JP2009078935A - "konpeito" (pointed sugar candy ball)-like composite silica sol - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a "konpeito" (pointed sugar candy ball)-like composite silica sol prepared by dispersing in a solvent "konpeito"-like silica fine particles having a plurality of warty protrusions on a silica fine particle surface. <P>SOLUTION: The "konpeito"-like composite silica sol is prepared by dispersing in a solvent "konpeito"-like composite silica fine particles which are composite silica fine particles having a plurality of warty protrusions comprising a metal oxide other than silica on a spherical silica fine particle surface, wherein the composite silica fine particles have a surface roughness (SA1)/(SA2) in a range of 1.7-5.0, wherein SA1 is a specific surface area measured by a BET method, and SA2 is a specific surface area converted from an average particle diameter (D2) measured by an image analysis method, and the average particle diameter (D2) measured by the image analysis is in a range of 7-150 nm. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a gold flat sugar-like composite silica sol in which gold flat sugar-like silica fine particles having a plurality of ridge-like projections on the surface of core particles are dispersed in a solvent, and further, the gold flat sugar-like composite silica sol The present invention relates to a polishing composition comprising

Among silica sols in which silica fine particles are dispersed in a solvent, as silica sols in which the silica fine particles have a shape other than a spherical shape, those having a chain shape, a bead shape or an oblong shape are known. Such a silica sol is used, for example, as various abrasives.
As an example having a protrusion-like structure on the surface of silica-based fine particles, JP-A-3-257010 (Patent Document 1) discloses a continuous surface having a size of 0.2 to 5 μm as observed on the surface of the silica particles with an electron microscope. There is a description relating to silica particles having irregular projections, an average particle diameter of 5 to 100 μm, a BET specific surface area of 20 m ² / g or less, and a pore volume of 0.1 mL / g or less. Moreover, the use as a filler is suggested as the use.

  Japanese Patent Application Laid-Open No. 2002-38049 (Patent Document 2) discloses silica-based fine particles having substantially spherical and / or hemispherical protrusions on the entire surface of the base particles, and the protrusions are converted into base particles by chemical bonding. There is a description of silica-based fine particles characterized by being bound. Furthermore, (A) a step of hydrolyzing and condensing a specific alkoxysilane compound to produce polyorganosiloxane particles, (B) a step of surface-treating the polyorganosiloxane particles with a surface adsorbent, and (C) the above There is a description of a method for producing silica-based fine particles, including a step of forming protrusions on the entire surface of the polyorganosiloxane particles surface-treated in the step (B) using the alkoxysilane compound. About this silica type fine particle, the use as a filler or electroconductive fine particle is suggested.

  Japanese Patent Application Laid-Open No. 2002-338232 (Patent Document 3) discloses a geometric average particle diameter (X1) obtained from a transmission projection image of colloidal silica silica particles by an electron beam and an equivalent particle diameter calculated from the surface area of the silica particles. Secondary aggregation colloid characterized in that the ratio Y (X1 / X2) to (X2) is in the range of 1.3 to 2.5 and the geometric mean particle diameter is in the range of 20 to 200 nm. An invention relating to silica is disclosed, and its use includes polishing of a silicon wafer and the like.

  Japanese Patent Application Laid-Open No. 2004-35293 (Patent Document 4) discloses silica-based particles having substantially spherical and / or hemispherical protrusions on the entire surface of the base particle, and the protrusion is chemically bonded to the base. Silica-based particles are disclosed that are bound to particles and have different compressive elastic moduli at 10% compression between the base particles and the protrusions.

  However, the particles described in JP-A-3-257010 (Patent Document 1) are particles composed only of silica having an average particle size of 5 to 100 μm, and the particle size distribution was not controlled. About the silica type particle | grains disclosed by Unexamined-Japanese-Patent No. 2002-38049 (patent document 2), the composition consists only of silica substantially, and the average particle diameter is substantially 0.5-30 micrometers. Only have been disclosed. The particle size distribution of these silica particles is not controlled. Japanese Unexamined Patent Application Publication No. 2004-35293 (Patent Document 4) also discloses the same silica particles as in Japanese Unexamined Patent Application Publication No. 2002-38049 (Patent Document 2).

About the particle | grains of Unexamined-Japanese-Patent No. 2002-338232 (patent document 3), the surface is an uneven | corrugated silica fine particle, Comprising: Although the application to an abrasive material use etc. was suggested, the component which comprises particle | grains Consisted essentially of silica.
JP-A-3-257010 JP 2002-38049 A JP 2002-338232 A JP 2004-35293 A

  The present invention relates to a gold flat sugar-like silica fine particle having a plurality of hook-like protrusions on the surface of the silica fine particle, wherein the gold flat sugar-like composite silica fine particles in which the hook-like protrusions are made of a metal oxide other than silica are dispersed in a solvent. It is an object to provide a composite silica sol. It is another object of the present invention to provide a polishing composition comprising the confetti-like composite silica sol.

  The gold flat sugar-like composite silica sol of the present invention is a composite silica fine particle having a plurality of hook-like protrusions containing a metal oxide other than silica on the surface of a spherical silica fine particle, and the specific surface area measured by the BET method is (SA1). The value of the surface roughness (SA1) / (SA2) when the specific surface area converted from the average particle diameter (D2) measured by the image analysis method is (SA2) is in the range of 1.7 to 5.0. In this case, gold-plated sugar-like composite silica fine particles having an average particle diameter (D2) measured by the image analysis method in the range of 7 to 150 nm are dispersed in a solvent.

It is preferable that the average height (H) of the hook-shaped protrusions corresponds to 3 to 30% of the average particle diameter (D2) of the confetti-like composite silica fine particles.
It is preferable that the metal oxide other than the silica is selected from zirconium oxide, cerium oxide, tungsten oxide, or titanium oxide.
It is preferable that the sphericity of the gold flat sugar-like composite silica fine particles is in the range of 0.8-1.
It is preferable that a particle diameter variation coefficient (CV value) of the gold flat sugar-like composite silica fine particles is in a range of 10 to 50%.

  The gold flat sugar-like composite silica sol of the present invention is a composite silica fine particle having a plurality of hook-like protrusions containing a metal oxide other than silica on the surface of a spherical silica fine particle, and the specific surface area measured by the BET method is (SA1). The value of the surface roughness (SA1) / (SA2) when the specific surface area converted from the average particle diameter (D2) measured by the image analysis method is (SA2) is in the range of 1.7 to 5.0. A frigate saccharide-like composite silica sol in which gold candy sugar-like composite silica fine particles having an average particle diameter (D2) measured by the image analysis method in the range of 7 to 150 nm are dispersed in a solvent, wherein The particle diameter variation coefficient (CV value) of the fine particles is in the range of 10 to 50%.

The abrasive of the present invention is composed of the above-described konpeito-like composite silica sol.
The polishing composition of the present invention contains the abrasive.
The gold flat sugar-like composite silica sol of the present invention is characterized in that the gold flat sugar-like composite silica fine particles having hook-like protrusions containing a metal oxide having a hardness different from that of silica are dispersed in a solvent on the surface of the spherical silica fine particles. is there.

The gold flat sugar-like composite silica sol of the present invention is a sol in which gold flat sugar-like composite silica fine particles having a plurality of hook-shaped protrusions are dispersed. These hook-shaped protrusions are mainly composed of a metal oxide other than silica, and generally have a strength higher than that of silica although it depends on the type of metal oxide. For this reason, for example, it can be conveniently used as a component of an abrasive or a polishing composition. In particular, since the core particle of the silica fine particle is made of silica and the hook-shaped protrusion is made of a metal oxide other than silica, a metal having a higher raw material price than silica can be used effectively.

[Konpeira sugar-like composite silica sol]
The gold flat sugar-like composite silica sol according to the present invention is a composite silica fine particle having a plurality of hook-shaped protrusions containing a metal oxide other than silica on the surface of a spherical silica fine particle, and has a specific surface area measured by the BET method (SA1). And the value of the surface roughness (SA1) / (SA2) is 1.7 to 5.0 when the specific surface area converted from the average particle diameter (D2) measured by the image analysis method is (SA2). In the range, the gold flat sugar-like composite silica fine particles having an average particle diameter (D2) measured by the image analysis method in the range of 7 to 150 nm are dispersed in a solvent.

[Surface roughness]
The confetti-like composite silica fine particles are spherical fine particles having a plurality of ridge-like projections on the surface thereof, and the structure is generally similar to that of confetti. The surface of such a surface having a plurality of hook-shaped protrusions is defined by the surface roughness.
In the present invention, the surface roughness is a ratio converted from an average particle diameter (D2) measured by an image analysis method, where (SA1) is a specific surface area [surface area per unit mass] measured by the BET method. When the surface area value is (SA2), the surface roughness is defined as (SA1) / (SA2).

  Here, the specific surface area (SA1) measured by the BET method is to detect the amount of nitrogen adsorbed by allowing the measurement target particles to equilibrate and adsorb nitrogen at a liquid nitrogen temperature and then raise the temperature. It can be said that it reflects the actual surface area of the sample. In place of the BET method, the specific surface area measured by the Sears method described later may be used as (SA1).

Further, regarding the specific surface area (SA2) converted from the average particle diameter (D2) measured by the image analysis method, an arbitrary 50 in a photograph projection view obtained by photographing a sample silica sol with a scanning electron microscope. Assuming that the average value when the maximum diameter (DL) of each particle is measured is the average particle diameter (D2), and then the silica fine particles dispersed in the sample silica sol are ideal spherical particles, The specific surface area (SA2) is calculated from 1).
SA2 = 6000 / (D2 × ρ) (1)
However, in formula (1), ρ represents the density of the sample particles, and is 2.2 for silica.

  In addition, although the gold flat sugar-like composite silica fine particles according to the present invention are composite fine particles of silica and a metal oxide other than silica, the amount of silica in the mass ratio of the silica and the metal oxide other than silica is greatly increased. Only the density of silica may be used as the density. Moreover, the gold flat sugar-like composite silica fine particles according to the present invention have ridge-like projections and do not have a porous structure. For this reason, the density range of the gold flat sugar-like composite silica fine particles according to the present invention is very close to 2.2 which is the density of silica.

  Here, since the specific surface area represents the surface area per unit mass, the value of the surface roughness (SA1) / (SA2) is such that the more the particles are spherical and the surface of the particle has more ridge-like projections (SA1 ) / (SA2) value increases, the smaller the number of wrinkles on the particle surface and the smoother, the smaller the value of (SA1) / (SA2), and the value approaches 1.

  The surface roughness of the gold flat sugar-like composite silica fine particles according to the present invention is preferably in the range of 1.7 to 5.0. When the surface roughness is less than 1.7, the ratio of the ridge-like protrusions is small, or the ridge-like protrusions themselves are extremely smaller than the particle diameter of the composite silica fine particles, and become close to spherical fine particles. When the surface roughness value exceeds 5.0, synthesis is not easy. As the surface roughness range, a range of 1.8 to 4.5 is more preferable.

[Average height of hook-shaped protrusions]
It is desirable that the average height of the ridge-like projections in the confetti-like composite silica fine particles according to the present invention corresponds to 3 to 30% of the average particle diameter of the confetti-like composite silica fine particles.
When the ratio of the height of the ridge-like projections to the average particle diameter of the confetti-like composite silica fine particles is less than 3%, it is very close to the case where the fine particle surface is smooth. In this case, for example, even when used as an abrasive, a difference in effect is not seen as compared with the case where silica fine particles having a smooth surface are used. Moreover, about what exceeds 30%, it is not easy to synthesize | combine. About this range, the range of 3 to 20% is more preferable.

[Sphericity]
The gold-plated sugar-like composite silica particles need to be spherical as a whole, and do not include irregular-shaped particles such as rod-shaped, slanted-ball-shaped, elongated, beaded, or egg-shaped. The gold flat sugar-like composite silica particles of the present invention are spherical and are distinguished from irregular shaped composite silica particles. In the present invention, the term “spherical” means that the sphericity is in the range of 0.8 to 1.0. Here, the sphericity is the maximum diameter (DL) and the short diameter (DS) orthogonal to each of any 50 particles in a photographic projection obtained by photographing with a transmission electron microscope. Mean ratio (DS / DL). When the sphericity is less than 0.8, it may not be said that the confetti-like composite silica fine particles are spherical, and may correspond to the irregular shaped particles.

[Average particle size]
With regard to the gold flat sugar-like composite silica particles obtained by the production method according to the present invention, those having an average particle diameter (D2) value measured by an image analysis method in the range of 7 to 150 nm are suitably obtained.
In the case of preparing a confetti-like composite silica sol according to the present invention, which will be described later, when the average particle size (D2) exceeds 150 nm, it generally depends on the size of the seed silica fine particles as a raw material. Protrusions are difficult to form, but rather tend to flatten. In addition, when the average particle diameter (D2) is less than 7 nm, it is not easy to prepare the gold flat sugar-like composite silica fine particles having the necessary surface roughness. About the average particle diameter of the said gold flat sugar-like composite silica fine particle, the range of 10-130 nm is recommended, and the range of 10-80 nm is more preferable.

[Particle diameter variation coefficient (CV value)]
In the case of applying the gold flat sugar-like composite silica sol according to the present invention as an abrasive or a polishing composition, it is particularly preferable that the particle size distribution of the gold flat sugar-like composite silica sol in the gold flat sugar-like composite silica sol is high. Specifically, those having a particle diameter variation coefficient (CV value) in the range of 10 to 50% are excellent in the polishing rate, and are also suitable for suppressing the occurrence of linear marks on the substrate to be polished. Here, the particle diameter variation coefficient (CV value) is defined by the following equation (2).
CV value [%] = standard deviation of particle diameter (σ) / average particle diameter (Dn) × 100 (2)
(However, σ = nΣ | Di−Dn | / (n−1) × Dn, where Di represents the particle size of each particle.)
A range of 10 to 40% is more preferable as the range of the particle diameter variation coefficient (CV value).

[Metal oxide]
The metal oxide contained in the hook-shaped projections is not particularly limited, but considering the use of the confetti-like composite silica sol, one having a difference in hardness from silica is preferably selected. Examples thereof include zirconium oxide, cerium oxide, tungsten oxide, titanium oxide, magnesium oxide, aluminum oxide, iron oxide and the like.

  By selecting the type of these metal oxides constituting the hook-shaped protrusions, it is possible to impart properties not found in conventional spherical silica fine particles to the confetti-like composite silica fine particles. For example, when a metal oxide that is harder than silica and has a high breaking strength is selected, it becomes gold flat sugar-like composite silica fine particles having hook-like protrusions harder than silica, and is useful as an abrasive, for example.

  In addition, the present invention is not limited to this example, and in the case of the gold-peeled composite silica sol of the present invention, a metal oxide that is rarer and more expensive than silica can be used efficiently depending on the application, which contributes to resource and cost savings. It becomes. In addition, when a silicic acid solution is added together with a metal peroxide to prepare a gold flat sugar-like composite silica sol as will be described later, the proportion of the metal oxide in the components constituting the hook-shaped protrusions decreases, and the silica component occupies The rate increases. For this reason, it is also possible to adjust the strength of the hook-shaped protrusions by adjusting the ratio of the silica component.

[solvent]
As a solvent as a dispersion medium in which the gold flat sugar-like silica fine particles are dispersed, any of water, an organic solvent, and a mixed solvent thereof can be used. As the organic solvent, a water-soluble organic solvent is more preferable. Specifically, the following examples can be given.

Water such as pure water, ultrapure water, ion exchange water;
Alcohols such as methanol, ethanol, isopropanol, n-butanol, methyl isocarbinol;
Ketones such as acetone, 2-butanone, ethyl amyl ketone, diacetone alcohol, isophorone, cyclohexanone;
Amides such as N, N-dimethylformamide and N, N-dimethylacetamide;
Ethers such as diethyl ether, isopropyl ether, tetrahydrofuran, 1,4-dioxane, 3,4-dihydro-2H-pyran;
Glycol ethers such as 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, ethylene glycol dimethyl ether;
Glycol ether acetates such as 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-butoxyethyl acetate;

Esters such as methyl acetate, ethyl acetate, isobutyl acetate, amyl acetate, ethyl lactate, ethylene carbonate;
Aromatic hydrocarbons such as benzene, toluene, xylene;
Aliphatic hydrocarbons such as hexane, heptane, iso-octane, cyclohexane;
Halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, dichloropropane, chlorobenzene;
Sulfoxides such as dimethyl sulfoxide;
Examples include pyrrolidones such as N-methyl-2-pyrrolidone and N-octyl-2-pyrrolidone.

[First production method of gold-peeled composite silica sol]
In the first production method of the gold flat sugar-like composite silica sol according to the present invention, the pH and temperature of a seed silica sol formed by dispersing silica fine particles in a solvent are adjusted within a predetermined range, and 1) of a metal oxide (excluding silica) It is prepared by adding a precursor or a predetermined amount of the precursor of the metal oxide and the silicic acid solution continuously or intermittently.

[Seed silica sol]
In the method for producing the gold flat sugar-like composite silica sol of the present invention, the method for producing the seed silica sol used as the raw material core particles is not particularly limited, and a commercially available silica sol or a known silica sol can be applied.

Regarding the method for producing such a silica sol, for example,
1) Heating a silicic acid solution obtained by dealkalizing a water-soluble silicate selected from alkali metal silicate, tertiary ammonium silicate, quaternary ammonium silicate or guanidine silicate in the presence of alkali. A method for producing a silica sol comprising a step of polymerizing silicic acid by
2) A silica hydrogel obtained by neutralizing a silicate with an acid, washing the silica hydrogel, removing salts, adding an alkali, and then heating the silica hydrogel by heating, and a method for producing a silica sol,
3) A method for producing a silica sol, which includes a step of hydrolyzing a silicon compound having a hydrolyzable group and polymerizing the resulting silicic acid.

The structure of the silica fine particles in the seed silica sol is spherical, and the average particle diameter of the silica fine particles can be used as long as it is smaller than the average particle diameter of the target saccharoform complex silica sol. A particle diameter of less than 94% is preferable with respect to the average particle diameter of the confetti-like composite silica sol. About this particle diameter range, when measuring by the image analysis method, it can be said that the range whose average particle diameter (D2) is 3-140 nm is suitable. Further, those having an average particle diameter (D2) of 5 to 100 nm are preferably used. When a silica fine particle-dispersed sol having an average particle diameter (D2) of less than 3 nm is applied, it is not possible to confirm the formation of confetti-like composite silica fine particles. In the case of a silica fine particle-dispersed sol having an average particle diameter (D2) exceeding 140 nm, there is a problem in practicality because it takes a long time for particle growth after forming a coating of a metal oxide other than silica.
In addition, even when the average particle diameter of the silica fine particles in the seed silica sol is measured by the dynamic light scattering method, it is usually applicable as a seed silica sol if the average particle diameter (D2) is in the range of 3 to 140 nm. is there.

  The pH of the seed silica sol is preferably in the range of 8-12. When the pH is less than 8, there is a problem with the stability of the silica sol. It is not easy to prepare a confetti-like composite silica sol. On the other hand, when the pH exceeds 12, the solubility is too high to be suitable for particle growth. About pH range, pH 8.5-10.5 is recommended suitably.

Regarding the SiO ₂ solid content concentration of the seed silica sol, a concentration in the range of 1 to 50% by weight is usually used. If it is less than 1% by weight, silica sol cannot be produced efficiently. On the other hand, if it exceeds 50% by weight, the stability of the silica sol is lowered and it tends to aggregate, which is not desirable.
The seed silica sol is preferably an aqueous solvent silica sol. Since the silica sol of the aqueous solvent is an alkaline oxide, it is preferable when it is coated with a metal oxide other than silica.

In the method of the present invention, it is desirable that such a seed silica sol is diluted with pure water as necessary to adjust the silica solid content concentration to 2 to 50%.
When it is intended to use the gold flat sugar-like composite silica sol according to the present invention as an abrasive, the gold flat sugar-like composite silica sol having a particle size variation coefficient (CV value) in the range of 10 to 50% is used as the seed silica sol. It is desirable to do. By using a seed silica sol having a particle size variation coefficient of 10 to 50% as a raw material of the production method according to the present invention, the final product, the gold sugar-like composite silica sol, having a particle size variation coefficient of 10 to 50% Can be obtained.

About the manufacturing method of such a silica sol, the manufacturing method which combines a classification process with the manufacturing method quoted in following (1)-(4) suitably is used suitably.
(1) A metal-alkoxide is added to a water-alcohol dispersion in which a metal oxide or a metal hydroxide is dispersed as a seed while keeping the dispersion alkaline, and then hydrolyzed and contained in the dispersion. A method in which a metal alkoxide decomposition product is deposited on a seed so as to perform particle growth (Japanese Patent Laid-Open No. 62-275005).

(2) Tetraethoxysilane is added to a water-organic solvent dispersion in which seed particles are dispersed, and this tetraethoxysilane is converted into the following formula [I]:
_{(CH 3 O) n · (} C 2 H 5 O) 4-n · Si ··· [I] (wherein, n is 1-4.)
A method of causing particle growth by hydrolyzing in the presence of alkoxysilane and attaching silica onto seed particles in a dispersion (Japanese Patent Laid-Open No. 3-218915).
(3) A tetraalkoxysilane and a silicic acid solution are added to a water-alcohol dispersion in which a metal oxide or a metal hydroxide is dispersed as a seed while keeping such a dispersion alkaline. A method of causing particle growth by attaching a hydrolysis product of the above and a silicic acid polymer to a seed contained in a dispersion (Japanese Patent Laid-Open No. 4-21515).

(4) An alkali silicate aqueous solution and / or an alkali aqueous solution and an acidic silicate solution are mixed, and after adjusting the molar ratio of SiO ₂ / M ₂ O (M is an alkali metal) in the mixture to a predetermined range, 60 ° C. or more A seed solution is prepared by heating at a predetermined temperature, and an acidic silicic acid solution is added at a predetermined addition rate (JP-A 63-45114, JP-A 63-45113, or JP-A 63-64911, etc.) Can be mentioned.
By using a seed silica sol having a particle size variation coefficient of 10 to 50%, it is easy to obtain a gold flat sugar-like composite silica sol as a final product having a particle size variation coefficient of 10 to 50%.

[Formation of hook-shaped protrusions]
After adjusting the seed silica sol to a temperature of 60 to 200 ° C. and a pH of 9 to 12, the metal oxide precursor is added continuously or intermittently. When the temperature is less than 60 ° C., the seed silica sol aggregates and is unstable, and when it exceeds 200 ° C., the productivity is lowered and scale is likely to occur. When the pH is less than 9, the tendency of the seed silica sol to aggregate becomes strong, and when the pH exceeds 12, the tendency of the metal oxide precursor to aggregate becomes strong. By adjusting the pH to the range of 9 to 12, the potential of the silica sol increases, and therefore, it becomes difficult to agglomerate. Therefore, the stability of the seed silica sol is maintained even when a silicic acid solution is added in a later step. Be drunk.

  In addition, about the said temperature range, when adding only a metal oxide precursor, it is 70-180 degreeC suitably, When adding the mixture of a metal oxide precursor and a silicic acid solution, it is preferably 70-150. A range of ° C is recommended. To adjust the pH, an aqueous alkali solution such as an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution can be used.

[Metal oxide precursor]
The metal oxide precursor in the present invention is a main component of the ridge-like projections formed on the surface of the silica fine particles, and reacts with the surface of the silica fine particles, which is the dispersoid of the seed silica sol, to form the metal oxide. A hook-shaped protrusion is formed. Such metal oxide precursors are preferably selected from alkali metal salts of metal oxo acids, alkaline earth metal salts of metal oxo acids, ammonium salts of metal oxo acids or quaternary ammonium salts of metal oxo acids. Used for.

  As the metal, a material selected from zirconium, cerium, titanium or tungsten is preferably used. Specific examples include ammonium zirconium carbonate, ammonium zirconium nitrate, and cerium ammonium nitrate. In addition, a metal peroxide is not contained here as a metal oxide precursor. In general, the reaction rate between the metal peroxide and the silica fine particles is remarkably slower than the case of the metal oxide precursor, so that it is not easy to apply to the first production method of the gold flat sugar-like composite silica sol according to the present invention. Because.

About the addition amount of a metal oxide precursor, 0.001 ≦ m / a ≦ 0.1 (where a represents the number of moles of SiO ₂ in the seed silica sol, and m is included in the metal oxide precursor) The number of moles of metal to be converted (in oxide equivalent).
When the value of m / a exceeds 0.1, the amount of metal oxide becomes excessive, so that the tendency of uniform particle growth increases, and the formation of hook-like protrusions may not be observed. When the value of m / a is less than 0.001, since the amount of the metal oxide is relatively small, generation of hook-like protrusions is not observed. The metal oxide precursor may be diluted with water and used as an aqueous solution of the metal oxide precursor, or an undiluted product may be used. Although it does not restrict | limit especially about the density | concentration of the metal oxide precursor in the case of a water dilution goods, For example, the range of 0.1 mass%-30 mass% can be mentioned.

[Silica solution]
In the production method of the present invention, a silicic acid solution can be added together with the metal oxide precursor as desired.
Silicic acid liquid is prepared by dealkalizing water-soluble silicate, and usually low polymerization of silicic acid obtained by dealkalization by a method such as treating an aqueous silicate solution with a cation exchange resin. It is an aqueous solution of the product. This type of silicic acid solution has a pH of 2 to 4 and a SiO ₂ concentration of about 10% by mass or less, preferably 2 to 7% by mass. Used as a practical raw material.

The silicic acid solution is used in the range of 0 ≦ c / m ≦ 1 (m is defined in the same manner as described above, and c is the number of moles of SiO ₂ in the silicic acid solution). When c / m exceeds 1, the ratio of the metal oxide to the component of a hook-shaped protrusion falls, and the component of a hook-shaped protrusion becomes close to a silica.
The silicic acid solution is added simultaneously with the metal oxide precursor, or a mixture of the metal oxide precursor and the silicic acid solution is prepared and added to the seed silica sol. In general, the metal oxide precursor is rapidly hydrolyzed in the alkali region, and therefore, it is not preferable to add them all at once because it is difficult to form hook-like protrusions and aggregation easily occurs. For this reason, the addition of the metal oxide precursor to the seed silica sol is performed continuously or intermittently. The addition rate of the metal oxide precursor is not easy to define clearly because it depends on the production scale, pH, or temperature, but on the laboratory scale, for example, 0.001 g for the metal oxide precursor. A range of from / min to 5 g / min is preferred.

  With respect to the formation of a plurality of hook-shaped protrusions on the surface of the silica fine particles by the first production method of the gold flat sugar-like composite silica sol according to the present invention, the amount of the metal oxide is less than the amount capable of uniformly covering the surface of the silica fine particles. By using the precursor, it is presumed that the metal oxide grows in the shape of spots and the confetti-like composite silica fine particles are formed.

[Second Production Method of Konpei Sugar-like Composite Silica Sol]
According to the second method for producing the gold flat sugar-like composite silica sol according to the present invention, the pH and temperature of a seed silica sol formed by dispersing silica fine particles in a solvent are adjusted within a predetermined range, and 1) a metal peroxide or 2) a metal peroxide. A predetermined amount of oxide and silicic acid solution is added all at once at a time.

[Seed silica sol]
As for the seed silica sol, a silica sol similar to the seed silica sol used in the first production method can be used.

[Grain growth]
After adjusting the seed silica sol to a temperature of 60 to 200 ° C. and a pH of 9 to 12, a metal peroxide is added. When the temperature is lower than 60 ° C., the seed silica sol tends to aggregate and becomes unstable. When the temperature exceeds 200 ° C., the productivity is easily reduced or the scale is easily generated. When the pH is less than 9, the tendency of the seed silica sol to aggregate increases. When the pH exceeds 12, aggregation of the metal peroxide tends to occur after the addition of the metal compound oxide. By adjusting the pH to the range of 9 to 12, the potential of the silica sol is increased, so that aggregation is difficult to occur, and the stability of the seed silica sol is maintained even when the silicic acid solution is added together with the metal peroxide. Be drunk.
In addition, about the said temperature range, when adding only a metal peroxide, Preferably it is 70-180 degreeC, When adding a silicic acid liquid with a metal peroxide, the range of 70-150 degreeC is suitable suitably. Recommended. To adjust the pH, an aqueous alkali solution such as an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution can be used.

[Metal peroxide]
Examples of metal peroxides include peroxotitanic acid (TiO ₃ ), zirconium peroxide, cerium peroxide (CeO ₃ ), tungsten peroxide, nickel peroxide (NiO ₂ ), barium peroxide (BaO ₂ ), etc. Can be mentioned.
It is necessary to add the metal peroxide by adding the entire amount of the metal peroxide all at once. Since metal peroxide generally has low reactivity, for example, when it is sequentially added, the progress of the reaction may be insufficient, and the target level of hook-shaped protrusions may not be formed.
Here, the operation of adding the whole amount of the metal peroxide at once is dependent on the production scale, pH or temperature, but it is preferable to add the whole amount in about 1 to 30 seconds on the laboratory scale. .

As for the amount of metal peroxide added, 0.001 ≦ n / a ≦ 0.1 (where a represents the number of moles of SiO ₂ in the seed silica sol, and n represents the amount of the metal contained in the metal peroxide. The number of moles (representing oxide) is required.
When the value of n / a exceeds 0.1, the amount of the metal oxide to be generated becomes excessive, so that the tendency for uniform particle growth increases and the formation of hook-shaped protrusions may not be observed. When the value of n / a is less than 0.001, since the amount of metal peroxide is relatively small, the formation of hook-like projections is not observed. The metal peroxide may be diluted with water and used as an aqueous solution, or an undiluted product may be used. In the case of a water-diluted product, the concentration of the metal peroxide is not particularly limited, but examples thereof include a range of 0.1% by mass to 30% by mass.

[Silica solution]
In the production method of the present invention, a silicic acid solution can be added together with a metal peroxide as desired. The silicic acid solution is as described in the first manufacturing method.
The silicic acid solution is used in the range of 0 ≦ c / n ≦ 1 (b is defined in the same manner as described above, and c is the number of moles of SiO ₂ in the silicic acid solution). When c / n exceeds 1, the ratio of the metal oxide to the component of a hook-shaped protrusion falls, and the component of a hook-shaped protrusion becomes close to a silica.

The silicic acid solution is added simultaneously with the metal peroxide, or a mixture of the metal peroxide and the silicic acid solution is prepared and added to the seed silica sol. Since the metal peroxide is slowly hydrolyzed in the alkaline region, it is difficult to form a coating on the surface of the silica fine particles including the hook-shaped protrusions when sequentially added.
In the second production method of the confetti-like composite silica sol according to the present invention, a plurality of hook-shaped protrusions are formed on the surface of the silica fine particles. The amount of metal peroxidation is less than the amount capable of uniformly covering the surface of the silica fine particles. By using the product, it is assumed that metal oxide grows in the shape of spots, and confetti-like composite silica fine particles are formed.

[Abrasive and polishing composition]
The fried sugar-like composite silica sol of the present invention can be applied as an abrasive by itself, and can also constitute a normal polishing composition together with other components (such as a polishing accelerator).

  The confetti-like composite silica sol of the present invention is blended as a component of the polishing composition and exhibits an excellent polishing effect. The gold plain sugar-like composite silica sol of the present invention includes an aluminum disk (aluminum or a plating layer on a substrate thereof), an aluminum wiring of a semiconductor multilayer wiring board, an optical disk, a glass substrate for a magnetic disk, a glass substrate for a liquid crystal display, and a glass substrate for a photomask. It can be used as a component of a polishing composition applied to polishing applications such as mirror finishing of glassy materials.

  The composition of the polishing composition is prepared by concentrating or diluting the gold flat sugar-like composite silica sol (aqueous system) of the present invention and further blending other components as necessary, and making it into a slurry if desired. . Here, examples of other components added to the polishing silica sol include polishing accelerators, surfactants, buffers, stabilizers, and aqueous media. Moreover, you may use together abrasive | polishing agents other than the gold flat sugar-like composite silica sol of this invention.

In the polishing composition of the present invention, examples of other components used together with the gold flat sugar-like composite silica sol of the present invention are listed below, but are not limited thereto.
In the case of a polishing composition intended for silicon wafers, aluminum disks, glass disks, etc., as the other components, as a polishing accelerator, in the alkaline system, metal hydroxides such as potassium hydroxide and sodium hydroxide, Metal oxides such as sodium carbonate and ammonium carbonate, amines such as ammonia, monoethanolamine and piperazine, quaternary ammonium hydroxides such as tetramethylammonium, etc. In the oxide system, hydrogen peroxide, chlorine compounds, etc. Can be mentioned.

As the surfactant, anionic, cationic, nonionic or amphoteric surfactants can be used.
As ions used as a buffering agent, although depending on the pH range to be adjusted, the cation is at least one of quaternary ammonium ion and alkali metal ion, and the anion is carbonate ion, bicarbonate ion, boron. It is preferable that it is at least 1 type or more of an acid ion and phenol. Particularly preferred are a mixture of carbonate ions and bicarbonate ions, borate ions, and the like.

Examples of the stabilizer include celluloses such as carboxymethyl cellulose and hydroxyethyl cellulose, water-soluble polymers such as polyvinyl alcohol, water-soluble alcohols such as ethanol, ethylene glycol, propylene glycol and glycerin, and sodium alkylbenzene sulfonate. Examples thereof include surfactants, organic polyanionic substances such as polyacrylates, inorganic salts such as magnesium chloride and potassium acetate.
The SiO ₂ concentration in the polishing composition is usually 3 to 20% by weight, but is not necessarily limited to this range.

[Preferred embodiment of the confetti-like composite silica sol according to the present invention]
Preferred embodiments of the present invention include the following embodiments.
[1] A composite silica fine particle having a plurality of ridge-like protrusions containing zirconium oxide on the surface of a spherical silica fine particle, the average surface area measured by an image analysis method with a specific surface area measured by a nitrogen adsorption method as (SA1) The value of the surface roughness (SA1) / (SA2) when the specific surface area converted from the particle diameter (D2) is (SA2) is in the range of 1.7 to 5.0 and measured by the image analysis method. An average particle diameter (D2) of an average particle size (D2) of an average particle size (D2) of 7 to 150 nm, an average particle size (H) of the rod-shaped projections, It corresponds to 3-30% of the average particle diameter (D2) of the confetti sugar composite silica fine particles, and the particle diameter variation coefficient (CV value) of the confetti sugar composite silica fine particles is in the range of 10-50%. Features that are A gold-peeled composite silica sol.

[2] A composite silica fine particle having a plurality of ridge-like projections containing cerium oxide on the surface of the spherical silica fine particle, and the average surface area measured by an image analysis method with a specific surface area measured by a nitrogen adsorption method as (SA1) The value of the surface roughness (SA1) / (SA2) when the specific surface area converted from the particle diameter (D2) is (SA2) is in the range of 1.7 to 5.0 and measured by the image analysis method. An average particle diameter (D2) of an average particle size (D2) of an average particle size (D2) of 7 to 150 nm, an average particle size (H) of the rod-shaped projections, It corresponds to 3-30% of the average particle diameter (D2) of the confetti sugar composite silica fine particles, and the particle diameter variation coefficient (CV value) of the confetti sugar composite silica fine particles is in the range of 10-50%. It is characterized by being That confetti-like composite silica sol.

[3] A composite silica fine particle having a plurality of ridge-like projections containing zirconium oxide on the surface of the spherical silica fine particle, and the average surface area measured by an image analysis method with a specific surface area measured by a nitrogen adsorption method as (SA1) The value of the surface roughness (SA1) / (SA2) when the specific surface area converted from the particle diameter (D2) is (SA2) is in the range of 1.7 to 5.0 and measured by the image analysis method. An average particle diameter (D2) of an average particle size (D2) of an average particle size (D2) of 7 to 150 nm, an average particle size (H) of the rod-shaped projections, It corresponds to 3-30% of the average particle diameter (D2) of the confetti sugar composite silica fine particles, and the particle diameter variation coefficient (CV value) of the confetti sugar composite silica fine particles is in the range of 10-50%. A certain kind of confetti Abrasives or polishing composition containing the same consists of coupling the silica sol.

[4] A composite silica fine particle having a plurality of ridge-like projections containing cerium oxide on the surface of the spherical silica fine particle, the average surface area measured by an image analysis method with a specific surface area measured by a nitrogen adsorption method as (SA1) The value of the surface roughness (SA1) / (SA2) when the specific surface area converted from the particle diameter (D2) is (SA2) is in the range of 1.7 to 5.0 and measured by the image analysis method. An average particle diameter (D2) of an average particle size (D2) of an average particle size (D2) of 7 to 150 nm, an average particle size (H) of the rod-shaped projections, It corresponds to 3-30% of the average particle diameter (D2) of the confetti sugar composite silica fine particles, and the particle diameter variation coefficient (CV value) of the confetti sugar composite silica fine particles is in the range of 10-50%. A certain kind of confetti Abrasives or polishing composition comprising it consists Rikazoru.

[Analysis methods used in Examples and Comparative Examples]
Hereinafter, preferred examples of the present invention will be described. The measurement methods of various characteristics in the examples and comparative examples were carried out as described below unless otherwise specified. The results are shown in Table 1.

[1] Measurement of specific surface area (SA1) by BET method 50 ml of silica sol was adjusted to pH 3.5 with HNO ₃ , 40 ml of 1-propanol was added, and the sample was dried at 110 ° C. for 16 hours. Baked at 500 ° C. for 1 hour to obtain a measurement sample. And the specific surface area was computed by the BET 1-point method from the adsorption amount of nitrogen using the specific surface area measuring apparatus (the product made from Yuasa Ionics, multisorb 12).

  Specifically, 0.5 g of a sample is taken in a measurement cell, degassed for 20 minutes at 300 ° C. in a mixed gas stream of 30% by volume of nitrogen / 70% by volume of helium, and then the sample is placed in the mixed gas stream. At a liquid nitrogen temperature, and nitrogen is adsorbed on the sample by equilibrium. Next, the sample temperature was gradually raised to room temperature while flowing the mixed gas, the amount of nitrogen desorbed during that time was detected, and the specific surface area (SA1) of the silica sol was calculated using a calibration curve prepared in advance.

[2] Measurement of specific surface area (SA1) and average particle diameter (D1) by Sears method 1) A sample corresponding to 1.5 g as SiO ₂ was collected in a beaker and transferred to a constant temperature reaction vessel at 25 ° C. Add water to bring the volume to 90 ml. The following operation was performed in a constant temperature reaction tank maintained at 25 ° C.
2) Add 0.1 mol / L hydrochloric acid aqueous solution so that pH becomes 3.6.
3) Add 30 g of sodium chloride, dilute to 150 ml with pure water and stir for 10 minutes.
4) A pH electrode is set, and 0.1 mol / L aqueous sodium hydroxide solution is added dropwise with stirring to adjust the pH to 4.0.

5) The sample adjusted to pH 4.0 was titrated with a 0.1 mol / L sodium hydroxide aqueous solution, and the titration amount and pH value in the range of pH 8.7 to 9.3 were recorded at 4 points or more. A calibration curve is prepared, where X is the titration amount of 1 mol / L sodium hydroxide aqueous solution and Y is the pH value at that time.
6) Consumption V (ml) of 0.1 mol / L sodium hydroxide aqueous solution required for pH 4.0 to 9.0 per 1.5 g of SiO _{2 was obtained} from the following formula (3), and the following formula (4) ) To calculate the specific surface area.
Moreover, average particle diameter D1 (nm) is calculated | required from Formula (5).

V = (A × f × 100 × 1.5) / (W × C) (3)
SA1 = 29.0V−28 (4)
D1 = 6000 / (ρ × SA1) (5) (ρ: density of sample)
However, the meanings of the symbols in the above formula (3) are as follows.
A: Titration amount of 0.1 mol / L sodium hydroxide solution required for pH 4.0 to 9.0 per 1.5 g of SiO ₂ (ml)
f: Potency of 0.1 mol / L sodium hydroxide solution C: SiO ₂ concentration of sample (%)
W: Sampling amount (g)

[3] Measurement method of average particle diameter (D2) by image analysis and calculation method of specific surface area (SA2) Photograph of sample silica sol at a magnification of 250,000 with a scanning electron microscope (H-800, manufactured by Hitachi, Ltd.) The maximum diameter (DL) of any 50 particles in a photograph projection view obtained by photographing was measured, and the average value was defined as the average particle diameter (D2). Further, the specific surface area (SA2) was determined by substituting the value of the average particle diameter (D2) into the formula (1).

[4] Measurement of average height of ridge-like projections of confetti-like complex silica fine particles by image analysis Obtained by photographing a sample silica sol at a magnification of 250,000 with a scanning electron microscope (H-800, manufactured by Hitachi, Ltd.) Measure the distance from the apex of any saddle-shaped protrusion to the contact point between the saddle-shaped protrusion and the spherical fine particle part for each of 50 arbitrary gold-plated sugar-like composite silica particles in the photograph projection figure, and the average value of all of them Was calculated as the average height (H) of the hook-shaped projections.
Next, (H / D2) × 100 (%) was calculated using the average particle diameter (D2) of the confetti-like composite silica fine particles.

[5] Method for measuring sphericity Any 50 of the photographic projections obtained by photographing a sample silica sol at a magnification of 250,000 times with a scanning electron microscope (H-800, manufactured by Hitachi, Ltd.) About each particle | grain, ratio (DS / DL) of the largest diameter (DL) and the short diameter (DS) orthogonal to this was measured, and those average values were made into sphericity.

[6] Measurement of solid content of composite silica fine particle dispersion 2 g of sample (composite silica fine particle dispersion) was evaporated to dryness with a crucible, and the resulting solid was fired at 1000 ° C. for 1 hour, then placed in a desiccator and cooled. Weigh. The content of the composite silica fine particles was determined from these weight differences.

[7] Average Particle Size Measurement by Dynamic Light Scattering Method The average particle size of the seed silica sol was measured by a dynamic light scattering method using a particle size distribution measuring device (manufactured by Particle Sizing Systems: “NICOMP MODEL 380”). .

[8] Method for Measuring Density Regarding the specific gravity of the composite silica fine particles, first, 10 g of a sample is collected in a crucible and dried at 110 ° C. for 2 hours. Next, after cooling with a desiccator, 3 to 4 g is put into a 25 ml pycnometer, distilled water is added and suspended, vacuum deaeration is performed at 60 mmHg for 1 hour, and the temperature is adjusted in a 25 ° C. constant temperature bath. Distilled water is added to the mark of the pycnometer to adjust the volume, and the sample volume (ml) is calculated from the difference between the pycnometer volume (25 ml) and the distilled water volume (ml). The density was determined from the weight (g) of the added sample and the calculated volume (ml).

[9] Evaluation method of polishing characteristics for aluminum substrate
Preparation of Slurry for Slurry To the gold flat sugar-like silica sol having a silica concentration of 20% by mass obtained in each Example and each Comparative Example, H ₂ O ₂ , HEDP (1-hydroxyethylidene-1,1-disulfonic acid) and ultrapure water were added. In addition, a polishing slurry of 9% by weight of silica, 0.5% by weight of H ₂ O _{2 and} 0.5% by weight of 1-hydroxyethylidene-1,1-disulfonic acid was prepared, and if necessary, HNO ₃ was added. In addition, a polishing slurry having a pH of 2 was prepared.

Polishing substrate An aluminum disk substrate was used as the polishing substrate. This aluminum disk substrate is a substrate (95 mmΦ / 25 mmΦ-1.27 mmt) obtained by electrolessly plating Ni-P to a thickness of 10 μm (a hard Ni-P plating layer having a composition of Ni88% and P12%) on an aluminum substrate. It was used. This substrate was first polished and the surface roughness (Ra) was 0.17 nm.

Polishing test The above substrate to be polished is set in a polishing apparatus (manufactured by Nano Factor Co., Ltd .: NF300), and a polishing pad (“Apollon” manufactured by Rodel) is used and polished at a substrate load of 0.05 MPa and a table rotation speed of 30 rpm. Polishing was performed by supplying the slurry for 5 minutes at a rate of 20 g / min.
The polishing rate was calculated by determining the weight change of the substrate to be polished before and after polishing. Further, the polishing rate was the ratio of each polishing rate with the confetti sugar silica sol or the silica sol when the polishing rate with the silica sol of Comparative Example 5 was 1.

1000 g of silica sol (silica concentration 3% by mass, average particle size 11 nm measured by dynamic light scattering method, specific surface area 250 m ² / g, particle size variation coefficient (CV value) 35%) was injected into a reaction vessel equipped with a stirrer, At room temperature, 10 g (0.125 mol) of an aqueous sodium hydroxide solution (sodium hydroxide concentration 5 mass%) was added, and the pH was measured and found to be 11.0.
The silica sol to which this aqueous sodium hydroxide solution was added was heated at a temperature of 80 ° C. for 1 hour, and while maintaining the temperature at 80 ° C., 60 g of zirconium carbonate aqueous solution concentration (5.0 mass%) was added at an addition rate of 1 g / min. Over 60 minutes.
As a result, gold-plated sugar-like fine particles formed by forming hook-like protrusions made of zirconium oxide on the surface of the silica fine particles were produced.

Silica sol (Catalyst Kasei Kogyo Co., Ltd., Cataloid SI-45P, silica concentration 3 mass%, average particle size 45 nm measured by dynamic light scattering method, specific surface area 61 m ² / g, particle size variation coefficient (CV value) 25 %) Was poured into a reaction vessel equipped with a stirrer, and at room temperature, 10 g (0.125 mol) of an aqueous sodium hydroxide solution (sodium hydroxide concentration 5 mass%) was added, and the pH was measured to be 11.2. It was.
The silica sol to which this sodium hydroxide aqueous solution was added was heated at a temperature of 80 ° C. for 1 hour, and while maintaining the temperature at 80 ° C., 15 g of zirconium carbonate aqueous solution concentration (5.0 mass%) was added at an addition rate of 1 g / min. , Added over 15 minutes.
As a result, gold-plated sugar-like fine particles formed by forming hook-like protrusions made of zirconium oxide on the surface of the silica fine particles were produced.

Silica sol (manufactured by Catalyst Kasei Kogyo Co., Ltd., Cataloid SI-80P, silica concentration 3 mass%, average particle size 80 nm measured by dynamic light scattering method, specific surface area 34 m ² / g, particle size variation coefficient (CV value) 15 %) Was poured into a reaction vessel equipped with a stirrer, 10 g (0.125 mol) of an aqueous sodium hydroxide solution (sodium hydroxide concentration 5 mass%) was added at room temperature, and the pH was measured to be 11.3. It was.
The silica sol to which this aqueous sodium hydroxide solution was added was heated at a temperature of 80 ° C. for 1 hour, and while maintaining the temperature at 80 ° C., 9 g of zirconium carbonate aqueous solution concentration (5.0 mass%) was added at an addition rate of 1 g / min. , Added over 9 minutes.
As a result, gold-plated sugar-like fine particles formed by forming hook-like protrusions made of zirconium oxide on the surface of the silica fine particles were produced.

Silica sol (manufactured by Catalyst Kasei Kogyo Co., Ltd., Cataloid SI-50, silica concentration 3 mass%, average particle size 25 nm measured by dynamic light scattering method, specific surface area 109 m ² / g, particle size variation coefficient (CV value) 30 %) Was poured into a reaction vessel equipped with a stirrer, and at room temperature, 10 g (0.125 mol) of an aqueous sodium hydroxide solution (sodium hydroxide concentration 5 mass%) was added, and the pH was measured to be 11.1. It was.
The silica sol to which this aqueous sodium hydroxide solution was added was heated at a temperature of 80 ° C. for 1 hour, and while maintaining the temperature at 80 ° C., 30 g of zirconium carbonate aqueous solution concentration (5.0 mass%) was added at an addition rate of 1 g / min. Over 30 minutes.
As a result, gold-plated sugar-like fine particles formed by forming hook-like protrusions made of zirconium oxide on the surface of the silica fine particles were produced. A polishing test was conducted on the confetti-like composite silica sol, and the results are shown in Table 1.

Silica sol (catalyst SI-45P manufactured by Catalytic Chemical Industry Co., Ltd., silica concentration 3 mass%, average particle diameter 45 nm measured by dynamic light scattering method, specific surface area 61 m ² / g, particle diameter variation coefficient (CV value) 25% ) 1000 g was poured into a reaction vessel equipped with a stirrer, 10 g (0.125 mol) of an aqueous sodium hydroxide solution (sodium hydroxide concentration 5 mass%) was added at room temperature, and the pH was measured to be 11.1. .
The silica sol to which the aqueous sodium hydroxide solution was added was heated at a temperature of 80 ° C. for 1 hour, and while maintaining the temperature at 80 ° C., 50 g of zirconium carbonate aqueous solution concentration (5.0 mass%) was added at an addition rate of 1 g / min. Over 50 minutes.
As a result, gold-plated sugar-like fine particles formed by forming hook-like protrusions made of zirconium oxide on the surface of the silica fine particles were produced.

Silica sol (catalyst SI-45P manufactured by Catalytic Chemical Industry Co., Ltd., silica concentration 3 mass%, average particle diameter 45 nm measured by dynamic light scattering method, specific surface area 61 m ² / g, particle diameter variation coefficient (CV value) 25% ) 1000 g was poured into a reaction vessel equipped with a stirrer, 10 g (0.125 mol) of an aqueous sodium hydroxide solution (sodium hydroxide concentration 5 mass%) was added at room temperature, and the pH was measured to be 11.2. .
The silica sol to which this sodium hydroxide aqueous solution was added was heated at a temperature of 80 ° C. for 1 hour, and while maintaining the temperature at 80 ° C., 5 g of zirconium nitrate ammonium aqueous solution concentration (5.0 mass%) was added at an addition rate of 1 g / min. Added over 5 minutes.
As a result, gold-plated sugar-like fine particles formed by forming hook-like protrusions made of zirconium oxide on the surface of the silica fine particles were produced. A polishing test was conducted on the produced confetti-like composite silica sol, and the results are shown in Table 1.

1000 g of silica sol (silica concentration 3% by mass, average particle size 11 nm measured by dynamic light scattering method, specific surface area 250 m ² / g, particle size variation coefficient (CV value) 35%) was injected into a reaction vessel equipped with a stirrer, Thereto was added 10 g (0.125 mol) of an aqueous sodium hydroxide solution (sodium hydroxide concentration 5 mass%), and the pH was measured to be 11.0.
The silica sol to which this aqueous sodium hydroxide solution was added was heated at a temperature of 80 ° C. for 1 hour. Immediately after the heating, 60 g of an aqueous cerium ammonium nitrate solution (concentration: 5.0% by mass) was added over 60 minutes at an addition rate of 1 g / min. As a result, gold-plated sugar-like fine particles in which ridge-like protrusions made of cerium oxide were formed on the surface of the silica fine particles were produced.

Comparative Example 1

Silica sol (catalyst SI-45P manufactured by Catalytic Chemical Industry Co., Ltd., silica concentration 3 mass%, average particle diameter 45 nm measured by dynamic light scattering method, specific surface area 61 m ² / g, particle diameter variation coefficient (CV value) 25% ) 1000 g was poured into a reaction vessel equipped with a stirrer, 10 g (0.125 mol) of an aqueous sodium hydroxide solution (sodium hydroxide concentration 5 mass%) was added, and the pH was measured to be 11.1.
The silica sol to which this aqueous sodium hydroxide solution was added was heated at a temperature of 80 ° C. for 1 hour. Immediately after the heating, 20 g of zirconium ammonium carbonate aqueous solution concentration (5.0 mass%) was added at an addition rate of 10 g / min over 2 minutes.
The surface of the silica fine particles in the obtained sol was covered with a zirconium compound, but no clear ridge-like projections were formed.

Comparative Example 2

Silica sol (catalyst SI-50 manufactured by Catalytic Chemical Industry Co., Ltd., silica concentration 3 mass%, average particle diameter 25 nm measured by dynamic light scattering method, specific surface area 109 m ² / g, particle diameter variation coefficient (CV value) 30% ) 1000 g was poured into a reaction vessel equipped with a stirrer, 50 g (0.625 mol) of an aqueous sodium hydroxide solution (sodium hydroxide concentration 5 mass%) was added thereto, and the pH was measured to be 11.1.
The silica sol to which this aqueous sodium hydroxide solution was added was heated at a temperature of 80 ° C. for 1 hour. Immediately after the heating, 1000 g of zirconium ammonium carbonate aqueous solution concentration (5.0 mass%) was added over 10 minutes at an addition rate of 100 g / min.
The surface of the silica fine particles in the obtained sol was covered with a zirconium compound, but no clear ridge-like projections were formed.

Comparative Example 3

Reaction with 1000 g of silica sol (cataloid SI-45P, silica concentration 3 mass%, average particle diameter 45 nm measured by dynamic light scattering method, specific surface area 61 m ² / g, particle diameter variation coefficient (CV value) 25%) with stirrer The solution was poured into a container, 10 g (0.125 mol) of an aqueous sodium hydroxide solution (sodium hydroxide concentration 5 mass%) was added thereto, and the pH was measured to be 11.1.
The silica sol to which this aqueous sodium hydroxide solution was added was heated at a temperature of 80 ° C. for 1 hour. Immediately after the heating, 1000 g of zirconium ammonium nitrate aqueous solution concentration (5.0 mass%) was added at an addition rate of 100 g / min over 10 minutes.
The surface of the silica fine particles in the obtained sol was covered with a zirconium compound, but no clear ridge-like projections were formed.

Silica sol (average particle size 11 nm measured by dynamic light scattering method, specific surface area 250 m ² / g measured by BET method, particle size variation coefficient (CV value) 35%, silica concentration 20% by mass, dispersion medium: pure Pure water is added to water), and 1000 g of silica sol adjusted to a silica concentration of 3% by mass is poured into a reaction vessel equipped with a stirrer, and 10.0 g of aqueous sodium hydroxide solution (sodium hydroxide concentration of 5% by mass) is added thereto. The pH was then 11.1.
Next, this silica sol was heated at a temperature of 80 ° C. for 1 hour with stirring. Immediately after the heating, 60 g of a peroxotitanic acid (TiO ₃ ) aqueous solution (TiO ₃ concentration: 5.0% by mass) was added all at once and stirred for 30 minutes.
As a result, gold-plated sugar-like fine particles formed by forming hook-like protrusions made of titanium oxide on the surface of the silica fine particles were produced.

Silica sol (Catalyst Kasei Kogyo Co., Ltd., Cataloid SI-45P, average particle size 45 nm measured by dynamic light scattering method, specific surface area 61 m ² / g measured by BET method, particle size variation coefficient (CV value) 25 %, Silica concentration 20% by mass, dispersion medium: pure water), and 1000 g of silica sol prepared by adjusting the silica concentration to 3% by mass is poured into a reaction vessel equipped with a stirrer. 10.0 g of sodium oxide concentration (5% by mass) was added to adjust the pH to 11.2.
Next, this silica sol was heated at a temperature of 80 ° C. for 1 hour with stirring. Immediately after the heating, 15 g of a peroxotitanic acid (TiO ₃ ) aqueous solution (TiO ₃ concentration 5.0% by mass) was added all at once and stirred for 30 minutes.
As a result, gold-plated sugar-like fine particles formed by forming hook-like protrusions made of titanium oxide on the surface of the silica fine particles were produced.

Silica sol (manufactured by Catalytic Chemical Industry Co., Ltd., Cataloid SI-80P, average particle size of 80 nm measured by dynamic light scattering method, specific surface area of 34 m ² / g measured by BET method, particle size variation coefficient (CV value) 15 %, Silica concentration 20% by mass, dispersion medium: pure water), and 1000 g of silica sol prepared by adjusting the silica concentration to 3% by mass is poured into a reaction vessel equipped with a stirrer. 10.0 g of sodium oxide concentration (5% by mass) was added to adjust the pH to 11.3.
Next, this silica sol was heated at a temperature of 80 ° C. for 1 hour with stirring. Immediately after the heating, 10 g of a peroxotitanic acid (TiO ₃ ) aqueous solution (TiO ₃ concentration: 5.0% by mass) was added all at once and stirred for 30 minutes.
As a result, gold-plated sugar-like fine particles formed by forming hook-like protrusions made of titanium oxide on the surface of the silica fine particles were produced.

Silica sol (manufactured by Catalyst Kasei Kogyo Co., Ltd., Cataloid SI-50P, average particle size 25 nm measured by dynamic light scattering method, specific surface area 109 m ² / g measured by BET method, particle size variation coefficient (CV value) 30 %, Silica concentration 20% by mass, dispersion medium: pure water), and 1000 g of silica sol prepared by adjusting the silica concentration to 3% by mass is poured into a reaction vessel equipped with a stirrer. 10.0 g of sodium oxide concentration (5% by mass) was added to adjust the pH to 11.1.
Next, this silica sol was heated at a temperature of 80 ° C. for 1 hour with stirring. Immediately after the heating, 30 g of a peroxotitanic acid (TiO ₃ ) aqueous solution (TiO ₃ concentration of 5.0% by mass) was added all at once and stirred for 30 minutes.
As a result, gold-plated sugar-like fine particles formed by forming hook-like protrusions made of titanium oxide on the surface of the silica fine particles were produced.

Silica sol (Catalyst Kasei Kogyo Co., Ltd., Cataloid SI-45P, average particle size 45 nm measured by dynamic light scattering method, specific surface area 61 m ² / g measured by BET method, particle size variation coefficient (CV value) 25 %, Silica concentration 20% by mass, dispersion medium: pure water), and 1000 g of silica sol prepared by adjusting the silica concentration to 3% by mass is poured into a reaction vessel equipped with a stirrer. 10.0 g of sodium oxide concentration (5% by mass) was added to adjust the pH to 11.1.
Next, this silica sol was heated at a temperature of 80 ° C. for 1 hour with stirring. Immediately after the heating, 50 g of a peroxotitanic acid (TiO ₃ ) aqueous solution (TiO ₃ concentration 5.0% by mass) was added all at once and stirred for 30 minutes.
As a result, gold-plated sugar-like fine particles formed by forming hook-like protrusions made of titanium oxide on the surface of the silica fine particles were produced.

Silica sol (Catalyst Kasei Kogyo Co., Ltd., Cataloid SI-45P, average particle size 45 nm measured by dynamic light scattering method, specific surface area 61 m ² / g measured by BET method, particle size variation coefficient (CV value) 25 %, Silica concentration 20% by mass, dispersion medium: pure water), and 1000 g of silica sol prepared by adjusting the silica concentration to 3% by mass is poured into a reaction vessel equipped with a stirrer. 10.0 g of sodium oxide concentration (5% by mass) was added to adjust the pH to 11.1.
Next, this silica sol was heated at a temperature of 80 ° C. for 1 hour with stirring. Immediately after the heating, 5 g of a peroxotitanic acid (TiO ₃ ) aqueous solution (TiO ₃ concentration of 5.0% by mass) was added all at once and stirred for 30 minutes.
As a result, gold-plated sugar-like fine particles formed by forming hook-like protrusions made of titanium oxide on the surface of the silica fine particles were produced.

Comparative Example 4

Preparation of core particle dispersion liquid Water was added to 24.8 g of silica sol (manufactured by Catalyst Kasei Kogyo Co., Ltd .: Cataloid SI-40, average particle diameter 21.2 nm measured by image analysis method, SiO ₂ concentration 40.7 mass%). 1010 g (SiO ₂ concentration 1% by mass), and a 5% by mass sodium hydroxide aqueous solution was added so that the silica sol had a pH of 11. Next, the temperature of the silica sol was raised to 80 ° C. and maintained at 80 ° C. for 30 minutes to obtain a core particle dispersion (liquid A).

708 g of core particle growth water glass (manufactured by Dokai Chemical Co., Ltd .: JIS No. 3 water glass, SiO ₂ concentration 24 mass%) was diluted with 2692 g of water to prepare 3400 g of an aqueous alkali silicate solution (liquid B). Moreover, 2899 g of water was added to 120.8 g of ammonium sulfate (made by Mitsubishi Chemical Corporation) as an electrolyte to prepare 3019.8 g of an aqueous electrolyte solution. Then, with respect to the total amount of the core particle dispersion (liquid A) maintained at 80 ° C., the alkali silicate aqueous solution (liquid B) and the electrolyte aqueous solution are respectively added at 80 ° C. over 5 hours. The particle growth was carried out.
Here, the equivalent ratio E _A / E _E of B solution alkaline and electrolyte was 1.0. Next, after aging at 80 ° C. for 1 hour, washing was performed with an ultrafiltration membrane until the pH reached 9.4. Subsequently, it was concentrated to obtain a confetti-like silica sol having a SiO ₂ concentration of 20% by mass.
The results of the polishing test for this silica sol are shown in Table 1.

Comparative Example 5

Pure water was added to silica sol (manufactured by Catalyst Kasei Kogyo Co., Ltd .: Cataloid SI-80, average particle size 110 nm measured by image analysis method, SiO ₂ concentration 40.5% by mass) to make the SiO ₂ concentration 20% by mass.
The results of the polishing test for this silica sol are shown in Table 1.

Comparative Example 6

Silica sol (manufactured by Catalyst Kasei Kogyo Co., Ltd., Cataloid SI-50P, average particle size 25 nm measured by dynamic light scattering method, specific surface area 109 m ² / g measured by BET method, particle size variation coefficient (CV value) 30 %, Silica concentration 20% by mass, dispersion medium: pure water), and 1000 g of silica sol prepared by adjusting the silica concentration to 3% by mass is poured into a reaction vessel equipped with a stirrer. 10.0 g of sodium oxide concentration (5% by mass) was added to adjust the pH to 11.1.
Next, this silica sol was heated at a temperature of 80 ° C. for 1 hour with stirring. Immediately after the heating, 1000 g of a peroxotitanic acid (TiO ₃ ) aqueous solution (TiO ₃ concentration of 5.0% by mass) was added all at once and stirred for 30 minutes.
The surface of the silica fine particles in the obtained sol was covered with a titanium compound, but no clear ridge-like projections were formed.

Comparative Example 7

Silica sol (Catalyst Kasei Kogyo Co., Ltd., Cataloid SI-45P, average particle size 45 nm measured by dynamic light scattering method, specific surface area 61 m ² / g measured by BET method, particle size variation coefficient (CV value) 25 %, Silica concentration 20% by mass, dispersion medium: pure water), and 1000 g of silica sol prepared by adjusting the silica concentration to 3% by mass is poured into a reaction vessel equipped with a stirrer. 10.0 g of sodium oxide concentration (5% by mass) was added to adjust the pH to 11.1.
Next, this silica sol was heated at a temperature of 80 ° C. for 1 hour with stirring. Immediately after the heating, 1000 g of a peroxotitanic acid (TiO ₃ ) aqueous solution (TiO ₃ concentration of 5.0% by mass) was added all at once and stirred for 30 minutes.
The surface of the silica fine particles in the obtained sol was covered with a titanium compound, but no hook-shaped protrusions were formed.

  The fried sugar-like composite silica sol of the present invention is useful as an abrasive and a polishing composition, and is an aluminum disk (aluminum or a plating layer on a substrate thereof), an aluminum wiring of a semiconductor multilayer wiring board, a glass substrate for an optical disk or a magnetic disk. It can be used for glass substrates for liquid crystal displays, glass substrates for photomasks, mirror finishing of glassy materials, and the like. It can also be used as a filler for resin moldings and coating films, cosmetic ingredients, adsorbents, coagulation promoters, suspending agents, thickeners, soil hardeners, and the like.

Claims (9)

  A composite silica fine particle having a plurality of ridge-like projections containing a metal oxide other than silica on the surface of the spherical silica fine particle, the specific surface area measured by the BET method being (SA1), and the average measured by the image analysis method The value of the surface roughness (SA1) / (SA2) when the specific surface area converted from the particle diameter (D2) is (SA2) is in the range of 1.7 to 5.0 and measured by the image analysis method. A gold flat sugar-like composite silica sol obtained by dispersing gold flat sugar-like composite silica fine particles having an average particle diameter (D2) in the range of 7 to 150 nm in a solvent.   The average height (H) of the hook-shaped projections corresponds to 3 to 30% of the average particle diameter (D2) of the flat-like sugar-like composite silica fine particles. Silica sol.   3. The gold flat sugar-like composite silica sol according to claim 1, wherein the metal oxide other than silica is selected from zirconium oxide, cerium oxide, tungsten oxide and titanium oxide.   4. The frivolous complex silica sol according to claim 1, wherein the sphericity of the confetti complex silica fine particles is in the range of 0.8 to 1. 5.   5. The confetti-like composite silica sol according to claim 1, wherein a particle diameter variation coefficient (CV value) of the confetti-like composite silica fine particles is in the range of 10 to 50%. .   A composite silica fine particle having a plurality of ridge-like projections containing a metal oxide other than silica on the surface of the spherical silica fine particle, the specific surface area measured by the BET method being (SA1), and the average measured by the image analysis method The value of the surface roughness (SA1) / (SA2) when the specific surface area converted from the particle diameter (D2) is (SA2) is in the range of 1.7 to 5.0 and measured by the image analysis method. A gold-peeled sugar-like composite silica sol obtained by dispersing gold-peeled sugar-like composite silica fine particles having an average particle diameter (D2) in the range of 7 to 150 nm in a solvent, and a particle diameter variation coefficient (CV value) of the gold-peeled sugar-like composite silica fine particles. ) In the range of 10 to 50%.   A polishing material comprising the confetti-like composite silica sol according to claim 6.   A polishing composition comprising the abrasive according to claim 7.   A gold flat sugar-like composite silica sol in which gold flat sugar-like composite silica fine particles having hook-like protrusions containing metal oxides having hardness different from that of silica are dispersed in a solvent on the surface of spherical silica fine particles.