JPH0350105A - Production of inorganic oxide grains - Google Patents

Abstract

PURPOSE:To obtain the inorg. oxide grains having a desired diameter at a high concn. without causing agglomeration by dispersing inorg. oxide seed grains in an aq. alcoholic soln. contg. an alkylene glycol and adding an organometallic compd. to the suspension to grow the seed grains. CONSTITUTION:The inorg. oxide grains are dispersed as seed grains in an aq. alcoholic soln., an organometallic compd. capable of being hydrolyzed and condensed is added to the suspension of the seed grains to grow the seeds, and the inorg. oxide grains having a larger diameter than the seed grain are produced. In this method, 1-50wt.% of a 2-8C alkylene glycol is incorporated into the aq. alcoholic soln., and the inorg. oxide grains as an excellent monodisperse system are obtained. The organometallic compd. shown by the formula (M is a metallic element, R<1> is H, unsaturated aliphatic residues, etc., R<2> is an alkyl, (m) is 0 or an integer, (n)>=1, and (m+n) is the valence of the metallic element), and Si, Ti, Zr and Al are preferably exemplified as the M.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an industrially advantageous method for producing inorganic oxide particles in which the formation of agglomerated particles is prevented and the particle diameter is arbitrarily controlled. The particles have industrial value as carriers for chromatography, materials for catalysts, pigments, solid lubricants, paints or fillers for synthetic resin molded products such as fibers and films.

(Prior Art) Conventionally, methods for producing inorganic oxide particles include a method in which a metal oxide sol is sprayed into a heated non-polar solvent to form a gel, a method in which a metal salt solution is spray-dried and then fired, and a method in which a metal salt solution is spray-dried and then fired. A method of emulsifying a solution and interfacial polymerization, a method of hydrolyzing or thermally decomposing a metal alkoxide in an organic solvent or in a gas phase, and the like are known. Among these, particles are produced by hydrolyzing or neutralizing a raw material compound in a solution.
The so-called wet method is widely adopted because it is easy to control the particle diameter and prevent the formation of agglomerated particles.

Among the wet methods, the method of hydrolyzing a metal alkoxide in an organic solvent has been attracting attention as a method for obtaining particles with a narrow particle size distribution and excellent dispersibility.

For example, a method for obtaining amorphous silica particles using tetraalkoxysilane as a raw material (W, 5t6ber et al., J, C
o11oid and Interface 5cle
nce 26+ 62-69 (196B), etc.), a method for obtaining hydrous titanium oxide particles using tetraethoxytitanium as a raw material (Barrillnget et al., Langmuir
1.414 (1985), etc.), a method for obtaining hydrated aluminum oxide particles using trisec-butoxyaluminum as a raw material (D, L, Catone et al., J, Co1
1 and Interface 5 tier
, +4EL 291 (1974), etc.).

From these documents, basic reaction conditions for obtaining spherical monodispersed particles by hydrolyzing an alkoxy metal compound in an organic solvent such as alcohol can be deduced. However, once the type of raw material alkoxy metal compound is determined, there is a limit to the particle size produced even if the reaction conditions such as the organic solvent, the type and composition of the catalyst, and the reaction temperature are changed. Among these, when using tetraalkoxysilane as a raw material and a monohydric alcohol as an organic solvent, the larger the number of carbon atoms in the -hydric alcohol, the larger the particle size of the produced silica particles, but the maximum diameter was 2 μm. Furthermore, when trying to increase the concentration of the raw material tetraalkoxysilane to increase the concentration of the produced particles or increase the diameter of the produced particles in consideration of industrial productivity, the problem arises that the particle size distribution widens and the particles eventually aggregate. there were.

In order to solve these problems, as a method for producing silica particles, Japanese Patent Application Laid-Open No. 62-72514 discloses that fine silica particles in a slurry obtained by hydrolyzing tetraalkoxysilane in a hydroalcoholic solution are used as seed particles. A method of supplying raw material alkoxysilane has been proposed. However, although this method can increase the particle size, when the concentration of raw materials is increased to increase productivity, the formation of agglomerated particles becomes noticeable, making it difficult to use as an industrial method for producing monodisperse silica particles. Furthermore, in JP-A No. 62-72516, alkali metal ions are supplied when the raw material alkoxysilane compound is sequentially supplied into an alcoholic (-hydric alcohol) solution to increase the particle size of the produced particles sequentially. A method is proposed. However, this method has disadvantages in that alkali metals are mixed into the silica particles and the reaction takes a long time, resulting in poor productivity.

<Problems to be Solved by the Invention> Therefore, an object of the present invention is to provide a novel method for producing inorganic oxide particles.

Another object of the present invention is to provide an industrially advantageous method for producing inorganic oxide particles of any desired particle size at a high concentration without causing aggregation.

A method for producing inorganic oxide particles whose particle size is controlled to a desired size by adding an organic metal compound that can be hydrolyzed and condensed to a particle suspension to grow nuclide particles. This is achieved by a method for producing inorganic oxide particles, which comprises containing 1 to 50% by weight of an alkylene glycol having 2 to 8 carbon atoms in the hydroalcoholic solution.

The present invention will be explained in detail below.

In the present invention, a hydroalcoholic solution is defined as having alcohol including alkylene glycol (A) (described later) and water as essential components, and containing all other optionally added catalysts, organic solvents other than alcohol, surfactants, etc. refers to the solution containing the

The alcohol is limited to m alcohols, but may be polyhydric alcohols of dihydrity or higher. For example, m alcohols such as methanol, ethanol, isopropanol, butanol, isoamyl alcohol, ethylene glycol, diethylene glycol, propylene glycol, 1 .Dihydric alcohols such as 4-butanediol and hexanediol;
Trihydric alcohols such as glycerin can be used alone or in mixtures. In the present invention, among the dihydric alcohols shown above, those having 2 to 8 carbon atoms are referred to as alkylene glycol (A), and the amount of the alkylene glycol (A) is 1 to 50% by weight in the hydroalcoholic solution. % by weight, preferably in the range of 1 to 30% by weight. If it deviates from the above range, the formation of agglomerated particles, which is the object of the present invention, will be prevented, and inorganic oxide particles with excellent monodispersity cannot be produced with good productivity.

Water in the solution is present in an amount greater than the equivalent amount necessary to hydrolyze the organometallic compound. Since the water content affects the growth process of the seed particles, it is necessary to control it to a preferable amount.It varies depending on the type and amount of the organometallic compound, but the water content should be in the range of 3 to 30% in the hydroalcoholic solution. Suitable, preferably 6 to 25% by weight.

The catalysts present in the solution include N) 14"Na",
Compounds that can generate cations such as K" and anions such as SO#t, H!PO, -, or organic amine compounds such as ethanolamine, isopropanolamine, and tetramethylammonium hydroxide are used. However, Its presence or absence and amount are selected depending on the raw material.

Organic solvents other than alcohol such as dioxane, acetone, diethyl ether, ethyl acetate, benzene, toluene, hexane, etc. can be used, and surfactants such as anionic, cationic, and nonionic surfactants can improve the dispersibility of the particles. It can be present in solution for enhancing purposes.

Inorganic oxide fine particles as seed particles used in the present invention (
Hereinafter, they will be referred to as seed particles. ) The raw material has an average particle size of 0.01
As long as it is ~10 μm, it may be in the form of powder or slurry. The material for the seed particles is preferably an inorganic oxide whose main component is silicon oxide, titanium oxide, zirconium oxide, aluminum oxide, etc., and more preferably an inorganic oxide containing at least a metal element in an organometallic compound used in the growth reaction. .

The properties of inorganic oxide particles (hereinafter referred to as grown particles) obtained by growing seed particles are greatly influenced by the seed particles. That is, in order to obtain produced particles with excellent monodispersity, it is necessary not only to have a uniform particle size distribution of the seed particles themselves and the presence or absence of aggregated particles, but also to ensure that the seed particles are monodispersed in the hydroalcoholic solution. Furthermore, it was found that the surface properties of the seed particles also influenced the monodispersity of the produced particles. Here, monodisperse refers to a state in which the particles are uniform in shape, have a sharp particle size distribution, and have almost no aggregated particles.

Monodisperse seed particles can be produced, for example, by neutralizing water glass in an aqueous solution with an acid or ion exchange resin to form a silicate aqueous sol, or by gasifying an organometallic compound and condensing it by thermal decomposition or hydrolysis. or a method in which an organometallic compound such as a metal alkoxide is hydrolyzed and condensed in a water-containing organic solvent solution.

Such seed particles are monodispersed in a hydroalcoholic solution as a reaction solvent before performing a growth reaction. At that time, the seed particles are monodispersed in a part of the solution in advance to form a monodispersed seed particle slurry, and are finally combined with the remainder of the solution to form seed particles monodispersed in the hydroalcoholic solution. The method is preferred. Specific methods include, among the above-mentioned methods for producing seed particles, a method of producing a silicate water sol from water glass, and a method of producing inorganic oxide fine particles by hydrolyzing and condensing organometallic compounds such as metal alkoxides. Conventionally known methods for producing seed particle slurry, such as a method for producing an organic solution slurry, can be applied. A more preferable seed particle monodisperse slurry includes an alkylene glycol monodisperse of inorganic oxide fine particles.

The alkylene glycol monodisperse of the seed particles is, for example,
It can be obtained by replacing the solvent of a silicate aqueous sol or an organic solution slurry of inorganic oxide fine particles with alkylene glycol. It is preferable to use the seed particles as a monodisperse of alkylene glycol in that the effect of the present invention of preventing agglomeration of the generated particles can be further enhanced even when the concentration of the generated particles is increased. It is thought that this is because the particle surface of the particles has improved affinity with alkylene glycol. The basis for this is that alkylene glycol is bonded to the surface of the seed particles, and the amount of alkylene glycol bonded is 0.00% per gram of the seed particles.
It is inferred from the fact that the agglomeration prevention effect is further enhanced when the amount is 0.003 mmol or more, preferably 0.01 mmol or more, and more preferably 0.1 to 5 mmol.

A method for producing such a monodisperse of alkylene glycol in inorganic oxide fine particles is described in Japanese Patent Application Laid-open No. 185439/1983 and U.S. Pat.
The method described in SP 2,921.913 etc. can be applied.

For example, according to the method described in JP-A No. 63-185439, the pressure during the heat treatment may be reduced pressure, normal pressure, or pressurized, but reduced pressure or normal pressure is easier to operate (advantageous). The heat treatment temperature (Tt) is when the boiling point of alkylene glycol at the operating pressure is T8℃ (however, T8≧70
)70≦T≦T, preferably in the range of +10, more preferably in the range of T,≦T≦Tm+10.
'rs is a value determined by a boiling point curve showing the pressure-boiling point relationship of the single glycol in the case of a single type of alkylene glycol, and the pressure-boiling point relationship of the mixed glycol at the composition ratio in the case of a mixed glycol of two or more types.

For example, when the glycol is ethylene glycol, T is 197.6 (normal pressure), 100 (18 Torr),
75 (4,1 Torr). The pressure for other glycols is determined in the same way once the pressure is determined.

The reason why T may exceed T3 is that the boiling point of alkylene glycol is raised by fine particles. Therefore, the upper limit (TI+10)° C. of the heat treatment temperature (T”C) means the upper limit of the temperature in consideration of the increase in boiling point.

The higher the heat treatment temperature, the higher the dispersion stability effect, and the shorter the treatment time is, the more effective it is, requiring a long time at low temperature. T
<70, the heat treatment effect is small and unfavorable.

The method of adding seed particles as a monodisperse of alkylene glycol to finally form a seed particle suspension in a hydroalcoholic solution makes it possible to easily monodisperse the seed particles in the solution, and to add alkylene glycol as a monodisperse. This is the most preferred embodiment in that glycol can also be added at the same time.

In the present invention, the inorganic oxide of inorganic oxide fine particles as seed particles and inorganic oxide particles as grown particles refers to a metal oxygen compound in which metal atoms form a three-dimensional network through bonds with oxygen atoms. Metal atoms have groups that are not partially involved in the network, such as non-hydrolyzable groups derived from raw materials, unhydrolyzed hydrolyzable residues, hydroxyl groups, and groups treated with coupling agents. It also includes.

The organometallic compound that is the raw material for the grown particles has a hydrolyzable organic group and undergoes hydrolytic condensation to form a three-dimensional (metal-oxygen)
Compounds that can form bonded chains and are industrially available and inexpensive include silicon, titanium, zirconium,
Alkoxy metal compounds such as aluminum are preferably used. They have the general formula ■ R1,M(OR"), (1) (where M is a metal element, R1 is a hydrogen atom and an alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, which may have a substituent. ,
at least one group selected from the group consisting of an aryl group and an unsaturated aliphatic residue, R8 represents an alkyl group,
m is 0 or a positive integer, n is an integer of 1 or more, and m
+n=satisfies the valence of the metal element M. Also, m R
1 may be different, and n R1s may also be different. Preferable examples of the metal element M include silicon, titanium, zirconium, and aluminum.

R1 is preferably a lower alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms. Although an alkoxy metal compound in which n is 3 or more can be used alone, a compound represented by n-1 or 2 can be used together with a raw material having 3 or more hydrolyzable organic groups.

Specific examples of the organometallic compound represented by the above general formula R1, M(OR") include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, trimethoxysilane, triethoxysilane, methyltrimethoxy Silane, trimethoxyvinylsilane, triethoxyvinylsilane, 3-glycidoxypropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-(2-aminoethylaminopropyl)trimethoxysilane , phenyltrimethoxysilane, phenyltriethoxysilane, dimethoxydimethylsilane, dimethoxymethylsilane, jetoxymethylsilane, jetoxy-3-glycidoxypropylmethylsilane, 3-chloropropyldimethoxymethylsilane, dimethoxydiphenylsilane, dimethoxydimethylphenyl Silane, trimethylmethoxysilane, trimethylethoxysilane,
Dimethylethoxysilane, dimethoxyjethoxysilane, titanium tetramethoxide, titanium tetraethoxide, titanium tetraisopropoxide, titanium tetrabutoxide, titanium jetoxydipoxide, zirconium tetramethoxide, zirconium tetraethoxide, zirconium tetraisopropoxide ,
Examples include titanium tetra(2-ethylhexyl oxide), aluminum trimethoxide, aluminum triethoxide, aluminum triisopropoxide, aluminum tributoxide, and the like.

Other preferred organometallic compounds include derivatives of these alkoxy metal compounds. - For example, a compound in which some of the alkoxide groups (OR") are substituted with a group capable of forming a chelate compound, such as a carboxyl group or a β-dicarbonyl group, or a compound in which these alkoxy metal compounds or alkoxy group-substituted compounds are partially substituted. These include low-shrinkage products obtained by hydrolysis.

Other organometallic compounds include, for example, acylate compounds of titanium, zirconium or aluminum such as zirconium acetate, zirconium oxalate, zirconium lactate, titanium lactate, aluminum lactate; titanium acetylacetonate, zirconium acetylacetonate, titanium octyl glycolate; Examples include titanium triethanolaminate, aluminum acetylacetonate, and chelate compounds of titanium, zirconium, or aluminum, such as glycols, β-diketones, hydroxycarboxylic acids, ketoesters, ketoalcohols, aminoalcohols, and quinolines.

The grown particles are made from the above-mentioned seed particles and organometallic compounds, but in the growth reaction process, in addition to the above-mentioned organometallic compounds, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, boron, Composite particles of oxides of silicon, titanium, zirconium, and/or aluminum and oxides of the above metals are formed by coexisting organic metal compounds or inorganic salts such as gallium, isodium, tin, iron, and copper and hydrolyzing them. You can also. At this time, the proportion of silicon, titanium, zirconium and/or aluminum oxides in the final grown particles, including the composition of the seed particles, is not particularly limited, but is preferably 70% by weight or more.

As described above, the present invention is a method for growing seed particles by adding an organometallic compound to a seed particle suspension in which seed particles are dispersed in a hydroalcoholic solution containing alkylene glycol in a specific range. The reaction method is not particularly limited; specifically, a method in which the entire amount of the seed particle suspension is introduced into a reaction vessel equipped with a stirring device, and then the organometallic compound is added continuously or intermittently, or The method may be a batch method, a continuous method, or a combination thereof, such as a method of continuously supplying the seed particle suspension and the organometallic compound to a reaction vessel or a tubular line mixer.

Further, raw materials such as seed particles, alkylene glycol, alcohol other than alkylene glycol, water, catalyst, organic solvent other than alcohol, and organometallic compound can be separately supplied separately.

In this case, the hydroalcoholic solution refers to a solution having a composition excluding seed particles, organometallic compounds, and decomposition products thereof from among the above-mentioned raw materials added until the end of the growth reaction.

The reaction temperature in the growth reaction is in the range of 0 to 100°C, preferably in the range of 0 to 50°C, and the reaction time varies depending on other reaction conditions such as temperature, type and amount of catalyst, but is 10 minutes to 5 hours. is sufficient.

<Effect of the invention> An organometallic compound capable of hydrolysis and condensation is added to a seed particle suspension dispersed in a hydroalcoholic solution to grow seed particles, and inorganic oxide particles having an arbitrary particle size are grown. If the method of the present invention is followed in which alkylene glycol is allowed to coexist in a specific range of amounts in the hydroalcoholic solution during production, it is effective in preventing the formation of aggregated particles, increasing the particle concentration, and shortening the reaction time compared to conventional methods. Therefore, the method for producing inorganic oxide particles according to the present invention has good productivity and is an industrially inexpensive method. In addition, the inorganic oxide particles obtained by the method of the present invention have no agglomerated particles, and further have 0 to 5 seed particles. The result is monodispersed particles having a particle size in the range of ~15 μm and a coefficient of variation of 10% or less, preferably 5% or less.

<Examples> The present invention will be explained in more detail by Examples below, but the present invention is not limited to these Examples.

The physical properties of the spherical fine particles obtained in Examples and Comparative Examples were analyzed and evaluated by the following method.

*Average particle size and standard deviation value The average value and standard deviation value of the particle size of spherical fine particles were determined by processing the electron microscope images of 200 particles using an image processing device (electron microscope Hitachi S
-570 type, image processing device Pierce LA-1000)
.

However, *Presence or absence of aggregated particles was evaluated by observing the sample as a slurry under an optical microscope at 1000x magnification.

That is, when the particles in the slurry are monodispersed, there is a certain correlation between the respective average particle diameters obtained by an electron microscope and a centrifugal sedimentation type particle size distribution analyzer. However, if the particles aggregate, this relationship will deviate.

The degree of aggregation can be determined from the degree of deviation.

These evaluation results were comprehensively evaluated and the degree of presence or absence of aggregated particles was evaluated in four stages according to the following criteria.

■ There are no aggregated particles at all.

○ There are few aggregated particles.

△ There are some aggregated particles.

× There are many aggregated particles.

Example 1 707.3 g of ethanol, 275.3 g of 28% aqueous ammonia, and 24.0 g of water were added and mixed in a 2-glass reactor equipped with a stirrer, a dropping port, and a thermometer. The temperature of the mixture was adjusted to 30±0.5°C, and while stirring, 134.1 g of tetraethoxysilane was added dropwise from the dropping port over 1 hour. Stirring was continued for 1 hour after the addition, followed by hydrolysis.
Condensation was carried out to obtain a suspension of spherical silica particles (1-a).

Add 100 g of ethylene glycol to this suspension,
Concentrate at normal pressure using an evaporator until the internal temperature reaches 150℃.
When the temperature reached .degree. C., heating was continued for 1 hour to obtain a slurry of nyletine glycol (fine particle concentration: 26.8% by weight) consisting of spherical silica fine particles bound to ethylene glycol. This was used as a seed particle slurry (1-b).

586.9 g of methanol, 267.9 g of 28% ammonia water, 52 g of ethylene glycol, and 33.2 g of seed particle slurry (1-b) were added dropwise to a 2-liter glass reactor equipped with a stirrer, a dropping port, and a thermometer. Mixed. The temperature of the mixture was adjusted to 20±1'C, and while stirring, a solution of 373 g of tetraethoxysilane dissolved in 187 g of methanol was added dropwise from the dropping port over 3 hours. Stirring continued for 1 hour after the addition, followed by hydrolysis. Seed particles were grown by condensation to obtain a suspension of spherical silica particles (1-c).

The results are shown in Table-1.

Example 2 397.1 g of methanol was placed in a 2 liter glass reactor equipped with a stirrer, a dropping port and a thermometer.

204.7 g of 28% ammonia water, 1.4 g of water, 75 g of ethylene glycol, and a suspension of spherical silica fine particles obtained in Example 1 (1-a) 261.8 g (S
3.4% by weight of iO□) was added and mixed. Adjust the mixture to 20±1°C and add 187g of methanol while stirring.
A solution in which 373 g of tetraethoxysilane was dissolved was added dropwise from the dropping port over a period of 3 hours, and the mixture was stirred for 1 hour after dropping, followed by hydrolysis and condensation to grow seed particles to obtain a suspension of spherical silica particles. . The results are shown in Table-1.

Example 3 The same procedure as in Example 1 was repeated except that propylene glycol was used instead of ethylene glycol.

The results are shown in Table-1.

Example 4 675.4 g of methanol and 275.3 g of 28% aqueous ammonia were added to a 2 liter glass reactor equipped with a stirrer, a dropping port, and a thermometer and mixed. The temperature of the mixture was adjusted to 20±0.5°C, and while stirring, a solution of 111.8 g of tetramethoxysilane dissolved in 55.9 g of methanol was added dropwise from the dropping port over 1 hour.
After stirring for a period of time, hydrolytic condensation was carried out to obtain a suspension of spherical Rishika particles (4-a).

Add 150 g of ethylene glycol to this suspension, concentrate at normal pressure using an evaporator, and heat for 1 hour when the internal temperature reaches 190°C. Continue to make a slurry of nyletine glycol made of spherical silica particles bound to ethylene glycol. (Fine particle concentration: 28.0% by weight) was obtained. This was used as a seed particle slurry (4-b).

329.7 g of methanol, 267.9 g of 28% ammonia water, 24.0 g of water, and 71.1 g of seed particle slurry (4-b) were placed in a 2-liter glass reactor equipped with a stirrer, a dropping port, and a thermometer. Add and mix. Adjust the mixture to 20±1°C and add 269 g of methanol while stirring.
A solution in which 538 g of tetramethoxysilane was dissolved was added dropwise from the dropping port over a period of 1 hour, and after the addition, stirring was continued for 1 hour, followed by hydrolysis and condensation to grow seed particles to obtain a suspension of spherical silica fine particles. . The results are shown in Table-1.

Example 5 Suspension of spherical silica fine particles obtained in Example 1 (1
-a) was concentrated to dryness using an evaporator. The powder thus obtained was fired at 400° C. for 1 hour. After adding this powder to methanol, it was subjected to ultrasonic treatment to improve dispersion. This dispersion was filtered through a filter paper to obtain a seed particle slurry (5-b).

In a 2-rifle glass reactor equipped with a stirrer, a dropping port and a thermometer, 567.1 g of methanol, 267.9 g of 28% aqueous ammonia, 75.0 g of ethylene glycol and 30.0 g of seed particle slurry (5-b) were added. (Sing 25
．． 8%) and mixed. 20±1 of the mixture
℃, and while stirring, a solution of 373 g of tetraethoxysilane dissolved in 187 g of methanol was added dropwise from the dropping port over a period of 3 hours. After the addition, stirring was continued for 1 hour, followed by hydrolysis.
Seed particles were grown by condensation to obtain a suspension of spherical silica particles. The results are shown in Table-1.

Example 6 Suspension of spherical silica fine particles obtained in Example 1 (1
Add 500 g of ethylene glycol to -c), concentrate at normal pressure using an evaporator, raise the internal temperature to 197.6°C, and heat for 1 hour while gradually distilling ethylene glycol. Ethylene glycol slurry of silica particles (particle concentration 31.
2% by weight). This was used as a seed particle slurry (6-b).

389.7 g of methanol, 267.9 g of 28% aqueous ammonia, 60 g of ethylene glycol, and 51.4 g of seed particle slurry (6=b) were placed in a 2-glass reactor equipped with a stirrer, a dropping port, and a thermometer. Add and mix. The temperature of the mixture was adjusted to 20 ± 1°C, and while stirring, a solution of 487 g of tetraethoxysilane dissolved in 244 g of methanol was added dropwise from the dropping port over a period of 3 hours. After dropping, stirring was continued for 1 hour, followed by hydrolysis and condensation. The seed particles were grown to obtain a suspension of spherical silica particles (6-c).

Example 7 Suspension of spherical silica fine particles obtained in Example 6 (6
-c) Add 350 g of nyletine glycol to 1000 g, concentrate at normal pressure using an evaporator, heat the inner bath to 197.6°C, and gradually distill out ethylene glycol while heating for 1 hour. An ethylene glycol slurry of spherical silica fine particles (fine particle concentration: 25.0% by weight) was obtained. This was used as a seed particle slurry (7-b).

In a 2-liter glass reactor equipped with a stirrer, a dropping port, and a thermometer, 372.8 g of methanol, 294.6 g of 28% ammonia water, 37.2 g of ethylene glycol, and 60.4 g of seed particle slurry (7-b) were added. was added and mixed. The temperature of the mixed solution was adjusted to 20±1°C, and while stirring, a solution of 490 g of tetramethoxysilane dissolved in 245 g of methanol was added dropwise from the dropping port over 2 hours.
After stirring for a period of time, seed particles were grown by hydrolysis and condensation to obtain a suspension of spherical silica particles. The results are shown in Table-1.

Example 8 1368.7 g of methanol and 11.3 g of water were added to a 2 liter glass reactor equipped with a stirrer, a dropping port and a thermometer.
g and mixed. The mixture was adjusted to 20 ± 5°C, and while stirring, a solution of 60 g of tetraisopropoxy titanate dissolved in 60 g of methanol was added dropwise from the dropping port over 1 hour. After the addition, stirring was continued for 1 hour, followed by hydrolysis. Condensation was carried out to obtain a suspension of spherical titania fine particles.

Add 200 g of ethylene glycol to this suspension and concentrate it at normal pressure using an evaporator, so that the indoor water becomes 197.6 g.
When the temperature reached .degree. C., heating was continued for 1 hour to obtain an ethylene glycol slurry (fine particle concentration: 14.0% by weight) of spherical titania fine particles bound to ethylene glycol. This was used as a seed particle slurry (8-b).

336.5 g of methanol, 267.9 g of 28% aqueous ammonia, and 10 liters of seed particle slurry (8-b) were placed in a 2-liter glass reactor equipped with a stirrer, a dropping port, and a thermometer.
3.6g was added and mixed. The temperature of the mixture was adjusted to 20 ± 1°C, and while stirring, a solution of 264 g of tetramethoxysilane and 132 g of tetraisopropoxy titanate dissolved in 396 g of methanol was added dropwise from the dropping port over 4 hours, and stirring was continued for 1 hour after the addition. Next, seed particles were grown by hydrolysis and condensation to obtain a suspension of spherical titania-silica fine particles. The results are shown in Table-1.

Example 9 875.1 g of ethanol and 31.5 g of water were added to a 2 liter glass reactor equipped with a stirrer, a dropping spout and a thermometer.
was added and mixed. The temperature of the mixture was adjusted to 25±0.5°C, and while stirring, a solution of 134.1 g of tetrabutoxyzirconate dissolved in 134.1 g of ethanol was added dropwise from the dropping port over 1 hour. After stirring, hydrolysis and condensation were carried out to obtain a suspension of spherical zirconia fine particles.

Add 350 g of ethylene glycol to this suspension and concentrate at normal pressure using an evaporator until the internal temperature reaches 197.6.
When the temperature reached .degree. C., heating was continued for 1 hour to obtain an ethylene glycol slurry (fine particle concentration: 15.0% by weight) of spherical zirconia fine particles bonded with ethylene glycol. This was designated as seed particle slurry (9-b).

In a 2-liter glass reactor equipped with a stirrer, a dropping port, and a thermometer, 515.5 g of methanol, 267.9 g of 28% aqueous ammonia, and 130 g of seed particle slurry (9-b) were added.
．． 0g was added and mixed. Adjust the mixture to 20±1°C, and add 293.3 g of ethanol, 200 g of tetramethoxysilane, and tetrabutoxyzircone while stirring.
A solution in which 93.3 g of zirconia was dissolved was dripped over 4 hours from the dripping port, and the mixture was continued to be stirred for 1 hour after dropping, followed by hydrolysis and condensation to grow seed particles to obtain a suspension of spherical zirconia-silica fine particles. Ta. The results are shown in Table-1.

Example 10 827.8 g of isopropanol, 191.3 g of 28% aqueous ammonia, and 32.7 g of water were added and mixed in a 2-liter glass reactor equipped with a stirrer, a dropping port, and a thermometer. The temperature of the mixture was adjusted to 20±0.5°C, and while stirring, a solution of 98.0 g of aluminum triisopropoxide dissolved in 98.0 g of ilobanol was added dropwise from the dropping port over 1 hour. After stirring for 1 hour, hydrolysis and condensation were performed to obtain a suspension of fine spherical alumina particles.

Add 270 g'f of propylene glycol to this suspension and concentrate at normal pressure using an evaporator until the internal temperature reaches 1.
When the temperature reached 70°C, heating was continued for 1 hour to obtain a propylene glycol slurry (fine particle concentration: 15.0% by weight) of spherical alumina fine particles bound to propylene glycol and spherical alumina fine particles bound to propylene glycol. ° This was used as a seed particle slurry (10-b).

448.8 g of isopropanol in a 2 liter glass reactor equipped with a stirrer, addition port and thermometer.

267.9 g of 28% aqueous ammonia and 63.3 g of seed particle slurry (10-b) were added and mixed. The temperature of the mixture was adjusted to 20±1°C, and while stirring, a solution of 240 g of tetramethoxysilane dissolved in 360 g of inpropatol and 120 g of aluminum triisopropoxylate was added dropwise from the dropping port over 4 hours. After stirring for a long time, seed particles are grown through hydrolysis and condensation to form spherical alumina.
A suspension of silica fine particles was obtained. The results are shown in Table-1.

Comparative Example 1 The same procedure as in Example 2 was repeated except that ethylene glycol was replaced with methanol. The results are shown in Table-1.

Comparative Example 2 467.1 g of methanol, 204.7 g of 28% aqueous ammonia, 1.4 g of water, and 5.0 g of ethylene glycol were placed in a 2-liter glass reactor equipped with a stirrer, a dropping port, and a thermometer.
261.8 g (Sin23.4%
) was added and mixed. The temperature of the mixture was adjusted to 20 ± 1°C, and while stirring, a solution of 373 g of tetraethoxysilane dissolved in 187 g of methanol was added dropwise from the dropping port over 3 hours. After dropping, stirring was continued for 1 hour, followed by hydrolysis and condensation. The seed particles were grown to obtain a suspension of spherical silica particles.

The results are shown in Table-1.

Comparative Example 3 97.7 g of methanol, 541.2 g of ethylene glycol, 267.9 g of 28% aqueous ammonia, and the seed particles obtained in Example 1 were placed in a 2-liter glass reactor equipped with a stirrer, a dropping port, and a thermometer. Slurry (1b) 33.
2 g (26.8% by weight of SiO□) was added and mixed. The temperature of the mixture was adjusted to 20 ± 1°C, and while stirring, a solution of 373 g of tetraethoxysilane dissolved in 187 g of methanol was added dropwise from the dropping port over 3 hours. After dropping, stirring was continued for 1 hour, followed by hydrolysis and condensation. The seed particles were grown to obtain a suspension of spherical silica particles. The results are shown in Table-1.

Comparative Example 4 All procedures were carried out in the same manner as in Example 5 except that niretine glycol was replaced with metatsuru. The results are shown in Table-1.

Claims (1)

[Claims] 1. Adding an organometallic compound capable of hydrolysis and condensation to a seed particle suspension prepared by dispersing inorganic oxide particles as seed particles in a hydroalcoholic solution to grow the seed particles. hand,
In the method for producing inorganic oxide particles having a larger particle size than the seed particles, the hydroalcoholic solution contains 2 carbon atoms.
A method for producing inorganic oxide particles with excellent monodispersity, which comprises containing an alkylene glycol of 1 to 50% by weight. 2. Organometallic compounds have the general formula I R^1_mM(OR^2)_n(I) (where M is a metal element, R^1 is a hydrogen atom and an alkyl having 1 to 10 carbon atoms that may have a substituent) R^2 represents an alkyl group, m is 0 or a positive integer, n is an integer of 1 or more, and m+n
= satisfies the valence of the metal element, and the m R^1's may be different, and the n R^2's may also be different. 2. The method according to claim 1, wherein the compound is at least one selected from the group consisting of alkoxy metal compounds represented by: ) and derivatives thereof. 3. A claim comprising, when dispersing the seed particles in a hydro-alcoholic solution, heat-treating the seed particles in an alkylene glycol, making an alkylene glycol dispersion of the seed particles, adding the seed particles to the hydro-alcoholic solution, and dispersing the seed particles. The method described in Section 1. 4. The heat treatment temperature (T°C) when heat-treating the seed particles in alkylene glycol is 70≦T≦T_■+10 (where, T_■ represents the boiling point of alkylene glycol in the heat treatment operation, and T_■≧7.0 range)
4. The method according to claim 3, which is within the range of . 5. The method according to claim 1, wherein the seed particles have at least 0.003 mmol of alkylene glycol bound to their surfaces per gram of the seed particles. 6. The method according to claim 5, wherein the seed particles are particles having at least 0.01 mmol of alkylene glycol bound to their surfaces per gram of the seed particles. 7. The method according to claim 6, wherein the seed particles have 0.1 to 5 mmol of alkylene glycol bound to their surfaces per gram of the seed particles. 8. The method according to claim 1, wherein the seed particles and the inorganic oxide particles contain at least one member selected from the group consisting of silicon oxide, titanium oxide, zirconium oxide, aluminum oxide, and composite oxides thereof. 9. M in general formula I is Si, Ti, Zr and A
3. The method according to claim 2, wherein the method is at least one selected from the group consisting of: 10. The method according to claim 1, wherein the inorganic oxide particles are amorphous spherical, have an average particle size in the range of 0.1 to 20 μm, and have a coefficient of variation of particle size of 10% or less. 11. The method according to claim 1, wherein the hydroalcoholic solution contains 3 to 30% by weight of water. 12. The method according to claim 2, wherein R^2 in general formula I is an alkyl group having 1 to 8 carbon atoms. 13. The method according to claim 1, wherein the alkylene glycol has 2 to 4 carbon atoms. 14. The method according to claim 1, wherein the seed particles have an average particle diameter of 0.01 to 10 μm. 15. The method according to claim 1, wherein the growth reaction temperature is 0° to 100°C.