WO2015087965A1 - シリカ粒子及びその製造方法並びにシリカゾル - Google Patents
シリカ粒子及びその製造方法並びにシリカゾル Download PDFInfo
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- WO2015087965A1 WO2015087965A1 PCT/JP2014/082817 JP2014082817W WO2015087965A1 WO 2015087965 A1 WO2015087965 A1 WO 2015087965A1 JP 2014082817 W JP2014082817 W JP 2014082817W WO 2015087965 A1 WO2015087965 A1 WO 2015087965A1
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/141—Preparation of hydrosols or aqueous dispersions
- C01B33/1415—Preparation of hydrosols or aqueous dispersions by suspending finely divided silica in water
- C01B33/1417—Preparation of hydrosols or aqueous dispersions by suspending finely divided silica in water an aqueous dispersion being obtained
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/145—Preparation of hydroorganosols, organosols or dispersions in an organic medium
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- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
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- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C01P2004/54—Particles characterised by their aspect ratio, i.e. the ratio of sizes in the longest to the shortest dimension
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
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- C—CHEMISTRY; METALLURGY
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Definitions
- the present invention relates to silica particles, a method for producing the same, and silica sol.
- a method for obtaining silica sol by neutralization or ion exchange using water glass as a raw material is known.
- a method for obtaining silica fine powder by a thermal decomposition method of silicon tetrachloride is also known.
- a method for producing a high-purity silica sol a method in which an alkoxysilane is hydrolyzed in an alcohol-water solution containing a basic catalyst is also known.
- a peak signal area appearing at a chemical shift of ⁇ 94 ppm to ⁇ 103 ppm is defined as Q3, and a chemical shift is expressed at ⁇ 103 ppm to ⁇ 115 ppm.
- the peak signal area is Q4
- a method of hydrothermally treating an untreated silica having a Q4 / Q3 value of 0.5 to 5.0 has been proposed (see, for example, Patent Document 1).
- an untreated silica material having a median particle size of 58 nm measured by a dynamic light scattering method and an average particle size of 44 nm obtained by TEM observation is used. .
- silica-based hollow particles silicic acid or silicate is hydrolyzed and condensed in the presence of a basic catalyst to form a silica-based coating layer covering core particles such as calcium carbonate.
- a basic catalyst for example, see Patent Document 2.
- the method of obtaining silica sol by neutralization or ion exchange using water glass as a raw material cannot completely remove impurities such as metals.
- the thermal decomposition method of silicon tetrachloride the silica fine powder obtained is aggregated particles, and even when dispersed in water or the like, a monodispersed sol cannot be obtained.
- chlorine ions remain as impurities, the purity of the silica sol is low, and it cannot be used for applications requiring high purity.
- Non-Patent Document 1 many unhydrolyzed alkoxy groups remain in the silica particles, and alcohol is eliminated by heating or hydrolysis. For this reason, it is difficult to obtain highly dense silica particles, and it is difficult to produce a silica sol having excellent moisture absorption resistance.
- pores and silanol groups may remain inside the silica particles after the alkoxy groups are removed by hydrolysis, and there is a possibility that the properties of the resin may be impaired when silica is used as a resin filler. It was.
- an object of the present invention is to provide high-purity silica particles excellent in denseness and moisture absorption resistance, a method for producing silica particles, and a silica sol.
- Silica particles according to an embodiment of the present invention for solving the above-mentioned problems are characterized by satisfying the following requirements (a) to (c) using alkoxysilane as a raw material.
- (A) Content of alkali metal element with respect to silica solid content is 5 ppm or less.
- B) The moisture absorption at a relative humidity of 50% is 0.25 mg / m 2 or less, and the refractive index by the immersion method is 1.450 to 1.460.
- C The average primary particle size converted from the specific surface area measured by the nitrogen adsorption method is 10 to 100 nm.
- the aspect ratio of the particles obtained from the transmission electron micrograph is 1.0 to 2.0. Note that the closer the aspect ratio is to 1, the closer to a true sphere.
- the method for producing silica particles which is another aspect of the present invention that solves the above problems, is characterized by having the following steps (A) and (B).
- B A step of hydrothermally treating the silica particle aqueous dispersion at 150 to 350 ° C.
- the amount of at least one selected base is preferably adjusted so that the molar ratio (base / SiO 2 ) is 0.002 to 0.20.
- a silica sol which is still another embodiment of the present invention for solving the above-mentioned problems is characterized by containing the above silica particles.
- high-purity silica particles excellent in denseness and moisture absorption resistance a method for producing silica particles, and a silica sol can be provided.
- the silica particles of the present embodiment are based on alkoxysilane as a raw material and satisfy the following requirements (a) to (c).
- the silica particles of this embodiment will be described.
- This embodiment uses alkoxysilane as a raw material. According to this, compared with the conventional method using water glass, it becomes easy to obtain highly purified silica particles. That is, in the conventional method using water glass, metal impurities derived from the natural product raw material remain inside the particles, so that it is difficult to obtain high-purity silica particles. In addition, additional processes may be required to remove metal impurities. On the other hand, according to the present embodiment, it is possible to avoid mixing of the metal impurities as described above, and the need for an additional process for removing the metal impurities is eliminated.
- this embodiment using alkoxysilane as a raw material does not substantially contain a metal species that becomes a metal impurity by a conventional method using water glass.
- the metal species here include sodium, iron, aluminum, and the like, but typically an alkali metal element such as sodium. Moreover, it is 5 ppm or less with respect to a silica solid content that it does not contain substantially.
- this embodiment includes the requirement (a) that the content of alkali metal element with respect to the silica solid content is 5 ppm or less.
- the alkali metal element is not limited to sodium.
- a plurality of alkali metal elements may be contained, but the total content thereof needs to be 5 ppm or less with respect to the silica solid content.
- the silica particles of this embodiment are excellent in applicability to various uses and can be applied to electronic materials that require high purity.
- the moisture absorption resistance is also excellent, there is little possibility of impairing the moisture absorption resistance of the resin when, for example, it is highly filled as a resin filler.
- An alkoxysilane is an alkyl ester of a silicic acid monomer or a silicic acid oligomer having a polymerization degree of 2 to 3 and having an alkyl group having 1 to 2 carbon atoms from the viewpoint of solubility in a medium and availability.
- TMOS tetramethyl silicate
- TEOS tetraethyl silicate
- methyl triethyl silicate dimethyl diethyl silicate, trimethyl ethyl silicate, trialkyl silicate having 1 to 2 carbon atoms in the alkyl group, and the like are preferably used.
- Alkoxysilane may be used alone or in combination of two or more.
- the alkoxysilane mixed esters having different alkyl groups in the molecule and mixtures thereof can also be used.
- the present embodiment includes requirement (b) that the amount of moisture absorption at 50% relative humidity is 0.25 mg / m 2 or less and the refractive index by the immersion method is 1.450 to 1.460.
- the silica particles are used in resin composite materials, etc. due to the low density and moisture absorption resistance of the silica particles. Tends to decrease.
- the value of the moisture absorption amount of requirement (b) corresponds to the moisture adsorption amount per unit surface area of the silica particles, and can be measured by the means shown in the examples as an example. Such a value can eliminate the influence of moisture adsorption other than the inside of the particles, that is, the influence of the particle diameter, among the moisture absorption of the silica particles. That is, the value of the moisture absorption amount of requirement (b) can be grasped as an index of moisture absorption characteristics inside the particles.
- such a value of moisture absorption assumes a predetermined condition, for example, that all of the moisture reaches the inside of the particle or that one or two layers of moisture are adsorbed on the particle surface.
- moisture that can be adsorbed inside may not be sufficiently detected by measuring the amount of moisture absorption.
- the refractive index by the immersion method is 1.450 to 1.460.
- the moisture absorption characteristics inside the particle can be determined by the refractive index by the immersion method, in addition to the moisture absorption amount.
- the refractive index can be measured by the means shown in the examples as an example.
- the above-mentioned moisture absorption and refractive index can both evaluate the characteristics related to the denseness inside the silica particles, and a correlation is recognized to some extent.
- the above-mentioned moisture absorption amount is obtained on the assumption of the above-mentioned predetermined conditions, a complete correlation between them is not recognized.
- the requirement (b) is satisfied by satisfying any of the requirements of the moisture absorption amount and the refractive index, but the requirement (b) is not satisfied when it is recognized that at least one of the requirements is not satisfied.
- the refractive index by the immersion method is within the above range, it can be determined that the silica particles are excellent in denseness and moisture absorption resistance. Such silica particles rarely adversely affect the moisture absorption resistance of the resin composite when used in resin composite materials and the like.
- the refractive index is measured by the following method using the fact that when the dry powder is immersed in a liquid, the particles appear to be transparent when the refractive index of the particles is equal to the liquid.
- the mixing ratio of the two organic solvents is adjusted and mixed so as to have a refractive index equivalent to that of the sample, and a simple method is used in which the refractive index of the mixed solution is measured with an Abbe refractometer.
- the refractive index measurement method is not limited to the above example.
- the present embodiment includes requirement (c) that the average primary particle diameter converted from the specific surface area measured by the nitrogen adsorption method is 10 to 100 nm.
- the specific surface area by the nitrogen adsorption method is a surface area per unit mass of the silica particles, and the average primary particle diameter is an average value of the primary particle diameters of the silica particles calculated from the specific surface area.
- Such an average primary particle diameter can be measured by the method shown in an Example as an example.
- the average primary particle diameter is larger than the above range, the characteristics as nanoparticles are hardly exhibited, and when silica particles are contained in the resin, it is difficult to obtain various improvement effects of the resin by including the silica particles. Become. In addition, transparency may be lost when a sol of silica particles is used as a resin composite material.
- the average primary particle size is smaller than the above range, the dispersibility of the silica particles in the medium or the resin is lowered, and it becomes difficult to blend the silica particles at a high concentration.
- moisture adsorption on the surface of the silica particles tends to increase, and in order to prevent this, many modifiers are required when the particle surface is modified with an organic substance.
- the average primary particle size of the silica particles produced depends on various factors such as the average primary particle size of the silica particles used as a raw material and the degree of particle growth.
- silica particles with a large average primary particle size silica particles with a small average primary particle size are used as raw materials, and a highly basic catalyst is used to increase the silica concentration, increase the reaction temperature, extend the heating time. What is necessary is just to make the particle growth property of a silica large by various processes, such as.
- large particles can be obtained by a method in which the particles obtained in the present invention are partially mixed with the raw material and further grown as core particles.
- silica raw materials having a uniform particle size distribution may be used so that the silica particle growth property is not increased by various processes.
- silica particles with a large average primary particle size are used as the raw material, particles that cannot be dissolved remain as nuclei depending on the added base species, and particles around the remaining nuclei. May be easier to grow. Therefore, it is preferable to select the average primary particle diameter of the silica particles used as a raw material in consideration of the base species, production conditions, and the like.
- the silica particles of the present embodiment described above are made of alkoxysilane as a raw material and satisfy the above-mentioned requirements (a) to (c), so that the silica particles have high density and excellent moisture absorption resistance. Therefore, it can be suitably applied to various applications, and can be applied to, for example, electronic materials that require high purity.
- the silica particle of this embodiment uses alkoxysilane as a raw material, there is a possibility that an alkoxy group derived from alkoxysilane may remain in the particle. Therefore, if it is possible to measure the amount of alkoxy groups remaining due to the use of alkoxysilane as a raw material, based on this residual amount, the silica particles are obtained using alkoxysilane as a raw material. It becomes possible to specify.
- the aspect ratio of the particles obtained from a transmission electron micrograph is preferably 1.0 to 2.0. Note that the closer the aspect ratio is to 1, the closer to a true sphere. Since such silica particles have high sphericity, they can be filled with high density as, for example, a resin filler.
- a known transmission electron microscope (TEM) can be used, and the aspect ratio of the particles is that the longest part of the particle is the major axis D L , the longest part is perpendicular to the line connecting the major axis, and the longest part is the minor axis D. It can be measured as S. (D L / D S ) is evaluated as an aspect ratio, and about 300 particles can be evaluated for each aspect ratio to obtain an arithmetic average.
- TEM transmission electron microscope
- silica particles described above are contained, a high-purity silica sol having excellent denseness and moisture absorption resistance can be provided.
- a silica sol has little adverse effect on the moisture absorption resistance of the resin composite when used in a resin composite material or the like. And it is excellent in applicability to various uses and can be applied to electronic materials that require high purity.
- the manufacturing method of this embodiment has the following processes (A) and (B).
- A) Hydrolysis of alkoxysilane in the presence of at least one base selected from the group consisting of ammonia, primary amine, secondary amine and cyclic tertiary amine, and the specific surface area measured by the nitrogen adsorption method A step of obtaining an aqueous dispersion of silica particles having a converted average primary particle diameter of 3 to 20 nm.
- B A step of hydrothermally treating the silica particle aqueous dispersion at 150 to 350 ° C.
- alkoxysilane is hydrolyzed in the presence of at least one base selected from the group consisting of ammonia, primary amine, secondary amine, and cyclic tertiary amine, and measured by a nitrogen adsorption method.
- the silica particles in this aqueous dispersion serve as a raw material for producing silica particles having the above requirements (a) to (c).
- the silica particles used as the raw material have a relatively small particle diameter, specifically, an average primary particle diameter calculated from a specific surface area measured by a nitrogen adsorption method is 3 to 20 nm. According to this, the dissolution precipitation property of silica particles can be improved and the particles can be efficiently grown. Furthermore, it can be avoided that particles that cannot be completely dissolved remain as large nuclei, and the particles can be prevented from growing around the remaining large nuclei, so that silica particles having excellent internal density can be obtained. become.
- silica particles having an average primary particle diameter of 3 to 20 nm as described above can be used as a raw material to produce silica particles having an average primary particle diameter of, for example, 10 to 100 nm.
- the average primary particle size is basically larger than the average primary particle size of the silica particles used as a raw material. That is, when the average primary particle diameter of the silica particles used as a raw material is, for example, 20 nm, the average primary particle diameter of the silica particles after production is basically larger than 20 nm.
- the denseness of the silica particles used as a raw material is not limited as long as the gist of the present invention is not changed. If the silica particles are sufficiently dissolved and precipitated, and this is repeated, silica particles excellent in denseness up to the inside can be obtained.
- the aqueous dispersion can be obtained from a liquid mainly composed of water.
- the water here may be pure water or ultrapure water such as ion exchange water, ultrafiltration water, reverse osmosis water, or distilled water.
- ion exchange water such as ion exchange water
- ultrafiltration water such as ion exchange water
- reverse osmosis water such as distilled water
- distilled water such as distilled water
- the present invention is not limited to the above examples.
- various additives and hydrophilic organic solvents may be contained.
- hydrophilic organic solvent examples include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, ethylene glycol, acetonitrile, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, acetone, tetrahydrofuran, and diethylene glycol. Not limited. These hydrophilic organic solvents may be used alone or in combination of two or more.
- alkoxide method in which alkoxysilane is hydrolyzed and subjected to condensation polymerization, high-purity silica particles can be easily obtained as described above.
- Alkoxysilanes similar to those described above can be used, and may be added as a stock solution or diluted with an organic solvent.
- step (A) it is desirable to include a step of adjusting the amount of at least one base selected from the group consisting of ammonia, primary amine, secondary amine, and cyclic tertiary amine in the aqueous dispersion.
- This step is a step of adjusting the molar ratio (base / SiO 2 ) of the total amount of base added to the raw material silica sol to be 0.002 to 0.20. Accordingly, when an appropriate amount of ammonia or amine used for hydrolysis of alkoxysilane in step (A) remains in the silica dispersion, the addition of this base can be omitted.
- step (A) when an excess of a basic catalyst is used in step (A), it is preferable to reduce this amount so that it is less than an appropriate amount.
- the reduction method include a distillation method, washing by ultrafiltration, and an ion exchange method, but are not particularly limited.
- the molar ratio (base / SiO 2 ) of the total amount of base added to the raw material silica sol by adding the base is 0.002 to 0. It is preferable to adjust so that.
- the base at this time may be the same as or different from that used in step (A).
- the amount of the base By adjusting the amount of the base, the balance between dissolution and precipitation of the silica particles can be brought into a state suitable for particle growth.
- this type of weak base is used to provide a high-purity silica excellent in denseness and moisture absorption resistance. Particles can be obtained.
- the use of a strong base containing an alkali metal or the like can be omitted, so that it is possible to avoid mixing of a base species such as an alkali metal inside the particle.
- the above requirement (a) that the content of the alkali metal element with respect to the silica solid content is 5 ppm or less is also easily satisfied.
- the base catalyst that can be used in step (A) is ammonia, primary amine, secondary amine, or cyclic tertiary amine.
- primary amines include methylamine, ethylamine, propylamine, isopropylamine, butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, hexylamine, aminocyclohexane, methoxyethylamine, ethoxyethylamine, and 3-methoxypropyl.
- Aliphatic amines such as amine, 3-ethoxypropylamine, ethylenediamine, hexamethylenediamine, N, N-dimethylethylenediamine, 3- (diethylamino) propylamine, 3- (dibutylamino) propylamine; unsaturated alkyls such as allylamine
- amines include aromatic amines such as benzylamine, phenethylamine, and xylylenediamine.
- secondary amines include aliphatic monoamines such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, dipentylamine, dihexylamine and dicyclohexylamine; aromatic monoamines such as diphenylamine and dibenzylamine; N -Benzylamines such as methylbenzylamine, N-ethylbenzylamine, N-butylbenzylamine, N-pentylbenzylamine, N-hexylbenzylamine, and cyclics such as pyrrolidine, methylpyrrolidine, piperidine, methylpiperidine, piperazine, morpholine Examples include amines.
- cyclic tertiary amine examples include N-methylpyrrolidine, N-ethylpyrrolidine, N-methylpiperidine, N-methylmorpholine, quinuclidine, diazabicycloundenecene and diazabicyclononene.
- the reason why these amines can be used among the tertiary amines is that they are relatively strong bases because of the cyclic structure, and it is possible to prevent silica from being gelled during heating in the subsequent step (B).
- ammonia and water-soluble amines are preferable, and amines having a boiling point of 120 ° C. or lower are more preferable.
- ammonia, methylamine, dimethylamine, ethylamine, diethylamine, propylamine, dipropylamine, Isopropylamine and diisopropylamine are particularly preferred. Since these bases have a relatively low boiling point (for example, approximately 120 ° C. or less), they can be easily removed by distillation or the like, and hardly remain in the aqueous dispersion and adversely affect the purity of the silica sol.
- Said base may be used individually by 1 type, and may use 2 or more types together.
- the method of mixing the base and the molar ratio (base / SiO 2 ) of the total addition amount of the base to the alkoxysilane-derived silicon can also be adjusted as appropriate without departing from the scope of the present invention.
- the temperature range of the aqueous dispersion is 150 to 350 ° C., preferably 170 to 350 ° C., more preferably 190 to 350 ° C.
- the denseness of a silica particle is grasped
- the time for hydrothermal treatment of the aqueous dispersion within the above temperature range varies depending on the treatment temperature, and the target particles can be obtained in a shorter time as the temperature increases.
- the apparatus for hydrothermal treatment is not particularly limited, and a known apparatus may be used as long as it does not adversely affect the denseness, moisture absorption resistance and purity of the silica particles.
- silica particles of the present embodiment high-purity silica excellent in denseness and moisture absorption resistance is obtained using alkoxysilane, which is advantageous in that high-purity silica particles are easily obtained. Particles can be produced. If the silica particles after production are contained, a high-purity silica sol excellent in denseness and moisture absorption resistance can be produced.
- Step (A) is a step of obtaining an aqueous dispersion of silica particles having an average primary particle size of 3 to 20 nm by hydrolysis of alkoxysilane as described above.
- an aqueous dispersion of such silica particles can be obtained. If necessary, by-produced alcohol, excess organic solvent, base Obtained by removing catalyst and the like.
- Water used in the aqueous medium may be pure water or ultrapure water such as ion exchange water, ultrafiltration water, reverse osmosis water, or distilled water.
- ultrapure water such as ion exchange water, ultrafiltration water, reverse osmosis water, or distilled water.
- hydrophilic organic solvent examples include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, ethylene glycol, acetonitrile, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, acetone, tetrahydrofuran, and diethylene glycol. Not limited. These hydrophilic organic solvents may be used alone or in combination of two or more. Preferred organic solvents are methanol, ethanol, propanol, acetone and the like which have a low boiling point and can be easily removed in a later step.
- An alkoxysilane is an alkyl ester of a silicic acid monomer or a silicic acid oligomer having a polymerization degree of 2 to 3 and having an alkyl group having 1 to 2 carbon atoms from the viewpoint of solubility in a medium and availability.
- TMOS tetramethyl silicate
- TEOS tetraethyl silicate
- methyl triethyl silicate dimethyl diethyl silicate, trimethyl ethyl silicate, trialkyl silicate having 1 to 2 carbon atoms in the alkyl group, and the like
- An alkoxysilane may be used individually by 1 type, and may use 2 or more types together.
- mixed esters having different alkyl groups in the molecule and mixtures thereof can also be used.
- the base catalyst is preferably ammonia, primary amine, or secondary amine, more preferably ammonia or an amine having a boiling point of 100 ° C. or lower.
- the hydrolyzed silica sol dispersion can be concentrated by a known method such as distillation or ultrafiltration. At this time, it is possible to remove part or most of the base used as a catalyst and the alcohol produced by the reaction.
- the silica sol obtained by hydrolysis of alkoxysilane in this embodiment has a relatively small particle size, specifically, an average primary particle size of 3 converted from the specific surface area measured by the nitrogen adsorption method. Those with ⁇ 20 nm are used.
- dissolution and precipitation are improved by increasing the surface area, and silica particles can be efficiently grown.
- large particles that cannot be completely dissolved remain as nuclei, and particle growth is prevented from being promoted around the remaining large nuclei, thereby obtaining silica particles having excellent compactness not only on the surface but also inside. Be able to.
- the hydrothermal treatment in the step (B) from the group consisting of ammonia, primary amine, secondary amine and cyclic tertiary amine in an aqueous dispersion of silica particles having an average primary particle size of 3 to 20 nm. It is preferable to adjust the amount of at least one base selected so that the molar ratio (base / SiO 2 ) is 0.002 to 0.20.
- the preferred range of the molar ratio (base / SiO 2 ) here varies depending on the type of base. For example, when ammonia is used as the base, the molar ratio (base / SiO 2 ) is 0. It is preferably in the range of .005 to 0.20.
- the molar ratio (base / SiO 2 ) is preferably in the range of 0.002 to 0.10.
- the silica solubility is lowered, so that particle growth is difficult to occur, and as a result, it is difficult to obtain dense particles. Further, when a part of silica is dissolved during heating and the pH is lowered, an unstable region is formed, and the whole may be gelled or a part of particles may be fused to generate a gel-like material. On the other hand, if the molar ratio (base / SiO 2 ) is larger than the above range, the solubility of silica in the system is too high and particles are likely to be fused, and is unnecessary from the inside of the silica particles and the aqueous dispersion. It may take time to remove the base.
- a more preferable range of the amount of the base is that when ammonia is used as the base, the molar ratio (base / SiO 2 ) is preferably in the range of 0.009 to 0.20.
- the molar ratio (base / SiO 2 ) is preferably in the range of 0.006 to 0.10. Within these ranges, spherical particles are obtained, which are useful as nanofillers that can be highly filled into resins and the like.
- FIG. 1 is a graph showing the relationship between the average primary particle diameter of the silica particles after production, the amount of moisture absorbed at a relative humidity of 50%, and the molar ratio (base / SiO 2 ).
- the average primary particle diameter of silica particles as a raw material is 11 nm
- the concentration of silica particles in the aqueous dispersion is 10% by mass
- the temperature at which the aqueous dispersion is hydrothermally treated is 250 ° C.
- the hydrothermal treatment An example in which the time to perform is 5 hours is shown.
- the solid line when changing the molar ratio (base / SiO 2), the average primary particle size of the silica particles after preparation, the molar ratio (base / SiO 2), are shown relationships of. Further, the dotted line shows the relationship between the moisture absorption amount at a relative humidity of 50% and the molar ratio (base / SiO 2 ) when the molar ratio (base / SiO 2 ) is changed. Further, an example using ammonia as a base is shown by a round plot, and an example using a secondary amine such as diisopropylamine is shown by a triangular plot.
- a high-purity silica particle excellent in denseness and moisture absorption resistance can be obtained using a weak base such as ammonia. Can be manufactured.
- the particle diameter is smaller even in the range of a small molar ratio (base / SiO 2 ) than in the example shown by the solid line using ammonia.
- Large silica particles can be obtained. This is because secondary amines such as diisopropylamine are generally stronger bases than ammonia, so that the solubility of silica particles in the medium is promoted and dissolution precipitation is promoted.
- the medium can be appropriately stirred. Further, the above base remains in the medium from which the silica particles are obtained, and the active silicic acid is dissolved. Therefore, in this embodiment, a part of the base can be removed from the medium. According to this, the pH in the system can be lowered, and the active silicic acid remaining in the medium can be deposited on the surface of the silica particles. Therefore, it is possible to reduce the active silicic acid and prevent an adverse effect on the stability of the aqueous dispersion of silica particles.
- Examples of the method for removing the base include a distillation method, an ion exchange method, and an ultrafiltration method, and are not particularly limited, but a method of volatilizing the base by heating so that the temperature of the medium is equal to or higher than the boiling point is preferable. According to this, all or a part of the base can be reliably removed from the medium.
- the entire amount of the liquid in the container was taken out of the vessel and concentrated to 970 g under a reduced pressure of 100 Torr using a rotary evaporator.
- ammonia determined by titration with an SiO 2 concentration of 10.2% by mass, pH 7.5, acid.
- a silica sol having a concentration of 0.001% by mass, a dynamic scattering method particle size of 10.8 nm, and an average primary particle size (hereinafter referred to as a BET method particle size) of 10 nm converted from a specific surface area measured by a nitrogen adsorption method was obtained. .
- the silica powder obtained by drying this silica sol had a moisture absorption per surface area of 0.42 mg / m 2 and a particle refractive index of 1.447.
- Raw material silica sol [2] was prepared as follows. In the same reaction vessel as in Production Example 1, 2244 g of pure water and 3.4 g of 28% by mass ammonia water were charged, and the liquid temperature in the vessel was kept at 80 ° C. by an oil bath. Next, 253 g of commercially available tetramethyl silicate (TMOS) was continuously fed into the liquid over 0.9 hours in this vessel under stirring. After completion of this supply, stirring was continued for 1 hour while maintaining the liquid temperature in the container at 80 ° C., then the liquid temperature was raised to 90 ° C., and stirring was continued at this temperature for 1 hour to obtain a dispersion of silica particles. It was.
- TMOS tetramethyl silicate
- the liquid in the container was evaporated in the same manner as in Production Example 1, and the liquid was concentrated to 99 ° C. by discharging the vapor out of the vessel.
- the entire amount of the solution was taken out of the vessel and concentrated to 970 g under a reduced pressure of 100 Torr by a rotary evaporator.
- the ammonia concentration determined by titration with an SiO 2 concentration of 10.2% by mass, pH 7.4 and acid was 0.0075%.
- a silica sol having a dynamic scattering particle diameter of 15 nm and a BET particle diameter of 11 nm was obtained.
- the moisture absorption per surface area of the silica powder obtained by drying the silica sol was 0.43 mg / m 2 , and the refractive index of the silica particles was 1.446.
- Raw material silica sol [3] was prepared as follows. In the same reaction vessel as in Production Example 1, 2214 g of pure water and 25.3 g of 28 mass% ammonia water were charged, and the liquid temperature in the vessel was kept at 80 ° C. by an oil bath. Next, 260.5 g of commercially available tetraethyl silicate (TEOS) was continuously added dropwise to this stirred vessel over 3 hours. After completion of this supply, stirring was continued for 1 hour while maintaining the liquid temperature in the container at 80 ° C., then the liquid temperature was raised to 90 ° C., and stirring was continued at this temperature for 1 hour to obtain a dispersion of silica particles. It was.
- TEOS tetraethyl silicate
- the liquid in the container was evaporated in the same manner as in Production Example 1, and the liquid was concentrated to 99 ° C. by discharging the vapor out of the vessel.
- the entire amount of the solution was taken out of the vessel and concentrated to 980 g under a reduced pressure of 100 Torr by a rotary evaporator.
- the residual ammonia amount determined by titration with an SiO 2 concentration of 10% by mass, pH 7.8 and acid was 0.0068% by mass.
- a silica sol having a dynamic scattering particle diameter of 23 nm and a BET particle diameter of 16 nm was obtained.
- the silica powder obtained by drying this silica sol had a moisture absorption per surface area of 0.21 mg / m 2 and a refractive index of 1.446.
- Raw material silica sol [4] was prepared as follows. In the same reaction vessel as in Production Example 1, 2229 g of pure water and 10.1 g of 28 mass% ammonia water were charged, and the liquid temperature in the vessel was kept at 90 ° C. by an oil bath. Next, 260.5 g of commercially available tetraethyl silicate (TEOS) was continuously added dropwise to the stirred vessel over 2.5 hours. After completion of the supply, stirring was continued for 2 hours while maintaining the liquid temperature in the container at 90 ° C. to obtain a dispersion of silica particles. Next, the liquid in the container was evaporated in the same manner as in Production Example 1, and the liquid was concentrated to 99 ° C. by discharging the vapor out of the vessel.
- TEOS tetraethyl silicate
- the entire amount of the solution was taken out of the vessel and concentrated to 980 g under a reduced pressure of 100 Torr using a rotary evaporator.
- the residual ammonia amount determined by titration with an SiO 2 concentration of 10 mass%, pH 7.7 and acid was 0.0049 mass%.
- a silica sol having a dynamic scattering particle diameter of 26.7 nm and a BET particle diameter of 19 nm was obtained.
- a commercially available silica sol (trade name “Quartron (registered trademark) PL-06L” manufactured by Fuso Chemical Industry Co., Ltd.) has a residual ammonia content determined by titration with an SiO 2 concentration of 6.3% by mass and pH 7.5. The amount used was 0.0054% by mass and the BET particle diameter was 8 nm. The hygroscopic amount per surface area of the silica powder obtained by drying this commercially available silica sol was 0.48 mg / m 2 , and the refractive index of the silica particles was 1.440.
- a commercially available silica sol (trade name “Quartron (registered trademark) PL-3” manufactured by Fuso Chemical Industry Co., Ltd.) has a residual ammonia concentration determined by titration with an acid having a SiO 2 concentration of 19.5 mass% and a pH of 7.3. The amount used was 0.0026% by mass and the BET particle size was 35 nm.
- the moisture absorption per surface area of the silica powder obtained by drying this commercially available silica sol was 1.08 mg / m 2 , and the refractive index of the silica particles was 1.390.
- Example 1 180 g of silica sol (raw material silica sol [1]) produced in Production Example 1 (SiO 2 concentration 10.2 mass%, BET method particle diameter 10 nm) has a molar ratio of (total amount of base added) / (silica) of 0.0125. As a result, 0.253 g of 25% aqueous ammonia was added and sufficiently mixed to obtain a mixed solution.
- the total amount of base added refers to the total amount of ammonia remaining in the raw material silica sol and the newly added base species.
- this mixed solution was put into a 300 mL stainless steel autoclave, heated to 250 ° C. with a dryer, and held for 5 hours.
- silica sol has a dynamic light scattering particle size of 49.5 nm and a BET method particle size of 32 nm.
- the moisture absorption per surface area of the silica powder from which this silica sol is dried is 0.19 mg / m 2 ,
- the refractive index was 1.454.
- the amount of sodium contained in the silica particles was 1 ppm.
- Example 2 to 13 Using the same apparatus as in Example 1, silica sol was prepared in the same manner by changing the conditions such as the BET method particle diameter, base species, molar ratio, and autoclave treatment temperature as shown in Table 1, and the silica particles were prepared. evaluated.
- Example 3 A silica sol was prepared using the same apparatus and method as in Example 1 except that 0.609 g of 10% sodium hydroxide solution was added as a base species, and the molar ratio of (total amount of base added) / (silica) was 0.0053. Produced. The moisture absorption per surface area of the silica powder obtained by drying this silica sol was 0.14 mg / m 2 , and the refractive index of the silica particles was 1.456. However, when metal impurities were analyzed after cation exchange of the obtained silica sol, the amount of sodium contained in the silica particles was 80 ppm. From this, it was found that when sodium was used, sodium was taken into the particles during particle growth, and high-purity silica particles could not be obtained.
- Example 4 A silica sol was prepared in the same container and method as in Example 1 except that the SiO 2 concentration of the raw material silica sol [6] was adjusted to 10% by mass and 0.236 g of 25% aqueous ammonia was added.
- the silica powder obtained by drying the silica sol had a moisture absorption amount per surface area of 0.50 mg / m 2 and a refractive index of 1.390. The moisture absorption amount was not low, and the particles could not be densified.
- the average primary particle diameter was measured by the nitrogen adsorption method (BET method) as follows for the silica particles used as raw materials in the above Examples and Comparative Examples and the silica particles obtained by the above Examples and Comparative Examples. That is, the silica sol was subjected to cation exchange to remove the base, and the silica gel obtained by drying in an 80 ° C. vacuum dryer was pulverized in a mortar and further dried at 180 ° C. for 3 hours to obtain a silica dry powder. The specific surface area (m 2 / g) of this powder by the nitrogen adsorption method was measured, and the average primary particle size was determined by the following formula (1). The measurement was performed using Monosorb (manufactured by Quantachrome Corporation). As described above, in Comparative Examples 1 and 2, gelation of the silica particles was confirmed, and the average primary particle size could not be calculated.
- the hygroscopic property was measured as follows. That is, the same 180 g dry powder as that used for measurement of the specific surface area was collected in 0.2 g weighing bottles, and the weight was measured. The bottle was allowed to stand for 48 hours in an atmosphere of 23 ° C. and 50% relative humidity with the lid open, and then the lid was capped and the weight was measured again. And based on the BET method specific surface area, the amount of moisture absorption per specific surface area was calculated from the following formula (2).
- the refractive index was measured as follows. That is, for the silica sols of Examples 1 to 13 and Comparative Examples 1 to 4, 0.1 g of the same dry powder used for the measurement of the specific surface area was placed in a 10 cc glass bottle, and then the ratio of special grade 2-propanol and special grade toluene was determined. When the powder in the container became transparent, the supernatant was measured with an Abbe refractometer to obtain the refractive index of the silica particles.
- silica particle shape after hydrothermal treatment About the silica particle obtained by said Example and comparative example, the shape was measured as follows using the transmission electron micrograph. That is, for about 300 particles, the longest part of the particle is measured as the major axis D L , the longest part is perpendicular to the line connecting the major axes, and the longest part is measured as the minor axis D S , and (D L / D S ) Was evaluated as an aspect ratio, and an arithmetic average was obtained.
- Examples 1 to 13 were produced by the method having the steps (A) to (B) described above, whereby high-purity silica particles and silica sols excellent in denseness and moisture absorption resistance were obtained. Was found to be obtained.
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Abstract
Description
(a)シリカ固形分に対するアルカリ金属元素の含有量が5ppm以下である。
(b)相対湿度50%における吸湿量が0.25mg/m2以下、かつ液浸法による屈折率が1.450~1.460である。
(c)窒素吸着法により測定される比表面積から換算される平均一次粒子径が10~100nmである。
(A)アルコキシシランをアンモニア、1級アミン、2級アミン及び環状3級アミンからなる群から選ばれる少なくとも1種の塩基の共存下で加水分解して、窒素吸着法により測定される比表面積から換算される平均一次粒子径が3~20nmであるシリカ粒子の水分散液を得る工程。
(B)前記シリカ粒子の水分散液を150~350℃で水熱処理する工程。
(a)シリカ固形分に対するアルカリ金属元素の含有量が5ppm以下である。
(b)相対湿度50%における吸湿量が0.25mg/m2以下、かつ液浸法による屈折率が1.450~1.460である。
(c)窒素吸着法により測定される比表面積から換算される平均一次粒子径が10~100nmである。
以下、本実施形態のシリカ粒子について説明する。
(A)アルコキシシランをアンモニア、1級アミン、2級アミン及び環状3級アミンからなる群から選ばれる少なくとも1種の塩基の共存下で加水分解して、窒素吸着法により測定される比表面積から換算される平均一次粒子径が3~20nmであるシリカ粒子の水分散液を得る工程。
(B)前記シリカ粒子の水分散液を150~350℃で水熱処理する工程。
〔製造例1〕
原料シリカゾル[1]を以下のように作製した。攪拌機及びコンデンサー付き3リットルのステンレス製反応容器に、純水2244gと28質量%のアンモニア水3.4gを仕込み、オイルバスにより容器内液温を80℃に保った。次いで、攪拌下のこの容器内に、253gの市販テトラメチルシリケート(TMOS)を、1.8時間かけて連続的に液中に供給した。この供給の終了後、容器内液温を80℃に保ったまま1時間攪拌を続けた後、液温を90℃まで上昇させ、この温度で1時間攪拌を続けてシリカ粒子の分散液を得た。次いで、容器につけたコンデンサーを枝付き管につけ替え、枝付き管の先に冷却管をつけてから反応液の温度を沸点まで上昇させ、容器内の液を蒸発させ、蒸気を器外に排出させることにより、液温が99℃になるまで濃縮した。
原料シリカゾル[2]を以下のように作製した。製造例1と同じ反応容器に、純水2244gと28質量%のアンモニア水3.4gを仕込み、オイルバスにより容器内液温を80℃に保った。次いで、攪拌下のこの容器内に、253gの市販テトラメチルシリケート(TMOS)を、0.9時間かけて連続的に液中に供給した。この供給の終了後、容器内液温を80℃に保ったまま1時間攪拌を続けた後、液温を90℃まで上昇させ、この温度で1時間攪拌を続けてシリカ粒子の分散液を得た。
原料シリカゾル[3]を以下のように作製した。製造例1と同じ反応容器に、純水2214gと28質量%のアンモニア水25.3gを仕込み、オイルバスにより容器内液温を80℃に保った。次いで、攪拌下のこの容器内に、260.5gの市販テトラエチルシリケート(TEOS)を、3時間かけて連続的に滴下し供給した。この供給の終了後、容器内液温を80℃に保ったまま1時間攪拌を続けた後、液温を90℃まで上昇させ、この温度で1時間攪拌を続けてシリカ粒子の分散液を得た。
原料シリカゾル[4]を以下のように作製した。製造例1と同じ反応容器に、純水2229gと28質量%のアンモニア水10.1gを仕込み、オイルバスにより容器内液温を90℃に保った。次いで、攪拌下のこの容器内に、260.5gの市販テトラエチルシリケート(TEOS)を、2.5時間かけて連続的に滴下し供給した。この供給の終了後、容器内液温を90℃に保ったまま2時間攪拌を続けてシリカ粒子の分散液を得た。次いで、製造例1と同様に容器内の液を蒸発させ、蒸気を器外に排出させることにより、液温が99℃になるまで濃縮した。
市販品であるシリカゾル(扶桑化学工業株式会社製、商品名「クォートロン(登録商標)PL-06L」)は、SiO2濃度6.3質量%、pH7.5、酸による滴定法で求めた残存アンモニア量は0.0054質量%、BET法粒子径8nmのものを使用した。この市販品シリカゾルを乾燥して得られるシリカ粉末の表面積当たりの吸湿量は0.48mg/m2、シリカ粒子の屈折率は1.440であった。
市販品であるシリカゾル(扶桑化学工業株式会社製、商品名「クォートロン(登録商標)PL-3」)は、SiO2濃度19.5質量%、pH7.3、酸による滴定法で求めた残存アンモニア量は0.0026質量%、BET法粒子径35nmのものを使用した。この市販品シリカゾルを乾燥して得られるシリカ粉末の表面積当たりの吸湿量は1.08mg/m2、シリカ粒子の屈折率は1.390であった。
製造例1で作製したシリカゾル(原料シリカゾル[1])180g(SiO2濃度10.2質量%、BET法粒子径10nm)に(塩基の総添加量)/(シリカ)のモル比が0.0125となるように25%アンモニア水を0.253g添加し、十分に撹拌することで混合液を得た。ここで、塩基の総添加量とは、原料シリカゾル中に残存するアンモニアと新たに添加した塩基種の総量をいう。次いでこの混合液を300mLのステンレス製のオートクレーブに入れ、乾燥器で250℃まで昇温した後、5時間保持した。その後室温まで冷却し、容器より取り出してシリカゾルを得た。このゾルは動的光散乱法粒子径49.5nmであり、BET法粒子径32nmであり、このシリカゾルを乾燥していられるシリカ粉末の表面積当たりの吸湿量は0.19mg/m2、シリカ粒子の屈折率は1.454であった。また、シリカ粒子に含有されるナトリウム量は1ppmであった。
実施例1と同様の装置を用いて、表1に示すようなBET法粒子径、塩基種、モル比、及びオートクレーブ処理温度等の条件を変えて同様の方法でシリカゾルを作製し、シリカ粒子を評価した。
塩基種としてトリエチルアミンを0.306g添加した以外は実施例1と同様の装置及び方法でオートクレーブ処理を行なったが、ゲル化したためシリカゾルを得ることができず、シリカ粒子の評価が不可能であった。
塩基種として35%テトラメチルアンモニウムヒドロキシドを1.562g添加した以外は実施例1と同様の装置及び方法でオートクレーブ処理を行なったが、ゲル化したため、シリカゾルを得ることができず、シリカ粒子の評価が不可能であった。
塩基種として10%水酸化ナトリウム溶液を0.609g添加し、(塩基の総添加量)/(シリカ)のモル比を0.0053とした以外は実施例1と同様の装置及び方法でシリカゾルを作製した。このシリカゾルを乾燥して得られるシリカ粉末の表面積当たりの吸湿量は0.14mg/m2、シリカ粒子の屈折率は1.456であった。しかし、得られたシリカゾルを陽イオン交換した後に金属不純物分析をしたところ、シリカ粒子に含有されるナトリウム量は80ppmであった。このことから、ナトリウムを用いた場合、粒子成長時に粒子内部にナトリウムが取り込まれてしまい、高純度のシリカ粒子を得られないことが分かった。
原料シリカゾル[6]のSiO2濃度を10質量%に濃度調整し、25%アンモニア水を0.236g添加した以外は、実施例1と同様の容器及び方法でシリカゾルを作製した。このシリカゾルを乾燥して得られるシリカ粉末の表面積当たりの吸湿量は0.50mg/m2、屈折率は1.390であり、吸湿量は低くならず、粒子内部まで緻密化できていなかった。
上記の実施例及び比較例で原料としたシリカ粒子や、上記の実施例及び比較例により得られたシリカ粒子につき、以下のように窒素吸着法(BET法)により平均一次粒子径を測定した。すなわち、シリカゾルを陽イオン交換して塩基を除去し、80℃真空乾燥器で乾燥して得られたシリカゲルを乳鉢で粉砕した後、更に180℃で3時間乾燥してシリカ乾燥粉末を得た。この粉末の窒素吸着法による比表面積(m2/g)を測定し、平均一次粒子径は以下の式(1)で求めた。測定は、Monosorb(Quantachrome Corporation 製)を用いて行った。尚、上記のように比較例1~2ではシリカ粒子のゲル化が確認され、平均一次粒子径を算出できなかった。
平均一次粒子径=2720/比表面積(m2/g) (1)
動的光散乱法測定装置:Zetasizer Nano(Malvern Instruments Ltd 製)を用いて公知の方法により測定した。
上記の実施例及び比較例により得られたシリカ粒子につき、以下のように吸湿性を測定した。すなわち、比表面積の測定に用いたものと同じ180℃乾燥粉を各0.2g秤量瓶に採取し、重量を測定した。この瓶を、蓋を開けた状態で23℃相対湿度50%の雰囲気下に48時間静置した後、蓋をして再び重量を測定した。そして、BET法比表面積を基に、以下の式(2)より、比表面積あたりの吸湿量を計算した。
吸湿量(mg/m2)=増加重量(mg)/(サンプル量(g)×比表面積(m2/g)) (2)
上記の実施例及び比較例により得られたシリカ粒子につき、以下のように屈折率を測定した。すなわち、実施例1~13及び比較例1~4のシリカゾルについて、比表面積の測定に用いたものと同じ乾燥粉0.1gを10ccのガラス瓶に入れ、次いで特級2-プロパノール及び特級トルエンの比率を変えて添加し、容器内の粉体が透明になったときの上澄みをアッベ屈折計で測定し、シリカ粒子の屈折率とした。
本発明の実施例1及びアルカリ金属を含む強塩基である水酸化ナトリウム(NaOH)を用いた上記の比較例3につき、得られたシリカ粒子に対して以下のように測定した。すなわち、実施例1及び比較例3のシリカゾルについて、ナトリウムはシリカゾルを白金皿中で希硝酸とフッ酸で溶解後乾固し、ついで白金皿に希硝酸を添加して得た水溶液を原子吸光分析法で測定した。
上記の実施例及び比較例により得られたシリカ粒子につき、透過型電子顕微鏡写真を用い以下のように形状を測定した。すなわち、およそ300個程度の粒子について、その粒子の一番長い部分を長径DL、長径を結ぶ線と直行していて一番長い部分を短径DSとして測定し、(DL/DS)をアスペクト比として評価し、算術平均を求めた。
Claims (5)
- アルコキシシランを原料とし、下記の要件(a)~(c)を満たすことを特徴とするシリカ粒子。
(a)シリカ固形分に対するアルカリ金属元素の含有量が5ppm以下である。
(b)相対湿度50%における吸湿量が0.25mg/m2以下、かつ液浸法による屈折率が1.450~1.460である。
(c)窒素吸着法により測定される比表面積から換算される平均一次粒子径が10~100nmである。 - 透過型電子顕微鏡写真から求められる粒子のアスペクト比が1.0~2.0であることを特徴とする請求項1に記載のシリカ粒子。
- 下記の工程(A)及び(B)を有することを特徴とするシリカ粒子の製造方法。
(A)アルコキシシランをアンモニア、1級アミン、2級アミン及び環状3級アミンからなる群から選ばれる少なくとも1種の塩基の共存下で加水分解して、窒素吸着法により測定される比表面積から換算される平均一次粒子径が3~20nmであるシリカ粒子の水分散液を得る工程。
(B)前記シリカ粒子の水分散液を150~350℃で水熱処理する工程。 - 前記(B)工程の水熱処理を行う前に平均一次粒子径が3~20nmであるシリカ粒子の水分散液中のアンモニア、1級アミン、2級アミン及び環状3級アミンからなる群から選ばれる少なくとも1種の前記塩基の量をモル比(塩基/SiO2)が0.002~0.20となるように、調節することを特徴とする請求項3に記載のシリカ粒子の製造方法。
- 請求項1又は2に記載のシリカ粒子を含有することを特徴とするシリカゾル。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020167018323A KR102269433B1 (ko) | 2013-12-12 | 2014-12-11 | 실리카 입자 및 그 제조 방법 그리고 실리카 졸 |
EP14870123.8A EP3081531B1 (en) | 2013-12-12 | 2014-12-11 | Silica particles, manufacturing method for same, and silica sol |
US15/101,154 US10173901B2 (en) | 2013-12-12 | 2014-12-11 | Silica particles, manufacturing method for the same, and silica sol |
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JP2021147267A (ja) * | 2020-03-18 | 2021-09-27 | 三菱ケミカル株式会社 | シリカ粒子の製造方法、シリカゾルの製造方法、研磨方法、半導体ウェハの製造方法及び半導体デバイスの製造方法 |
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WO2023248949A1 (ja) * | 2022-06-20 | 2023-12-28 | 三菱ケミカル株式会社 | シリカ粒子とその製造方法、シリカゾル、研磨組成物、研磨方法、半導体ウェハの製造方法及び半導体デバイスの製造方法 |
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TW201534562A (zh) | 2015-09-16 |
CN113651335A (zh) | 2021-11-16 |
KR102269433B1 (ko) | 2021-06-24 |
JPWO2015087965A1 (ja) | 2017-03-16 |
KR20160097287A (ko) | 2016-08-17 |
US20170001870A1 (en) | 2017-01-05 |
JP6447831B2 (ja) | 2019-01-09 |
EP3081531B1 (en) | 2021-03-10 |
CN105813977A (zh) | 2016-07-27 |
TWI690489B (zh) | 2020-04-11 |
EP3081531A4 (en) | 2017-06-14 |
US10173901B2 (en) | 2019-01-08 |
EP3081531A1 (en) | 2016-10-19 |
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