 g of a sodium silicate aqueous solution having a SiO ₂ equivalent concentration of 1.50 mol (mol / L) and 1800 g of an aluminum sulfate aqueous solution having an Al ₂ O ₃ equivalent concentration of 0.10 mol (mol / L) were prepared. Moreover, 5 mass% NaOH aqueous solution and 5 mass% sulfuric acid aqueous solution were prepared.
Next, a container was prepared, and the mixed solution obtained in the container was stirred while the sodium silicate aqueous solution and the aluminum sulfate aqueous solution were poured into the container little by little. Here, the pH of the mixed solution obtained in the container was always measured using a pH meter, and the above two aqueous solutions were poured so that the pH was maintained at 6. Moreover, 5 mass% NaOH aqueous solution and 5 mass% sulfuric acid aqueous solution were poured in a suitable quantity as needed, and pH was adjusted.

Thus, after pouring the whole quantity of sodium silicate aqueous solution and aluminum sulfate aqueous solution in a container, stirring was stopped and it was left to stand at 25 degreeC for 1 hour. As a result, a silica-alumina gel was obtained.
Next, the obtained gel was transferred to Nutsche with a filter cloth, and after adding pure water having a mass about 100 times that of the gel to the gel, the gel was washed by filtration using a vacuum suction device.

  Next, the gel after washing was dried at 120 ° C. for 17 hours, and then the obtained dried body was pulverized and pulverized using an agate mortar. And the obtained fine powder was baked at 400 degreeC for 3 hours, and the inorganic oxide fine particle was obtained.

Next, the solid acid amount and solid base amount of the inorganic oxide fine particles thus obtained were measured. The measurement is performed by the above-described temperature programmed desorption method (NH ₃ -TPD, CO ₂ -TPD). A fully automatic temperature programmed desorption spectrometer (TPD-1-ATw, manufactured by Bell Japan) was used. A quadrupole mass spectrometer (Q-MASS) (mass number 1 to 100) was used as a detector.
The measurement results are shown in Table 1.

Next, 20 g of the obtained inorganic oxide fine particles were added to 1000 ml of pure water, and further added with a 5% by mass aqueous sodium hydroxide solution so that the pH was 11.5, a sand mill (media type: ZrO ₂ and media diameter: 50 μm) and pulverized and mixed for 6 hours. Then, an abrasive in which inorganic oxide fine particles were dispersed was obtained.
It was 11.0 when pH of the obtained abrasive | polishing agent was measured using the pH meter.

Next, the average particle diameter (median diameter) of the inorganic oxide fine particles contained in the obtained abrasive was measured. Specifically, a sample having a solid content of 0.2% by mass prepared by mixing pure water into 0.1 g of an abrasive was put in a quartz cell having a length of 1 cm, a width of 1 cm, and a height of 5 cm, The particle size distribution of the particle group measured using an ultrafine particle size analyzer (model ELS-Z2 manufactured by Otsuka Electronics Co., Ltd.) by a dynamic light scattering method was obtained, and this was calculated by cumulant analysis.
The measurement results are shown in Table 1.

Next, the test which evaluates the grinding | polishing characteristic of the obtained abrasive | polishing agent was done.
First, the polishing rate was measured. Specifically, a 29 mm square test substrate (substrate on which the SiO ₂ film was formed) was polished using NF300 manufactured by Nano Factor, and the polishing rate (nm / min) of the SiO ₂ film was measured. Here, the polishing conditions were polishing load: 350 g / cm ² , polishing time: 30 seconds, slurry flow rate: 70 ml / min, polishing pad: IC1000 manufactured by Rodel Nitta, polishing pad rotation speed: 30 rpm. In addition, what adjusted the density | concentration of the inorganic oxide in an abrasive | polishing agent to 20 mass% was used as a slurry.
The measurement results are shown in Table 1.

Next, the number of scratches was measured. Here, a 30 mm square substrate made of silica / alumina was used as the test substrate. The polishing conditions were the same as in the measurement of the polishing rate. Then, a 10 mm square near the center of the surface of the test substrate after polishing was divided into 30 fields of view with a metal microscope, observed at a magnification of 200 times, and the number of scratches (linear marks) was counted and totaled.
The measurement results are shown in Table 1.
In Table 1, “○” indicates that the number of scratches is 8 pieces / cm ² or less, and “△” indicates that there are 8 pieces / cm ^{2 or} more and 20 pieces / cm ² or less, and 20 pieces / cm ^{2 or} more. Was represented as “×”.

<Example 2>
In Example 1, first, a sodium silicate aqueous solution having a SiO ₂ equivalent concentration of 1.50 molar concentration (mol / L) and an aluminum sulfate aqueous solution having an Al ₂ O ₃ equivalent concentration of 0.10 molar concentration (mol / L). The silica-alumina gel was obtained by mixing these, and in Example 2, a sodium silicate aqueous solution having a SiO ₂ equivalent concentration of 1.33 mol (mol / L), and Al ₂ O _{3 An} aluminum sulfate aqueous solution having a converted concentration of 0.20 molar concentration (mol / L) was prepared, and these were mixed in the same manner as in Example 1 to obtain a silica-alumina gel.
Others were operated in the same manner as in Example 1 and the same measurement was performed.
The measurement results are shown in Table 1.

<Example 3>
In Example 1, first, a sodium silicate aqueous solution having a SiO ₂ equivalent concentration of 1.50 molar concentration (mol / L) and an aluminum sulfate aqueous solution having an Al ₂ O ₃ equivalent concentration of 0.10 molar concentration (mol / L). The silica-alumina gel was obtained by mixing these, and in Example 3, a sodium silicate aqueous solution having a SiO ₂ equivalent concentration of 1.17 mol concentration (mol / L), and Al ₂ O _{3 An} aluminum sulfate aqueous solution having a converted concentration of 0.30 molar concentration (mol / L) was prepared, and these were mixed in the same manner as in Example 1 to obtain a silica-alumina gel.
Others were operated in the same manner as in Example 1 and the same measurement was performed.
The measurement results are shown in Table 1.

<Example 4>
In Example 1, first, a sodium silicate aqueous solution having a SiO ₂ equivalent concentration of 1.50 molar concentration (mol / L) and an aluminum sulfate aqueous solution having an Al ₂ O ₃ equivalent concentration of 0.10 molar concentration (mol / L). The silica-alumina gel was obtained by mixing these, and in Example 4, a sodium silicate aqueous solution having a SiO ₂ equivalent concentration of 1.17 mol concentration (mol / L), and La ₂ O _{3 A} lanthanum nitrate aqueous solution having a converted concentration of 1.00 molar (mol / L) was prepared, and these were mixed in the same manner as in Example 1 to obtain a silica-lanthanium gel.
Others were operated in the same manner as in Example 1 and the same measurement was performed.
The measurement results are shown in Table 1.

<Example 5>
In Example 1, first, a sodium silicate aqueous solution having a SiO ₂ equivalent concentration of 1.50 molar concentration (mol / L) and an aluminum sulfate aqueous solution having an Al ₂ O ₃ equivalent concentration of 0.10 molar concentration (mol / L). Were prepared, and after stirring, the stirring was stopped, and the mixture was allowed to stand for 1 hour while maintaining a temperature of 25 ° C. to obtain a silica-alumina gel. In Example 5, the SiO ₂ equivalent concentration was 1.17 mol. Prepare a sodium silicate aqueous solution with a concentration (mol / L) and a zirconium nitrate aqueous solution with a ZrO ₂ equivalent concentration of 0.20 molar concentration (mol / L), and after mixing these, stirring is stopped and the temperature is kept at 40 ° C. This was left for 1 hour to obtain a silica / zirconia gel.
Others were operated in the same manner as in Example 1 and the same measurement was performed.
The measurement results are shown in Table 1.

<Example 6>
In Example 1, first, a sodium silicate aqueous solution having a SiO ₂ equivalent concentration of 1.50 molar concentration (mol / L) and an aluminum sulfate aqueous solution having an Al ₂ O ₃ equivalent concentration of 0.10 molar concentration (mol / L). The silica-alumina gel was obtained by mixing these, and in Example 6, a ZrO ₃ converted concentration of 1.00 mol concentration (mol / L) zirconyl ammonium carbonate aqueous solution, and TiO ₂ A titanium tetrachloride aqueous solution having a converted concentration of 0.30 molar concentration (mol / L) was prepared, and these were mixed in the same manner as in Example 1 to obtain a zirconia / titania gel.
Others were operated in the same manner as in Example 1 and the same measurement was performed.
The measurement results are shown in Table 1.

<Example 7>
In Example 1, first, a sodium silicate aqueous solution having a SiO ₂ equivalent concentration of 1.50 molar concentration (mol / L) and an aluminum sulfate aqueous solution having an Al ₂ O ₃ equivalent concentration of 0.10 molar concentration (mol / L). The silica-alumina gel was obtained by mixing these, and in Example 7, the sodium silicate aqueous solution having a SiO ₂ equivalent concentration of 1.17 mol (mol / L) and the TiO ₂ equivalent were obtained. A titanium tetrachloride aqueous solution having a concentration of 1.17 molar concentration (mol / L) was prepared, and these were mixed in the same manner as in Example 1 to obtain a silica-titania gel.
Others were operated in the same manner as in Example 1 and the same measurement was performed.
The measurement results are shown in Table 1.

<Example 8>
In Example 1, first, a sodium silicate aqueous solution having a SiO ₂ equivalent concentration of 1.50 molar concentration (mol / L) and an aluminum sulfate aqueous solution having an Al ₂ O ₃ equivalent concentration of 0.10 molar concentration (mol / L). The silica-alumina gel was obtained by mixing these, and in Example 8, a sodium silicate aqueous solution having a SiO ₂ equivalent concentration of 1.17 mol (mol / L) and an MgO equivalent concentration Prepared a magnesium nitrate aqueous solution having a 0.30 molar concentration (mol / L), and these were mixed in the same manner as in Example 1 to obtain a silica-magnesia gel.
Others were operated in the same manner as in Example 1 and the same measurement was performed.
The measurement results are shown in Table 1.

<Example 9>
In Example 1, first, a sodium silicate aqueous solution having a SiO ₂ equivalent concentration of 1.50 molar concentration (mol / L) and an aluminum sulfate aqueous solution having an Al ₂ O ₃ equivalent concentration of 0.10 molar concentration (mol / L). The silica-alumina gel was obtained by mixing these, and in Example 9, a sodium silicate aqueous solution having a SiO ₂ equivalent concentration of 1.17 mol (mol / L) and a CeO ₂ equivalent were obtained. A silica / ceria gel was obtained by preparing an aqueous cerium nitrate solution having a concentration of 1.17 molar concentration (mol / L) and mixing them in the same manner as in Example 1.
Others were operated in the same manner as in Example 1 and the same measurement was performed.
The measurement results are shown in Table 1.

<Comparative Example 1>
In Example 1, first, a sodium silicate aqueous solution having a SiO ₂ equivalent concentration of 1.50 molar concentration (mol / L) and an aluminum sulfate aqueous solution having an Al ₂ O ₃ equivalent concentration of 0.10 molar concentration (mol / L). The silica-alumina gel was obtained by mixing these, but in Comparative Example 1, 1800 g of 0.01 molar concentration (mol / L) sulfuric acid was prepared instead of the aluminum sulfate aqueous solution. Were mixed to obtain a solid content.
The solid content obtained here was handled in the same manner as the “gel” in Example 1, and the others were operated in the same manner as in Example 1 and the same measurement was performed.
The measurement results are shown in Table 1.

<Comparative example 2>
In Example 1, first, a sodium silicate aqueous solution having a SiO ₂ equivalent concentration of 1.50 molar concentration (mol / L) and an aluminum sulfate aqueous solution having an Al ₂ O ₃ equivalent concentration of 0.10 molar concentration (mol / L). The silica-alumina gel was obtained by mixing these, and in Comparative Example 2, instead of the sodium silicate aqueous solution having a SiO ₂ conversion concentration of 1.17 mol concentration (mol / L), ZrO ₃ Ammonium zirconium carbonate having a converted concentration of 1.00 mol (mol / L) was prepared, and 1.17 mol instead of an aluminum sulfate aqueous solution having an Al ₂ O ₃ converted concentration of 0.10 mol (mol / L) 1800 g of nitric acid having a concentration (mol / L) was prepared and mixed to obtain a solid content.
The solid content obtained here was handled in the same manner as the “gel” in Example 1, and the others were operated in the same manner as in Example 1 and the same measurement was performed.
The measurement results are shown in Table 1.

<Comparative Example 3>
In Example 1, first, a sodium silicate aqueous solution having a SiO ₂ equivalent concentration of 1.50 molar concentration (mol / L) and an aluminum sulfate aqueous solution having an Al ₂ O ₃ equivalent concentration of 0.10 molar concentration (mol / L). The silica-alumina gel was obtained by mixing these, but in Comparative Example 3, the aqueous solution of zirconyl ammonium carbonate having a ZrO ₃ conversion concentration of 1.00 mol concentration (mol / L) and TiO _{2 was obtained.} A titanium tetrachloride aqueous solution having a converted concentration of 0.30 molar concentration (mol / L) was prepared, and these were mixed in the same manner as in Example 1 to obtain a zirconia / titania gel.
In Example 1, the gel after washing was dried and then pulverized, and the obtained fine powder was fired at 400 ° C. for 3 hours. In Comparative Example 3, the fine powder obtained in the same manner was heated at 1000 ° C. for 3 hours. Firing was performed to obtain inorganic oxide fine particles.
Others were operated in the same manner as in Example 1 and the same measurement was performed.
The measurement results are shown in Table 1.

<Comparative example 4>
In Example 1, first, a sodium silicate aqueous solution having a SiO ₂ equivalent concentration of 1.50 molar concentration (mol / L) and an aluminum sulfate aqueous solution having an Al ₂ O ₃ equivalent concentration of 0.10 molar concentration (mol / L). The silica-alumina gel was obtained by mixing these, and in Comparative Example 4, the sodium silicate aqueous solution having a SiO ₂ equivalent concentration of 0.01 mol (mol / L) and the TiO ₂ equivalent were obtained. A titanium tetrachloride aqueous solution having a concentration of 0.30 molar concentration (mol / L) was prepared, and these were mixed in the same manner as in Example 1 to obtain a silica-titania gel.
Others were operated in the same manner as in Example 1 and the same measurement was performed.
The measurement results are shown in Table 1.

<Comparative Example 5>
In Example 1, first, a sodium silicate aqueous solution having a SiO ₂ equivalent concentration of 1.50 molar concentration (mol / L) and an aluminum sulfate aqueous solution having an Al ₂ O ₃ equivalent concentration of 0.10 molar concentration (mol / L). And a silica-alumina gel was obtained by mixing these. In Comparative Example 5, a ZrO3 ammonium carbonate aqueous solution having a ZrO ₃ equivalent concentration of 1.00 mol concentration (mol / L), and TiO _{2 was obtained.} A titanium tetrachloride aqueous solution having a converted concentration of 0.30 molar concentration (mol / L) was prepared, and these were mixed in the same manner as in Example 1 to obtain a zirconia / titania gel.
In Example 1, pure water was added to the inorganic oxide fine particles, and a 5% by mass aqueous sodium hydroxide solution was added so that the pH was 11.5, and the mixture was pulverized and mixed using a sand mill. In Comparative Example 5, a slurry obtained by adding pure water to inorganic oxide fine particles was pulverized and mixed using the same sand mill. That is, no sodium hydroxide aqueous solution was added. For this reason, the pH of the obtained abrasive | polishing agent was 4.0.
Others were operated in the same manner as in Example 1 and the same measurement was performed.
The measurement results are shown in Table 1.

The inorganic oxide fine particles contained in the abrasives of Examples 1 to 9 each had a solid acid amount of 0.02 mmol / g or more and an average particle size of 45 nm or less. Further, the amount of solid base was not detected except in Example 7, but Example 7 was 0.1 mmol / g. Moreover, pH of all abrasive | polishing agents was 11.0. And the polishing rate of the abrasive | polishing agent of such Examples 1-9 became high with 180 nm / min or more, and the number of scratches became 8 pieces / cm < ² > or less.

In Examples 1 to 3, a sodium silicate aqueous solution was used as an aqueous solution containing an element salt having a high valence, and an aluminum sulfate aqueous solution was used as an aqueous solution containing an element salt having a relatively low valence. Is. The molar concentration of SiO ₂ in terms of Si is tetravalent (mol / L): and [A], Al ₂ O ₃ molar Conversion Al trivalent (mol / L): [B ] and the The molar concentration ratio (“Molar concentration ratio [A / B]” in Table 1) is 1.0 or more. That is, the molar concentration in terms of oxide of an element having a high valence is higher.
In Example 4, a sodium silicate aqueous solution was used as an aqueous solution containing an element salt having a high valence, and an aqueous lanthanum nitrate solution was used as an aqueous solution containing an element salt having a relatively low valence. is there. The molar concentration (mol / L) of tetravalent Si in terms of SiO ₂ is 1.17, and the molar concentration of trivalent La in terms of La ₂ O ₃ (mol / L) is 1.00. The molar concentration ratio (“Molar concentration ratio [A / B]” in Table 1) is 1.2.
In Example 5, a sodium silicate aqueous solution and a zirconium nitrate aqueous solution were used, and the valences of Si and Zr were both 4. The molar concentration in terms of SiO ₂ (mol / L) is 1.17, the molar concentration in terms of ZrO ₂ (mol / L) is 0.20, and these molar concentration ratios (“ The molar ratio [A / B] ”) is 5.9.
In Example 6, an aqueous solution of ammonium zirconium carbonate was used as an aqueous solution containing an element salt having a high valence, and an aqueous titanium tetrachloride solution was used as an aqueous solution containing an element salt having a relatively low valence. Is. And the molar concentration (mol / L) in terms of ZrO _{3 of} hexavalent Zr is 1.00, the molar concentration (mol / L) in terms of TiO _{2 of} tetravalent Ti is 0.30, These molar concentration ratios ("Molar concentration ratio [A / B]" in Table 1) are 3.3.
In Example 7, a sodium silicate aqueous solution and a titanium tetrachloride aqueous solution were used, and the valences of Si and Ti were both 4. The molar concentration (mol / L) in terms of SiO ₂ is 1.17, the molar concentration in terms of TiO ₂ (mol / L) is 1.17, and the molar concentration ratio (“ The molar concentration ratio [A / B] ”) is 1.0.
In Example 8, a sodium silicate aqueous solution was used as an aqueous solution containing a salt of an element having a high valence, and a magnesium nitrate aqueous solution was used as an aqueous solution containing a salt of an element having a relatively low valence. is there. And the molar concentration (mol / L) in terms of SiO _{2 of} tetravalent Si is 1.17, and the molar concentration (mol / L) in terms of MgO of divalent Mg is 0.30. The molar concentration ratio (“Molar concentration ratio [A / B]” in Table 1) is 3.9.
In Example 9, a sodium silicate aqueous solution was used as an aqueous solution containing a salt of an element having a high valence, and a cerium nitrate aqueous solution was used as an aqueous solution containing a salt of an element having a relatively low valence. is there. And the molar concentration (mol / L) of tetravalent Si in terms of SiO ₂ is 1.17, and the molar concentration of trivalent Ce in terms of Ce ₂ O ₃ (mol / L) is 1.17. The molar concentration ratio (“Molar concentration ratio [A / B]” in Table 1) is 1.0.
Thus, in Examples 1-9, the molar concentration ratio [A / B] is all 1.0 or more.

On the other hand, the inorganic oxide fine particles in Comparative Example 1 consist only of silica, and neither solid acid amount nor solid base amount could be detected. That is, the amount of solid acid and the amount of solid base were almost zero. In this case, the polishing rate was as low as 100 nm / min. Further, the number of scratches was more than 8 / cm ^{2 and not} more than 20 / cm ² .

Also, Comparative Example 2 had almost the same result as Comparative Example 1. Specifically, the inorganic oxide fine particles in Comparative Example 2 consist only of silica, and neither solid acid amount nor solid base amount could be detected. The polishing rate was as low as 120 nm / min. Further, the number of scratches was very bad, exceeding 20 / cm ² .

The solid acid amount of the inorganic oxide fine particles in Comparative Example 3 was less than 0.01 mmol / g, and the solid base amount was not detected. This is considered to be due to the fact that the firing temperature was too high at 1000 ° C. In this case, the polishing rate was as low as 170 nm / min. Further, the number of scratches was very bad, exceeding 20 / cm ² .

The solid acid amount of the inorganic oxide fine particles in Comparative Example 4 was less than 0.01 mmol / g, and the solid base amount was not detected. This is probably because the mixing ratio of the two types of raw materials was not appropriate. That is, in Comparative Example 4, the oxide equivalent molar concentration (mol / L) of the aqueous solution containing the salt of the element having a low valence: [B], the oxide equivalent of the aqueous solution containing the salt of the element having a high valence. The molar ratio (mol / L): [A] ratio (the numerical value in the column represented by “molar concentration ratio [A / B]” in Table 1) is considered to be too low at 0.03. On the other hand, in Examples 1 to 9, this ratio (molar concentration ratio [A / B]) is a value larger than 1.0. That is, the molar concentration in terms of oxide (mol / mol) of an aqueous solution containing a salt of an element having a higher valence than the molar concentration in terms of oxide (mol / L) [B] of the aqueous solution containing the salt of an element having a lower valence. L) [A] is larger or the same.
In the case of Comparative Example 4, the number of scratches was very poor, exceeding 20 / cm ² .

The abrasive of Comparative Example 5 has a pH not 8.0 to 11.5. In this case, the polishing rate was as low as 150 nm / min. Further, the number of scratches was very bad, exceeding 20 / cm ² .

Claims (4)

  An abrasive having a pH of 8.0 to 11.5 in which inorganic oxide fine particles having a solid acid amount or a solid base amount of 0.01 mmol / g or more and an average particle size of 2 μm or less are dispersed in a dispersion medium. .   Is the oxide equivalent mass molar concentration (mol / kg) of an element having a relatively high valence the same as the oxide equivalent mass molar concentration (mol / kg) of an element having a relatively low valence? The abrasive according to claim 1, wherein the abrasive is the inorganic oxide fine particle mainly composed of an oxide containing two elements at a large ratio.   The inorganic oxide fine particles are at least 2 selected from the group consisting of Si, Al, B, Mg, Ca, Ba, Mo, Zr, Ga, Be, Sr, Y, La, Ce, Sn, Fe, Zn, and Ti. The abrasive | polishing agent of Claim 1 or 2 which has as a main component the oxide containing two elements. The inorganic oxide fine particles include at least one element selected from the group consisting of B, Ba, Mo, Ga, Be, Sr, Y, La, Fe, Ti, Al, Zr, Ce, Sn, and Zn; and Si, The main component is an oxide containing at least one element selected from the group consisting of Mg and Ca , the main component is an oxide containing Ti and Zr, or the main component is an oxide containing Mg and Si. to polishing agent according to claim 1.