JPH0662284B2 - Method for producing inorganic oxide particles - Google Patents

Description

TECHNICAL FIELD The present invention relates to an industrially advantageous method for producing inorganic oxide particles in which generation of agglomerated particles is prevented and the particle diameter is arbitrarily controlled. The particles have industrial value as a carrier for chromatography, a material for a catalyst, a pigment, a solid lubricant, a paint or a filler for fibers, a synthetic resin molding such as a film, and the like.

<Prior Art> Conventionally, as a method for producing inorganic oxide particles, a method of spray-pressing a metal oxide sol into a heated non-polar solvent to cause gelation, a method of spray-drying a metal salt solution and then firing, a metal Known methods include emulsifying a salt solution for interfacial polymerization, and hydrolyzing or thermally decomposing a metal alkoxide in an organic solvent or in a gas phase. Among them, particles are produced by hydrolyzing or neutralizing a raw material compound in a solution,
The so-called wet method is widely used because it is easy to control the particle size of generated particles and prevent the formation of aggregated particles. Among the wet methods, the method of hydrolyzing a metal alkoxide in an organic solvent has been attracting attention as a method of obtaining particles having a narrow particle size distribution and excellent dispersibility. For example, a method of obtaining amorphous silica particles using tetraalkoxysilane as a raw material (W. St.
ber et al., J. Colloid and Interface Scieuce 26 , 62
~ 69 (1968)), a method for obtaining hydrous titanium oxide particles using tetraethoxy titanium as a raw material (Barrilnger et al., Langmu et al.
ir 1, 414 (1985), etc.), tri sec - butoxy aluminum a method of obtaining a hydrous aluminum oxide particles as a raw material (such as DLCatone, J.Colloid and Interface Scienc
e., 48 , 291 (1974)).

From these documents, the basic reaction conditions can be inferred to obtain spherical monodisperse particles by hydrolyzing an alkoxy metal compound in an organic solvent such as alcohol. However, once the type of the raw material alkoxy metal compound is determined, there is a limit to the particle size of the produced particles even if the reaction conditions such as the organic solvent, the type and composition of the catalyst, and the reaction temperature are changed. In particular, when using tetraalkoxysilane as a raw material and a monohydric alcohol as an organic solvent, the larger the carbon number of the monohydric alcohol, the larger the particle size of the silica particles produced, but the higher the limit was 2 μm. Furthermore, considering the industrial productivity, if the concentration of the raw material tetraalkoxysilane is increased to increase the concentration of produced particles, or if it is attempted to increase the diameter of produced particles, the particle size distribution is broadened, and finally there is a problem that the particles aggregate. there were.

In order to solve these problems, as a method for producing silica particles, JP-A-62-72514 discloses that silica particles in a slurry obtained by hydrolyzing tetraalkoxysilane in a hydroalcoholic solution are used as seed particles. A method of supplying a raw material alkoxysilane has been proposed. However, even if the particle diameter can be increased by this method, when the raw material concentration is increased in order to increase the productivity, agglomerated particles are remarkably generated, and it is difficult to be an industrial production method of monodisperse silica particles. In addition, JP-A-62
-72516 proposes a method in which an alkali metal ion is supplied when the raw material alkoxysilane compound is sequentially supplied into an alcohol (monohydric alcohol) solution and the particle size of the produced particles is successively increased. . However, this method has the drawbacks that the alkali metal is mixed in 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 having a desired desired particle size at a high concentration without causing agglomeration.

<Means for Solving the Problems> These objects are to add a hydrolyzable and condensable organometallic compound to a seed particle suspension prepared by dispersing inorganic oxide fine particles as seed particles in a hydroalcoholic solution. The seed particles are grown to have an amorphous spherical shape, the average particle diameter is in the range of 0.1 to 20 μm, and the variation coefficient of the particle diameter is 10% or less. In the method for producing inorganic oxide particles having a controlled particle size, the inorganic oxide particles comprising the hydric alcoholic solution containing 1 to 50% by weight of an alkylene glycol having 2 to 8 carbon atoms. It is achieved according to the manufacturing method.

Hereinafter, the present invention will be described in detail.

In the present invention, the hydroalcoholic solution includes alcohol and water including alkylene glycol (A) described later as essential components, and catalysts optionally added, organic solvents other than alcohol, surfactants, etc. The included solution.

The alcohol is not limited to monohydric alcohol and may be polyhydric alcohol having a valence of 2 or more. For example, monohydric alcohols such as methanol, ethanol, isopropanol, butanol and isoamyl alcohol, dihydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol and hexanediol, and trihydric alcohols such as glycerin are used alone. Used in or in a mixture. In the present invention, among the dihydric alcohols as described 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 wt% in the hydrous alcoholic solution. %, Preferably 1 to 30% by weight.
If the amount is out of the above range, the production of aggregated particles, which is the object of the present invention, is prevented, and the inorganic oxide particles excellent in monodispersity cannot be produced with good productivity.

The water in the solution is present in an amount equal to or more than the amount required to hydrolyze the organometallic compound. The water content affects the growth process of the seed particles, so it is necessary to control it to a preferable amount, and it varies depending on the kind and addition amount of the organometallic compound, but the range of 3 to 30% by weight is suitable in the hydroalcoholic solution. And preferably 6 to 25% by weight.

The catalyst present in the solution produces cations such as NH ₄ ⁺ , Na ⁺ and K ⁺ and anions such as SO ₄ ²⁻ and H ₂ PO ₄ ⁻ for the purpose of controlling the hydrolysis and condensation reaction of the organometallic compound. Possible compounds, or ethanolamine, isopropanolamine,
Organic amine compounds such as tetramethylammonium hydroxide are used. However, the presence or absence and the amount thereof are selected depending on the raw material.

Dioxane, acetone, diethyl ether, ethyl acetate, benzene, toluene, hexane, etc., as organic solvents other than alcohol, and anionic, cationic, nonionic surfactants, etc. as surfactants further improve the dispersibility of generated particles. It can be present in the solution for the purpose of

The inorganic oxide fine particles (hereinafter referred to as seed particles) raw material used as seed particles in the present invention has an average particle diameter of 0.0
If it is 1 to 10 μm, it may be in the form of powder or slurry. The material of the seed particles is preferably an inorganic oxide containing silicon oxide, titanium oxide, zirconium oxide, aluminum oxide or the like as a main component, and more preferably an inorganic oxide containing at least a metal element in the organometallic compound used for the growth reaction. .

The properties of the inorganic oxide particles (hereinafter referred to as grown particles) obtained by growing the seed particles are greatly influenced by the seed particles. That is, in order to obtain the produced particles having excellent monodispersity, it is necessary that the seed particles are monodispersed in the hydroalcoholic solution in addition to the seed particles themselves, the particle size distribution, and the presence or absence of aggregated particles. It was also found that the surface properties of the seed particles also influence the monodispersity of the produced particles. Here, monodisperse refers to a state in which the particle shapes are uniform, the particle size distribution is sharp, and there are few aggregated particles.

The monodisperse seed particles are, for example, a method of neutralizing water glass in an aqueous solution with an acid or an ion exchange resin to obtain a silica water sol, and gasifying an organometallic compound to cause thermal decomposition or hydrolysis to condense it. It can be obtained by a method, a method of hydrolyzing and condensing an organic metal compound such as a metal alkoxide in a water-containing organic solvent solution, and the like.

Such seed particles are monodispersed in a hydroalcoholic solution as a reaction solvent before the growth reaction. At that time, seed particles are previously monodispersed in a part of the solution to form a seed particle monodisperse slurry, and finally combined with the rest of the solution to form seed particles monodispersed in a hydroalcoholic solution. The method is preferred. The specific method, in the method of manufacturing the seed particles described above, a method of silica water sol from water glass,
Hydrolyzes organometallic compounds such as metal alkoxides,
A conventionally known method for producing seed particle slurry, such as a method for condensing into an organic solution slurry of inorganic oxide fine particles, can be applied.
A more preferable seed particle monodisperse slurry is a monodisperse dispersion of alkylene glycol of inorganic oxide fine particles. The alkylene glycol monodisperse of the seed particles can be obtained, for example, by substituting the solvent such as silica water sol or the organic solution slurry of the inorganic oxide fine particles with alkylene glycol. The use of seed particles as a monodisperse dispersion of alkylene glycol is preferable in that the effect of the present invention of preventing agglomeration of produced particles can be further enhanced even if the produced particle concentration is increased. Although the reason is not clear, it is considered that the particle surface of the seed particles has improved affinity with alkylene glycol. As a basis for this, in particular, alkylene glycol is bound to the surface of the seed particles, and the amount of alkylene glycol bound is 1 g of seed particles.
It is inferred from the fact that the aggregation preventing effect is further enhanced by setting the concentration to 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 dispersion of inorganic oxide fine particles of alkylene glycol is disclosed in JP-A-63-185439 and USP 2,92.
The method described in No. 1,913 can be applied.

For example, according to the method described in JP-A-63-185439, the pressure during the heat treatment may be any of reduced pressure, atmospheric pressure and pressurized system, but the reduced pressure or atmospheric system is advantageous because it is easy to operate. The heat treatment temperature (T ° C.) is 70 ≦ when the boiling point of the alkylene glycol at the operating pressure is T _B ° C. (where T _B ≧ 70).
The range of T ≦ T _B +10 is preferable, and the range of T _B ≦ T ≦ T _B +10 is more preferable. T _B is a single glycol when one kind of alkylene glycol is used,
In the case of two or more kinds of mixed glycols, the value is determined by the boiling point curve showing the pressure-boiling point relationship of the mixed glycols in the composition ratio.

For example, when the glycol is ethylene glycol, T _B is
197.6 (normal pressure), 100 (18 Torr), 75 (4.1 Torr)
Is determined. The same applies to other glycols if the pressure is determined.

The reason that T may exceed T _B is because the boiling point of alkylene glycol is increased by the fine particles. Therefore, the upper limit (T _B +10) ° C. of the heat treatment temperature (T ° C.) means the upper limit of temperature in consideration of the boiling point increase. The higher the heat treatment temperature, the higher the dispersion stability effect, and the shorter the treatment time, the more effective.
The lower the temperature, the longer the time required. When T <70, the heat treatment effect is small and not preferable.

The method of adding seed particles as a monodisperse of alkylene glycol to finally form a suspension of seed particles in a hydroalcoholic solution is such that the seed particles can be easily monodispersed in the solution and the alkylene is This is the most preferred embodiment in that glycol can be added at the same time.

The inorganic oxide fine particles as the seed particles in the present invention and the inorganic oxide of the inorganic oxide particles that are grown particles, and an oxygen compound of the metal forming a three-dimensional network through the bond between the metal atom and the oxygen atom. A metal atom that has a group that is defined and is not partly involved in the network, such as a non-hydrolyzable group derived from a raw material, an unhydrolyzable hydrolyzable residue, a hydroxyl group, or a group treated with a coupling agent. It also includes.

The organometallic compound, which is a raw material for growing particles, has a hydrolyzable organic group, and is hydrolyzed and condensed into three-dimensional (metal-oxygen).
Silicon, titanium, zirconium, which is a compound capable of forming a bonding chain and which is industrially available and inexpensive
An alkoxy metal compound such as aluminum is preferably used. They are represented by the general formula I R ¹ _m M (OR ² ) _n (I) (where M is a metal element, R ¹ is a hydrogen atom and a carbon atom which may have a substituent, preferably 1 to 10, preferably 1 to 4). At least one group selected from the group consisting of an alkyl group, an aryl group and an unsaturated aliphatic residue, R ² represents an alkyl group, m is 0 or a positive integer, n is an integer of 1 or more,
Further, m + n = the valence of the metal element M is satisfied. Also, m
R ^{1 s} may be different, and n R ^{2 s} may also be different. ), The metal element M is preferably silicon, titanium, zirconium, or aluminum.

R ² is preferably a lower alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms. An alkoxy metal compound in which n is 3 or more can act alone, but the 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 R ¹ _m M (OR ² ) _n include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, trimethoxysilane,
Triethoxysilane, methyltrimethoxysilane, trimethoxyvinylsilane, triethoxyvinylsilane, 3
-Glycidoxypropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- (2-aminoethylaminopropyl) trimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethoxy Dimethylsilane, dimethoxymethylsilane, diethoxymethylsilane, diethoxy-3-glycidoxypropylmethylsilane, 3-chloropropyldimethoxymethylsilane, dimethoxydiphenylsilane, dimethoxydimethylphenylsilane, trimethylmethoxysilane, trimethylethoxysilane, dimethylethoxy Silane, Dimethoxydiethoxysilane, Titanium tetramethoxide, Titanium tetraethoxide, Titanium tetraisopropoxide, Titanium Tetrabutoxide, titanium diethoxydibutoxide, zirconium tetramethoxide, zirconium tetraethoxide, zirconium tetraisopropoxide, titanium tetra (2-ethylhexyl oxide), aluminum trimethoxide, aluminum triethoxide, aluminum triisopropoxide, Aluminum tributoxide and the like can be mentioned.

Further, other preferable organometallic compounds include derivatives of these alkoxymetal compounds. As an example, a compound in which a part of the alkoxide group (OR ² ) is substituted with a group capable of forming a chelate compound such as a carboxyl group or a β-dicarbonyl group, or a partial hydrolysis of these alkoxy metal compound or alkoxy group-substituted compound. It is a low shrinkage product obtained by decomposition.

Examples of other organometallic compounds include titanium, zirconium or aluminum acylate compounds such as zirconium acetate, zirconium oxalate, zirconium lactate, titanium lactate and aluminum lactate; titanium acetylacetonate, zirconium acetylacetonate, titanium octyl glycolate, Titanium triethanol aminate, aluminum acetylacetonate and the like, and chelate compounds such as titanium, zirconium or aluminum glycol, β-diketone, hydroxycarboxylic acid, ketoester, ketoalcohol, aminoalcohol and quinoline.

The grown particles, which are obtained by using the seed particles and the organometallic compound described above as raw materials, include sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, and boron in addition to the organometallic compound described above in the growth reaction process. A composite particle of an oxide of silicon, titanium, zirconium and / or aluminum and an oxide of the above metal, which is obtained by allowing an organic metal compound such as gallium, isodium, tin, iron, copper or the like or an inorganic salt to coexist and hydrolyze. You can also do it. At that time, the ratio of the oxides of silicon, titanium, zirconium and / or aluminum in the finally 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 hydrous alcoholic solution containing alkylene glycol in a specific range. The reaction method is not particularly limited. Specifically, the total amount of the seed particle suspension is introduced into a reaction vessel having a stirring device, and then a method of continuously or intermittently adding an organometallic compound, or the above-mentioned reaction vessel or a tubular line mixer. A batch method, a continuous method, or a combination thereof may be used, such as a method of continuously supplying the seed particle suspension and the organometallic compound. Further, the seed particles, alkylene glycol, alcohol other than alkylene glycol, water, catalyst, organic solvent other than alcohol, and raw materials such as organic metal compound may be separately supplied separately. At that time, the hydrous alcoholic solution means a solution having a composition in which the seed particles, the organometallic compound and the decomposition products thereof are excluded from the above-mentioned raw materials added by the time when the growth reaction is completed.

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, kind and amount of catalyst, but 10 minutes to 5 hours. Is enough.

<Effects of the Invention> To a seed particle suspension dispersed in a hydroalcoholic solution, a seed particle is grown by adding an organometallic compound capable of being hydrolyzed and condensed, and an inorganic oxide particle having an arbitrary particle diameter is added. According to the method of the present invention in which a specific amount of alkylene glycol is allowed to coexist in a hydroalcoholic solution at the time of production, it is effective in preventing the formation of aggregated particles, increasing the particle concentration, and shortening the reaction time as compared with the conventional method. Therefore, the method for producing inorganic oxide particles according to the present invention has good productivity and is an industrially inexpensive method, and the inorganic oxide particles obtained by the method according to the present invention have no agglomerated particles, and further seed particles and reaction conditions. Amorphous spheres with an average particle size of 0.1-
The monodispersed particles are in the range of 20 μm, preferably 0.5 to 15 μm, and the coefficient of variation is 10% or less, preferably 5% or less.

<Examples> The present invention will be described in more detail with reference to 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 methods.

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

However * Presence or absence of aggregated particles The sample was observed in a slurry state under an optical microscope of 1000 times and evaluated.

That is, when the particles in the slurry are monodispersed, there is a certain correlation between the respective average particle sizes obtained by an electron microscope and a centrifugal sedimentation type particle size distribution analyzer. However, when the particles are agglomerated, the relationship deviates.
The degree of aggregation can be judged from the degree of deviation. The evaluation results were comprehensively evaluated, and the degree of presence or absence of aggregated particles was evaluated in four levels according to the following criteria.

◎ No aggregated particles.

○ There are few aggregated particles.

△ There are some agglomerated particles.

× There are many agglomerated particles.

Example 1 707.3 g of ethanol, 275.3 g of 28% ammonia water and 24.0 g of water were added and mixed into a 2 liter glass reactor equipped with a stirrer, a dropping port and a thermometer.
The mixed solution was adjusted to 30 ± 0.5 ° C., 134.1 g of tetraethoxysilane was added dropwise from the dropping port over 1 hour while stirring, and after the dropping, stirring was continued for 1 hour to carry out hydrolysis and condensation to form spherical particles. A suspension (1-a) of fine silica particles was obtained.

Ethylene glycol (100 g) was added to this suspension, and the mixture was concentrated under atmospheric pressure using an evaporator. When the internal temperature reached 150 ° C, heating was continued for 1 hour, and ethylene glycol-bonded spherical silica fine particle slurry of ethylene glycol ( A fine particle concentration of 26.8% by weight) was obtained. This was used as seed particle slurry (1-b).

To a 2 liter glass reactor equipped with a stirrer, a dropping port and a thermometer, 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 dropped. Mixed. The mixed solution was adjusted to 20 ± 1 ° C. and stirred with methanol 1
A liquid in which 373 g of tetraethoxysilane was dissolved in 87 g was dropped from the dropping port over 3 hours, and after the dropping, stirring was continued for 1 hour to grow seed particles by hydrolysis and condensation to obtain a suspension of spherical silica fine particles (1- c) was obtained.

The results are shown in Table-1.

Example 2 In a 2 liter glass reactor equipped with stirrer, dropping port and thermometer, 397.1 g of methanol, 204.7 g of 28% ammonia water, 1.4 g of water, 75 g of ethylene glycol and obtained according to Example 1. 261.8 g (3.4% by weight of SiO ₂ ) of the obtained spherical silica fine particle suspension (1-a) was added and mixed. The mixed solution was adjusted to 20 ± 1 ° C., and 187 g of methanol was added to tetraethoxysilane 37 while stirring.
A liquid in which 3 g was dissolved was dropped from the dropping port over 3 hours, and after the dropping, stirring was continued for 1 hour to grow seed particles by hydrolysis and condensation to obtain a suspension of spherical silica fine particles. The results are shown in Table-1.

Example 3 The procedure of 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% ammonia water were added and mixed to a 2 liter glass reactor equipped with a stirrer, a dropping port and a thermometer. 20 times the mixture
Adjust to ± 0.5 ℃, stirring with stirring 55.9
The liquid in which 111.8 g of tetramethoxysilane was dissolved in g was added dropwise from the dropping port over 1 hour, and after the dropping, stirring was continued for 1 hour to carry out hydrolysis and condensation to obtain a suspension (4-a) of spherical lysica fine particles. Obtained.

150 g of ethylene glycol was added to this suspension, which was concentrated at normal pressure using an evaporator, and when the internal temperature reached 190 ° C., heating was continued for 1 hour, and a slurry of ethylene glycol of spherical silica fine particles bonded with ethylene glycol ( A fine particle concentration of 28.0% by weight was obtained. This was used as seed particle slurry (4-b).

In a 2 liter glass reactor equipped with a stirrer, a dropping port and a thermometer, 329.7 g of methanol, 267.9 g of 28% ammonia water, 24.0 g of water and seed particle slurry (4
-B) 71.1 g was added and mixed. 20 times the mixture
The temperature was adjusted to ± 1 ° C, and while stirring, a solution prepared by dissolving 538 g of tetramethoxysilane in 269 g of methanol was added dropwise over 1 hour, and stirring was continued for 1 hour after the addition to grow seed particles by hydrolysis and condensation. To obtain a suspension of spherical silica fine particles. The results are shown in Table-1.

Example 5 A suspension of spherical silica fine particles (1
-A) was concentrated to dryness with an evaporator. The powder thus obtained was calcined at 400 ° C. for 1 hour. After adding this powder to methanol, ultrasonic treatment was performed to improve dispersion. The dispersion was filtered with paper to obtain a seed particle slurry (5-b).

In a 2 liter glass reactor equipped with a stirrer, a dropping port and a thermometer, 567.1 g of methanol, 267.9 g of 28% ammonia water, 75.0 g of ethylene glycol and 30.0 g of seed particle slurry (5-b) ( SiO _{2 (} 25.8 wt%) was added and mixed. The mixed solution was adjusted to 20 ± 1 ° C., and a solution in which 373 g of tetraethoxysilane was dissolved in 187 g of methanol was added dropwise with stirring over 3 hours, and after the addition, stirring was continued for 1 hour by hydrolysis and condensation. The seed particles were grown to obtain a suspension of spherical silica fine particles. The results are shown in Table-1.

Example 6 A suspension (1) of spherical silica fine particles obtained in Example 1
Ethylene glycol (500 g) was added to -c), the mixture was concentrated at normal pressure using an evaporator, the internal temperature was adjusted to 197.6 ° C., and ethylene glycol was gradually distilled off while continuously heating for 1 hour. Slurry of fine particle ethylene glycol (fine particle concentration 31.
2% by weight). This was used as seed particle slurry (6-b).

To a 2 liter glass reactor equipped with a stirrer, a dropping port and a thermometer, 389.7 g of methanol, 267.9 g of 28% ammonia water, 60 g of ethylene glycol and 51.4 g of seed particle slurry (6-b) were added. Mixed. The mixed solution 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 over 3 hours, and stirring was continued for 1 hour after the addition, by hydrolysis and condensation. Seed particles were grown to obtain a suspension (6-c) of spherical silica fine particles.

Example 7 A suspension of spherical silica fine particles (6
-C) 350 g of ethylene glycol was added to 1000 g, and the mixture was concentrated under atmospheric pressure using an evaporator, and the internal temperature was adjusted to 197.6.
The mixture is heated to 1 ° C and ethylene glycol is gradually distilled off, and heating is continued for 1 hour. Ethylene glycol slurry of spherical silica fine particles bonded with ethylene glycol (fine particle concentration 2
5.0% by weight) was obtained. The seed particle slurry (7-
b).

A 2 liter glass reactor equipped with a stirrer, a dropping port and a thermometer was charged with 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). Add and mix. 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 over 2 hours from the dropping port, and stirring was continued for 1 hour after the dropping, by hydrolysis and condensation. The seed particles were grown to obtain a suspension of spherical silica fine particles. The results are shown in Table-1.

Example 8 To a 2 liter glass reactor equipped with a stirrer, a dropping port and a thermometer, 1368.7 g of methanol and 11.3 g of water were added and mixed. The mixed solution was adjusted to 20 ± 0.5 ° C., and while stirring, a solution of 60 g of tetraisopropoxy titanate dissolved in 60 g of methanol was dropped from the dropping port over 1 hour, and stirring was continued for 1 hour after the dropping to hydrolyze. Then, condensation was carried out to obtain a suspension of spherical titania fine particles.

200 g of ethylene glycol was added to this suspension, and the suspension was concentrated under atmospheric pressure using an evaporator, and the internal temperature was 197.6.
When the temperature reached 0 ° C., heating was continued for 1 hour to obtain a slurry of ethylene glycol of fine particles of spherical titania bonded with ethylene glycol (fine particle concentration 14.0% by weight). This was used as seed particle slurry (8-b).

In a 2 liter glass reactor equipped with a stirrer, a dropping port and a thermometer, 336.5 g of methanol, 267.9 g of 28% ammonia water and 103.6 of seed particle slurry (8-b).
g was added and mixed. The mixed solution was adjusted to 20 ± 1 ° C., and while stirring, 396 g of methanol and 264 g of tetramethoxysilane and 13 parts of tetraisopropoxy titanate were mixed.
A liquid in which 2 g was dissolved was dropped from the dropping port over 4 hours, and stirring was continued for 1 hour after the dropping, and 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 To a 2 liter glass reactor equipped with a stirrer, a dropping port and a thermometer, 875.1 g of ethanol and 31.5 g of water were added and mixed. The mixed solution was adjusted to 25 ± 0.5 ° C., and while stirring, a solution prepared by dissolving 134.1 g of tetrabutoxyzirconate in 134.1 g of ethanol was added through a dropping port.
The solution was dropped over a period of time, and after the dropping, stirring was continued for 1 hour to carry out hydrolysis and condensation to obtain a suspension of spherical zirconia fine particles.

To this suspension, 350 g of ethylene glycol was added and concentrated under atmospheric pressure using an evaporator, and the internal temperature was 197.6.
When the temperature reached ℃, heating was continued for 1 hour to obtain a slurry of ethylene glycol of fine particles of spherical zirconia bonded with ethylene glycol (fine particle concentration: 15.0% by weight). This was used 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% ammonia water and 130.
0 g was added and mixed. The mixed solution was adjusted to 20 ± 1 ° C., while stirring, 293.3 g of ethanol was added to 200 g of tetramethoxysilane and 9 parts of tetrabutoxyzirconate.
A liquid in which 3.3 g was dissolved was added dropwise from a dropping port over 4 hours, and after the dropping, stirring was continued for 1 hour to grow seed particles by hydrolysis and condensation to obtain a suspension of spherical zirconia-silica fine particles. The results are shown in Table-1.

Example 10 To a 2 liter glass reactor equipped with a stirrer, a dropping port and a thermometer, 827.8 g of isopropanol, 191.3 g of 28% aqueous ammonia and 32.7 g of water were added and mixed. The mixed solution was adjusted to 20 ± 0.5 ° C., and a solution of 98.0 g of aluminum triisopropoxide dissolved in 98.0 g of ipropanol was added dropwise from the dropping port over 1 hour, and after the dropping, 1 was added. Hydrolysis and condensation were carried out by continuously stirring for a period of time to obtain a suspension of spherical alumina fine particles.

270 g of propylene glycol was added to this suspension,
Concentrated at atmospheric pressure using an evaporator, the internal temperature is 170 ℃
At that point, heating was continued for 1 hour to obtain a slurry (fine particle concentration: 15.0% by weight) of propylene glycol of spherical alumina fine particles of propylene glycol bonded spherical alumina fine particles of propylene glycol bonded. This was used as seed particle slurry (10-b).

In a 2 liter glass reactor equipped with a stirrer, a dropping port and a thermometer, 448.8 g of isopropanol, 267.9 g of 28% aqueous ammonia and seed particle slurry (10-b).
63.3 g was added and mixed. 20 ± 1 ° C of the mixture
The solution prepared by dissolving tetramethoxysilane (240 g) in isopropanol (360 g) and aluminum triisopropoxide (120 g) was added dropwise with stirring over 4 hours, and stirring was continued for 1 hour after the addition to produce seeds by hydrolysis and condensation. The particles were grown to obtain a suspension of spherical alumina-silica fine particles. 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 In a 2 liter glass reactor equipped with a stirrer, a dropping port and a thermometer, 467.1 g of methanol, 204.7 g of 28% ammonia water, 1.4 g of water, and ethylene glycol of 5.
0 g and 261.8 g of a suspension (1-a) of spherical silica squid fine particles obtained in Example 1 (3.4% by weight of SiO ₂ ) were added and mixed. The mixed solution was adjusted to 20 ± 1 ° C., and 187 g of methanol was added to tetraethoxysilane 373 while stirring.
A liquid in which g was dissolved was added dropwise from the dropping port over 3 hours, and after the addition, stirring was continued for 1 hour to grow seed particles by hydrolysis and condensation to obtain a suspension of spherical silica fine particles. Table of results
Shown in 1.

Comparative Example 3 In a 2 liter glass reactor equipped with a stirrer, a dropping port and a thermometer, 97.7 g of methanol, 541.2 g of ethylene glycol, 267.9 g of 28% ammonia water and seed particles obtained in Example 1 were used. 33.2 g of slurry (1-b)
(26.8 wt% SiO ₂ ) was added and mixed. The mixture was adjusted to 20 ± 1 ° C. and stirred with methanol 187
A solution in which 373 g of tetraethoxysilane was dissolved in g was added dropwise over 3 hours from a dropping port, and after the dropping, stirring was continued for 1 hour to grow seed particles by hydrolysis and condensation to obtain a suspension of spherical silica fine particles. . The results are shown in Table-1.

Comparative Example 4 The same procedure as in Example 5 was repeated except that eletin glycol was replaced with methanol. The results are shown in Table-1.

Front page continued (72) Inventor, Yoji Akazawa, 992, Nishi-oki, Kinohama, Aboshi-ku, Himeji-shi, Hyogo, Japan Himeji Plant, Nippon Catalytic Chemical Co., Ltd. Yoshio Ishii, Examiner, Central Research Laboratory, Nippon Shokubai Kagaku Kogyo Co., Ltd. (56) Reference JP-A-63-182204 (JP, A) JP-A-62-132708 (JP, A)

Claims (1)

[Claims] 1. An organic metal compound capable of being hydrolyzed and condensed is added to a seed particle suspension prepared by dispersing inorganic oxide particles as seed particles in a hydrous alcoholic solution to grow the seed particles. Crystalline spheres with an average particle size of 0.1 to 2
A method for producing inorganic oxide particles having a particle size variation coefficient of 0 μm and a particle size variation coefficient of 10% or less, wherein the reaction is carried out by adding 1 to 2 carbon atoms of alkylene glycol to the hydroalcoholic solution. The method for producing inorganic oxide particles having excellent monodispersibility, characterized in that the content is in the range of 50 wt%.