JP2008184371A - Method for producing metal oxide particles, metal oxide particles and resin composition - Google Patents

Abstract

【Task】
A method of producing metal oxide particles that can be suitably used as a filler (filler) of a resin used as a sealant or a dental material of a semiconductor element / liquid crystal display element, while suppressing the formation of aggregates, Metal oxide particles obtained by the method and a resin composition containing the metal oxide particles are provided.
A method for producing metal oxide particles, characterized in that a mother particle comprising a specific metal oxide is surface-treated with a specific metal alkoxide compound or a partial hydrolyzate thereof and then fired. A metal oxide particle characterized by being obtained and a resin composition comprising the metal oxide particle.
[Selection figure] None

Description

The present invention relates to a method for producing metal oxide particles, metal oxide particles, and a resin composition.
More specifically, the present invention relates to a method for producing metal oxide particles that can be suitably used as a filler (filler) of a resin used as a sealant or dental material for a semiconductor element / liquid crystal display device, The present invention relates to a metal oxide particle obtained by the method and a resin composition containing the metal oxide particle.

  Conventionally, sintered inorganic oxide particles such as silica particles have been used as fillers (fillers) such as thermosetting and photo-curable resin compositions used as sealants and dental materials for semiconductor elements and liquid crystal display devices, for example. ).

  The silica particles can be obtained, for example, by a method in which tetraalkoxysilane or the like is hydrolyzed and condensed in an alcoholic solvent, and then dried and fired.

  However, since many Si—OH (silanol) groups exist on the surface of the silica particles obtained by the above method, condensation reaction (bonding with strong cohesive force) occurs between the particles in the drying and firing processes. When the aggregate was formed and it filled in resin etc., it had the subject that it was not disperse | distributed easily.

In order to solve the above-mentioned problem, for example, a method for suppressing the generation of aggregates by adding a relatively high boiling alcohol such as ethylene glycol during the synthesis of fine particles such as silica particles has been reported (for example, Patent Document 1). However, even in this method, the silica particles cannot withstand heating under vacuum or baking at several hundred degrees, and generate not a little agglomerates, which is sufficient as a method for solving the above problems. I couldn't say that.
Japanese Patent Laid-Open No. 3-50105

  Under such circumstances, the present invention provides metal oxide particles that can be suitably used as a filler (filler) for a resin used as a sealant or dental material for semiconductor elements and liquid crystal display devices. It is an object of the present invention to provide a method for producing while suppressing the formation of aggregates, a metal oxide particle obtained by the method, and a resin composition containing the metal oxide particle.

  As a result of intensive studies to achieve the above object, the present inventors have surface-treated mother particles containing at least one selected from specific metal oxides with a specific metal alkoxide compound, and then fired. As a result, it was found that metal oxide particles can be produced while suppressing the formation of aggregates, and the present invention has been completed based on this finding.

That is, the present invention
(1) General formula (I)
M ¹ _x O _y (I)
(Wherein M ¹ represents a metal atom selected from silicon, titanium, zirconium and aluminum;
When M ¹ is silicon, titanium, or zirconium, x = 1 and y = 2, and when M ¹ is aluminum, x = 2 and y = 3. A mother particle containing at least one selected from metal oxides represented by
Formula (II)
R ² _n M ² (OR ³ ) _m−n (II)
(Wherein R ² is a non-hydrolyzable group, R ³ is an alkyl group having 1 to 6 carbon atoms, M ² is a metal atom selected from silicon, titanium, zirconium and aluminum,
m is 4 when M ² is silicon, titanium or zirconium, 3 when M ² is aluminum, n is an integer of 1 to 3 when m is 4, and m is 3 An integer from 1 to 2,
When R ² are a plurality, each R ² may be different from one another identical, if the OR ³ there are a plurality, each OR ³ may be different even identical to each other. )
A metal oxide alkoxide compound represented by the formula:
(2) The metal oxide represented by the general formula (I) is represented by the general formula (III)
M ¹ (OR ¹ ) _z (III)
(Wherein R ¹ represents an alkyl group having 1 to 10 carbon atoms,
M ¹ represents a metal atom selected from silicon, titanium, zirconium and aluminum;
z is 4 when M ¹ is silicon, titanium or zirconium, and 3 when M ¹ is aluminum;
When there are a plurality of OR ¹ , each OR ¹ may be the same or different. The method for producing metal oxide particles according to (1) above, wherein the metal alkoxide compound represented by (1) or a partial hydrolyzate thereof is obtained by hydrolysis and condensation.
(3) The method for producing metal oxide particles according to (1) or (2), wherein the metal oxide represented by the general formula (I) is silica,
(4) The method for producing metal oxide particles according to any one of (1) to (3), wherein the metal alkoxide compound represented by the general formula (II) is a monoalkyltrialkoxysilane or a dialkyl dialkoxysilane. ,
(5) After the surface treatment synthesizes the mother particles composed of the metal oxide represented by the general formula (I), the metal alkoxide compound represented by the general formula (II) or the synthetic solution containing the mother particles or The method for producing metal oxide particles according to any one of the above (1) to (4), which is performed by adding the partial hydrolyzate,
(6) The metal oxide particles according to any one of (1) to (5), wherein the firing is performed under a condition that the R ² group in the metal alkoxide compound represented by the general formula (II) can be eliminated. Manufacturing method,
(7) The method for producing metal oxide particles according to any one of (1) to (6) above, wherein the average particle diameter of the obtained metal oxide particles is 0.01 to 5 μm,
(8) Metal oxide particles obtained by the method according to any one of (1) to (7) above, and (9) Metal oxide particles according to (8) above It provides the resin composition characterized by including.

  According to the present invention, there is provided a method for producing metal oxide particles while suppressing formation of aggregates by subjecting mother particles comprising a specific metal oxide to surface treatment with a specific metal alkoxide compound and then firing. Can be provided. Moreover, according to this invention, the resin composition containing the metal oxide particle obtained by the said method and this metal oxide particle can be provided.

First, the manufacturing method of the metal oxide particle of this invention is demonstrated.
The method for producing metal oxide particles of the present invention includes:
Formula (I)
M ¹ _x O _y (I)
(Wherein M ¹ represents a metal atom selected from silicon, titanium, zirconium and aluminum;
When M ¹ is silicon, titanium, or zirconium, x = 1 and y = 2, and when M ¹ is aluminum, x = 2 and y = 3. A mother particle containing at least one selected from metal oxides represented by
Formula (II)
R ² _n M ² (OR ³ ) _m−n (II)
(Wherein R ² is a non-hydrolyzable group, R ³ is an alkyl group having 1 to 6 carbon atoms, M ² is a metal atom selected from silicon, titanium, zirconium and aluminum,
m is 4 when M ² is silicon, titanium or zirconium, 3 when M ² is aluminum, n is an integer of 1 to 3 when m is 4, and m is 3 An integer from 1 to 2,
When R ² are a plurality, each R ² may be different from one another identical, if the OR ³ there are a plurality, each OR ³ may be different even identical to each other. )
After the surface treatment with a metal alkoxide compound represented by the formula (1) or a partial hydrolyzate thereof, firing is performed.

General formula (I) used in the process of the invention
M ¹ _x O _y (I)
M ¹ represents a metal atom selected from silicon, titanium, zirconium and aluminum, and when M ¹ is silicon, titanium or zirconium, x = 1 and y = 2. Yes, when M ¹ is aluminum, x = 2 and y = 3. That is, the metal oxide represented by the general formula (I) is specifically selected from silica (SiO ₂ ), titania (TiO ₂ ), zirconia (ZrO ₂ ), and alumina (Al ₂ O ₃ ). This means the metal oxide.

The metal oxide represented by the general formula (I) is preferably the general formula (III)
M ¹ (OR ¹ ) _z (III)
(Wherein R ¹ represents an alkyl group having 1 to 10 carbon atoms,
M ¹ represents a metal atom selected from silicon, titanium, zirconium and aluminum;
z is 4 when M ¹ is silicon, titanium or zirconium, and 3 when M ¹ is aluminum;
When there are a plurality of OR ¹ , each OR ¹ may be the same or different. ) Or a partial hydrolyzate thereof obtained by hydrolysis and condensation.

In the metal alkoxide compound represented by the general formula (III), R ¹ is an alkyl group having 1 to 10 carbon atoms, and this alkyl group may be linear, branched or cyclic. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl Groups and the like.

In the metal alkoxide compound represented by the general formula (III), z is 4 when M ¹ is silicon, titanium or zirconium, 3 when M ¹ is aluminum, and there are a plurality of OR ^1. In this case, each OR ¹ may be the same or different.

  Specific examples of such metal alkoxide compounds include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, and tetra-sec-butoxy. Silane, tetra-tert-butoxysilane, methoxytriethoxysilane, methoxytripropoxysilane, methoxytriisopropoxysilane, ethoxytrimethoxysilane, propoxytriethoxysilane, butoxytrimethoxysilane, and the silane in each of the above metal alkoxide compounds. And compounds substituted with titanium or zirconium. From the viewpoint of controllability of hydrolysis reaction, the metal alkoxide compound is preferably tetramethoxysilane or tetraethoxysilane.

  In the present specification, the metal alkoxide compound represented by the general formula (III) includes a dimer or an oligomer obtained by condensing the above various metal alkoxide compounds.

  Examples of the partially hydrolyzed product of the metal alkoxide compound represented by the general formula (III) include monohydroxytrialkoxysilane, dihydroxy dialkoxysilane and the like obtained by partially hydrolyzing the various metal alkoxide compounds.

  A metal oxide represented by the general formula (I) can be obtained by hydrolyzing and condensing the metal alkoxide compound represented by the general formula (III) or a partial hydrolyzate thereof.

  The hydrolysis and condensation reaction is preferably performed in an alkaline aqueous solution containing alkali, alcohol and water. As the alkali, ammonia derivatives such as ammonia, methylamine, ethylamine, and diethylamine are preferable. As the alcohol, methanol, ethanol, n-propanol, i-propanol, t-propanol, t-amyl alcohol, and the like are preferable.

  The alkaline aqueous solution preferably contains 5 times or more water in terms of moles relative to the metal alkoxide compound represented by the general formula (III) or a partial hydrolyzate thereof, and contains 10 to 50 times water. It is more preferable.

  The hydrolysis and condensation reaction is carried out while adding the metal alkoxide compound represented by the general formula (III) or a partial hydrolyzate thereof at a rate of about 0.1 g / min to 300 g / min with respect to the alkaline aqueous solution. It is preferable to do so. The metal alkoxide compound represented by the general formula (III) or a partial hydrolyzate thereof is preferably added sequentially to the alkaline aqueous solution, and the reaction temperature is preferably about 0 to 60 ° C.

  When the particle size of the metal oxide represented by the general formula (I) obtained by the above method is smaller than the desired particle size, the metal oxide is used as a seed particle and is further represented by the general formula (III). By adding a metal alkoxide compound or a partial hydrolyzate thereof in the presence of a catalyst such as an alkali, the metal alkoxide compound can be grown to a desired particle size.

  The metal oxide represented by the general formula (I) obtained by the above method may be further subjected to firing treatment, and the strength and hardness of the metal oxide can be increased by performing the firing treatment. The number of metal alkoxyl groups such as Si—OH (silanol) groups present on the surface of the metal oxide is reduced by performing the baking treatment, and the mother particles composed of the metal oxide represented by the general formula (I) And the metal alkoxide compound represented by the general formula (II) are less likely to proceed, so that the baking treatment is preferably not performed.

In the process of the present invention, the general formula (I)
M ¹ _x O _y (I)
(In the formula, M ¹ represents a metal atom selected from silicon, titanium, zirconium, and aluminum. When M ¹ is silicon, titanium, or zirconium, x = 1, y = 2, and M ¹ is (In the case of aluminum, x = 2 and y = 3.)
The mother particle containing at least one or more selected from the metal oxides represented by formula ( ₁ ) is any one selected from silica (SiO ₂ ), titania (TiO ₂ ), zirconia (ZrO ₂ ) and alumina (Al ₂ O ₃ ). One or more metal oxides are included, and as such mother particles, specifically, silica (SiO ₂ ), titania (TiO ₂ ), zirconia (ZrO ₂ ), and alumina (Al ₂ O ₃ ) Or a metal oxide particle selected from silica (SiO ₂ ), titania (TiO ₂ ), zirconia (ZrO ₂ ) and alumina (Al ₂ O ₃ ). those containing two or more can be mentioned, silica _(SiO 2), titania (TiO _2), zirconia (ZrO ₂₎ and any one metal oxide selected from alumina _(Al 2 _{O 3)} Preferably made of only, it is more preferably composed of only silica (SiO _2).

  The particle size of the mother particles is preferably 10 nm to 5 μm, more preferably 10 nm to 2 μm, and even more preferably 50 nm to 1 μm.

The case where the mother particles are composed of only one metal oxide selected from silica (SiO ₂ ), titania (TiO ₂ ), zirconia (ZrO ₂ ), and alumina (Al ₂ O ₃ ) is described above. In the method for producing a metal oxide, the mother particles can be produced by growing the particle size of the metal oxide to a desired particle size. In the case where the mother particle contains two or more kinds of the metal oxide particles, in the metal oxide production method described above, an alkoxide compound of two or more metals selected from silicon, titanium, zirconium and aluminum, or a portion thereof A method in which the hydrolyzate is hydrolyzed and condensed at the same time, or a particle made of a metal oxide selected from silica, titania, zirconia and alumina is produced as a core particle, and then a metal different from the metal constituting the core particle. The alkoxide compound or its partial hydrolyzate may be added to a solution containing the above core particles and grown to a desired particle size.

In the method of the present invention, the mother particle comprising the metal oxide represented by the general formula (I) is converted into the general formula (II).
R ² _n M ² (OR ³ ) _mn (II)
Surface treatment with a metal alkoxide compound represented by
In the general formula (II), R ² is a non-hydrolyzable group such as an alkyl group having 1 to 20 carbon atoms, a (meth) acryloyloxy group or an epoxy group having 1 to 20 carbon atoms, or 2 carbon atoms. -20 alkenyl group, a C6-C20 aryl group, or a C7-C20 aralkyl group is shown.

  Here, as a C1-C20 alkyl group, a C1-C10 thing is preferable, and this alkyl group may be linear, branched, or cyclic. Examples of this alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, and cyclopentyl. Group, cyclohexyl group and the like.

  As a C1-C20 alkyl group which has a (meth) acryloyloxy group or an epoxy group, a C1-C10 alkyl group which has these substituents is preferable, and this alkyl group is linear or branched. Any of an annular shape may be used. Examples of the alkyl group having this substituent include γ-acryloyloxypropyl group, γ-methacryloyloxypropyl group, γ-glycidoxypropyl group, 3,4-epoxycyclohexyl group, and the like.

  The alkenyl group having 2 to 20 carbon atoms is preferably an alkenyl group having 2 to 10 carbon atoms, and the alkenyl group may be linear, branched or cyclic. Examples of the alkenyl group include vinyl group, allyl group, butenyl group, hexenyl group, octenyl group and the like.

  As a C6-C20 aryl group, a C6-C10 thing is preferable, for example, a phenyl group, a tolyl group, a xylyl group, a naphthyl group etc. are mentioned.

  As a C7-20 aralkyl group, a C7-10 thing is preferable, for example, a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group etc. are mentioned.

On the other hand, R ³ is an alkyl group having 1 to 6 carbon atoms, which may be linear, branched or cyclic, and examples thereof include a methyl group, an ethyl group, an n-propyl group, and isopropyl. Group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, cyclopentyl group, cyclohexyl group and the like.

M ² represents a metal atom selected from silicon, titanium, zirconium and aluminum, m is 4 when M ² is silicon, titanium or zirconium, and 3 when M ² is aluminum, n is, m is an integer of 1 to 3 in the case of 4, m is 1 to 2 integer in the case of 3, when R ² are a plurality, even each R ² optionally substituted by one or more identical to each other Well, when there are a plurality of OR ³ , each OR ³ may be the same or different.

Specific examples of the metal alkoxide compound represented by the above general formula (II) in which M ² is silicon, titanium, zirconium, m is 4 and n is an integer of 1 to 3 include methyl Trimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, Vinyltrimethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-acryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, dimethyldimethoxysilane Such as methyl phenyl dimethoxy silane, and silane in the compound include a compound obtained by substituting titanium or zirconium.

Moreover, in the metal alkoxide compound represented by the above general formula (II), as a specific example of the metal alkoxide compound in which M ² is aluminum, m is 3, and n is an integer of 1 to 2, methyldimethoxyaluminum Methyldiethoxyaluminum, methyldipropoxyaluminum, ethyldimethoxyaluminum, ethyldiethoxyaluminum, propyldiethoxyaluminum and the like.

As the metal alkoxide compound represented by the general formula (II), monoalkyltrialkoxysilane or dialkyldialkoxysilane in which M ² is silicon is preferable.

  In the present specification, the metal alkoxide compound represented by the general formula (II) includes a dimer or oligomer obtained by condensing the above various metal alkoxide compounds.

  As a specific example of the partial hydrolyzate of the metal alkoxide compound represented by the above general formula (II), among the all alkoxyl groups constituting the above various metal alkoxide compounds, those obtained by replacing some alkoxyl groups with hydroxyl groups Can be mentioned.

  As the metal alkoxide compound represented by the general formula (II) or a partial hydrolyzate thereof, one kind may be used alone, or two or more kinds may be used in combination. As a method for surface-treating the mother particles comprising the metal oxide represented by the general formula (I) with the metal alkoxide compound represented by the general formula (II) or a partial hydrolyzate thereof, the above general formula (I) A method of adding the metal alkoxide compound represented by the general formula (II) or a partial hydrolyzate thereof to the liquid containing the mother particles composed of the metal oxide represented by formula (II) can be given. In particular, in the method of the present invention, after synthesizing the mother particles composed of the metal oxide represented by the general formula (I), the metal alkoxide represented by the general formula (II) is added to the synthesis solution containing the mother particles. A method of adding a compound or a partial hydrolyzate thereof can also be adopted, and according to this method, the process can be simplified because it can be used as it is in the synthesis solution without isolating the mother particles. Is possible.

  The mother particles are preferably dispersed in advance in a solvent containing one or more alcohols selected from methanol, ethanol, n-propanol, i-propanol, t-propanol, t-amyl alcohol, and the like. More preferably, the mother particles composed of the metal oxide represented by (I) are synthesized in a solvent containing alcohol, and then the mother particles dispersed in the synthesis solution are used in a solution state.

  The surface treatment is preferably performed in the presence of a catalyst, and the catalyst is preferably an alkali, and more preferably one or more ammonia derivatives selected from ammonia, methylamine, ethylamine, diethylamine and the like. The catalyst is preferably provided in the form of an aqueous solution, and is preferably added in advance to the mother particle-containing solution.

The addition amount (g) of the metal alkoxide compound represented by the general formula (II) or a partial hydrolyzate thereof can be defined by the following formula (α), for example.
{(A) / (B)} × addition magnification (α)
(Here, (A) is the amount of the metal oxide represented by the general formula (I) (g) × the surface area per unit amount (g) of the metal oxide represented by the general formula (I); B) means the minimum coverage area value of the metal alkoxide compound represented by the general formula (II) or a partial hydrolyzate thereof)
The addition ratio in the above formula (α) is preferably 0.01 to 10, more preferably 0.1 to 5.

It is preferable that the metal alkoxide compound represented by the general formula (II) or a partially hydrolyzed product thereof is sequentially added to the mother particle-containing liquid and stirred. 0-60 degreeC is preferable and, as for reaction temperature, 20-40 degreeC is more preferable.
The reactant-containing liquid obtained by the above reaction can be concentrated by subjecting it to a drying treatment, if desired, to obtain solid surface-treated mother particles.

The surface-treated mother particle can be considered to have a metal alkoxide compound represented by the general formula (II) or a partial hydrolyzate thereof attached to the mother particle, and the outermost surface has the general formula (II) It is considered that there are a large number of R ² groups derived from the metal alkoxide compound represented by the formula (1) or a partial hydrolyzate thereof.

The reactant is then calcined.
Firing is preferably performed under conditions that allow the R ² group in the metal alkoxide compound represented by the general formula (II) to be eliminated. The state of the surface of the mother particle after the elimination of the R ² group cannot be clarified at the present time because it is difficult to analyze, but the state after the elimination of the R ² group is present on the particle surface. It is considered that the aggregation of the surface-treated mother particles can be reduced by the presence of.

As such conditions, for example, the firing temperature can be set to a desorption start temperature of the R ² group in the metal alkoxide compound represented by the general formula (II) −10 ° C. or higher. The temperature is preferably 300 ° C. or higher, more preferably 500 ° C. or higher.

  The calcination treatment can be performed, for example, by placing the reactant in an alumina crucible and setting it in a muffle furnace, and heating at atmospheric pressure for 10 to 72 hours.

  The obtained metal oxide particles preferably have an average particle size of 0.01 to 5 μm.

Next, the metal oxide particles of the present invention will be described.
The metal oxide particles of the present invention are obtained by the method for producing metal oxide particles of the present invention.
Examples of the method for producing the metal oxide particles of the present invention include the same method as the method for producing the metal oxide particles of the present invention, and the average particle size of the metal oxide particles is also the metal of the present invention. This is the same as the metal oxide particles obtained by the method for producing oxide particles.

Next, the resin composition of the present invention will be described.
The resin composition of the present invention includes the metal oxide particles of the present invention.

  The resin composition of the present invention contains a matrix resin together with the metal oxide particles of the present invention, and an epoxy resin, an unsaturated polyester resin, a vinyl ester resin and glycidyl (meth) acrylate are added as the matrix resin. Can include any one or more selected from glycidyl (meth) acrylate-modified acrylic resins into which at least one double bond has been introduced.

  Among the matrix resins, the epoxy resin is a heat condensation curable resin, but the other resin is a radical curable resin, and if necessary, a polymerizable monomer having one polymerizable double bond, for example, , Styrene and (meth) acrylate monomers, or crosslinkable monomers having two or more polymerizable double bonds, such as triethylene glycol di (meth) acrylate and trimethylolpropane tri (meth) acrylate May be added, or the polymerizable monomer and the crosslinkable monomer may be used in combination.

  When the resin composition is used as a sealing agent for semiconductor elements, the matrix resin is preferably at least one selected from an epoxy resin, an unsaturated polyester resin, or a vinyl ester resin. When the resin composition is used as a dental material, the matrix resin is preferably a glycidyl (meth) acrylate-modified acrylic resin.

  The resin composition of this invention may contain a hardening | curing agent, a radical polymerization initiator, etc. as needed.

The resin composition of the present invention may contain only one type of the metal oxide particles of the present invention, or may contain two or more types having different average particle sizes and particle size distributions.
Moreover, when the resin composition obtained is 100 parts by weight, the content of metal oxide particles contained in the resin composition is preferably 10 to 90 parts by weight.

  The resin composition of the present invention can be obtained, for example, by kneading the metal oxide particles of the present invention and a matrix resin.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.

Example 1 (Production Example of Metal Oxide Particles)
(1) Production of seed particles A 50-liter reaction vessel equipped with a stirrer is set in a thermostatic bath, and methanol 14861 g, 25% aqueous ammonia 10320 g and ion-exchanged water 9288 g are mixed to obtain a mixed solution and stirred with a stirrer. The temperature was adjusted to 30 ° C.
While stirring the above mixed solution, 2321 g of tetraethoxysilane was continuously added at a rate of 50 g per minute. After the addition, concentration was performed with a rotary evaporator to obtain a dispersed aqueous solution of seed particles made of silica. When the seed particles were measured with a scanning electron microscope, the average particle size was 98 nm (0.098 μm).

(2) Production of mother particles made of silica A 100-liter reaction vessel equipped with a stirrer was set in a thermostatic bath, and methanol 26578 g, 25% ammonia water 17454 g and ion-exchanged water 7011 g were added, and further obtained in (1). A seed particle dispersion was obtained by adding 350 g of an aqueous dispersion of silica seed particles (concentration: 21.9 wt%). The dispersion is adjusted to a temperature of 30 ° C., and 29165 g of tetraethoxysilane is added at a rate of 50 g / min while mixing with a stirrer to carry out a hydrolytic condensation reaction to grow seed particles. 8243 g was obtained. The mother particles made of silica had a surface area per unit weight of 9.9 m ² / g and an average particle diameter measured by a scanning electron microscope of 410 nm (0.410 μm).

(3) Surface treatment of mother particles made of silica Methyltrimethoxysilane (desorption temperature of methyl group 340 ° C., minimum covering area 572 m ² / g) was added to the dispersion of mother particles made of silica obtained in (2) above. 440 g (corresponding to an addition ratio of 3.08 times in the general formula (α)) was added at a rate of 50 g per minute, and the surface treatment of the mother particles made of silica was performed. After the surface treatment, when the obtained reaction product was measured with a scanning electron microscope, the average particle size was 414 nm (0.414 μm).

(4) Drying treatment A nylon ball (φ25 mm) 15 kg for crushing and a vibration dryer (VHS-30 type, manufactured by Chuo Kako Co., Ltd.) equipped with a water-sealed vacuum pump, a condenser, and a heating jacket, 25 liters of the aqueous dispersion of the surface-treated mother particles obtained in 3) was added, and the operation was concentrated under reduced pressure to 53 kPa while heating the interior of the dryer to 105 ° C.
When the liquid volume was concentrated to 15 liters, 10 liters of the aqueous dispersion of the surface-treated mother particles obtained in (3) above was further introduced into the dryer, and the concentration operation was performed. By repeating such a concentration operation, 4 hours after first introducing the aqueous dispersion of the surface-treated mother particles, the aqueous dispersion obtained in (3) above was concentrated to 25 liters.
Next, only 5 liters of 25 liters of concentrated liquid in the drier were left, 20 liters of methanol was poured into this, and further concentrated for 1 hour to remove alcohol and ammonia.
After completion of the methanol injection, the silica gel powder was obtained by performing a concentration operation while applying vibration by a vibration force of 520 kgf to the vibration dryer. The obtained silica particles were further dried at 105 ° C. for 3 hours.

(5) Firing treatment The silica particles obtained in (4) above are placed in an alumina crucible and set in a muffle furnace. The temperature is raised from room temperature to 500 ° C. under atmospheric pressure over 3 hours, and this temperature is maintained for 9 hours. Then, the temperature was lowered to room temperature over 3 hours to obtain calcined silica particles.

Example 2 (Production Example of Resin Composition)
10 g of the fired silica particles obtained in Example 1 were weighed out into a plastic container with a lid exclusively for the kneading apparatus, and 40 g of epoxy ester 3002A manufactured by Kyoeisha Chemical Co., Ltd. was added.
Using Shintaro Awatori Nertaro MX-201, the fired silica particles and the epoxy polyester in the container were kneaded twice at 2000 rpm for 4 minutes to obtain a resin composition.

The obtained resin composition was visually observed, and the presence or absence of dispersion of the sintered silica particle mass was confirmed according to the following evaluation criteria. The results are shown in Table 1.
○: Particle lump is hardly observed
Δ: Particle clusters are observed
×: Many particle lumps are observed

Example 3 (Production Example of Metal Oxide Particles)
In Example 1 (3), instead of 440 g of methyltrimethoxysilane, dimethyldimethoxysilane (methyl group elimination temperature 340 ° C., minimum covering area 650 m ² / g) 500 g (general formula (α), addition ratio 3. Example 1 except that a reactant having an average particle size of 409 nm (0.409 μm) was obtained instead of a reactant having an average particle size of 414 nm (0.414 μm). The same treatment was performed to obtain calcined silica particles.

Example 4 (Production Example of Resin Composition)
A resin composition was obtained in the same manner as in Example 2 except that 10 g of the calcined silica obtained in Example 3 was used instead of the calcined silica particles obtained in Example 1, and calcined according to the same criteria as in Example 2. The presence or absence of dispersion of the silica particle mass was confirmed. The results are shown in Table 1.

Comparative Example 1 (Production Example of Metal Oxide Particles)
Sintered silica particles were produced in the same manner as in Example 1, except that “(3) Surface treatment of base particles made of silica” in Example 1 was not performed.

Comparative Example 2 (Production Example of Resin Composition)
Using the baked silica obtained in Comparative Example 1, a resin composition was prepared in the same manner as in Example 2, and the obtained resin composition was evaluated according to the same criteria as in Example 2. The results are shown in Table 1.

Comparative Example 3 (Production Example of Metal Oxide Particles)
(1) Production of seed particles 707.3 g of ethanol, 275.3 g of 28% ammonia water and 24.0 g of water were added to and mixed with 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., and 134.1 g of tetraethoxysilane was dropped from the dropping port over 1 hour while stirring, and the stirring and stirring were continued for 1 hour after the dropping, thereby causing hydrolysis and condensation reaction. A seed particle suspension composed of spherical silica fine particles was obtained.

(2) Ethylene glycol treatment 100 g of ethylene glycol was added to the suspension obtained in (1) above, concentrated at normal pressure using an evaporator, and when the internal temperature reached 150 ° C, heating was continued for 1 hour. A slurry of seed particles (fine particle concentration of 26.8% by weight) to which 2.0 mmol / g of glycol was bonded was obtained and used as a seed particle slurry. The average particle size of the seed particles in the obtained slurry was 0.96 μm.

(3) Particle size growth treatment Obtained with 586.9 g of methanol, 267.9 g of 28% aqueous ammonia, 52 g of ethylene glycol and (2) above in a 2 liter glass reactor equipped with a stirrer, dropping port and thermometer. 33.2 g of seed particle slurry was dropped and mixed to obtain a mixed solution.
The above mixed solution was adjusted to 20 ± 1 ° C., and while stirring, a solution obtained by dissolving 373 g of tetraethoxysilane in 187 g of methanol was dropped from the dropping port over 3 hours. After the dropping, stirring was continued for 1 hour, hydrolysis, Seed particles were grown by a condensation reaction to obtain a suspension of spherical silica fine particles, followed by drying to obtain spherical silica fine particles having an average particle size of 2.30 μm.

Comparative Example 4 (Production Example of Resin Composition)
Using the spherical silica fine particles obtained in Comparative Example 3, a resin composition was prepared in the same manner as in Example 2, and the obtained resin composition was evaluated according to the same criteria as in Example 2. The results are shown in Table 1.

  As shown in Table 1, in the resin composition of the present invention obtained in Example 2 and Example 4, almost no particle mass was observed in the resin composition as a result of visual observation.

  On the other hand, in Comparative Example 2 in which the resin composition was prepared using baked silica prepared without treating the surface of the mother particles with the metal alkoxide, the observation result by visual observation showed that the particle mass in the resin composition Many were observed. In addition, in Comparative Example 4 in which ethylene glycol was added to the reaction solution, the resin composition was prepared using spherical silica particles prepared without treating the surface of the particles with a metal alkoxide or subsequent firing treatment. As a result of visual observation, particle lumps were observed in the resin composition.

  By comparing Example 2 and Example 4 with Comparative Example 2 and Comparative Example 4, the surface of the mother particles was treated with a metal alkoxide compound, and the surface-treated mother particles were baked to produce aggregates (particle agglomerates). It can be seen that the metal oxide particles can be produced while suppressing the generation of).

ADVANTAGE OF THE INVENTION According to this invention, the metal oxide particle which can be used suitably as a resin filler (filler) used as a sealing agent, a dental material, etc. of a semiconductor element is manufactured, suppressing the production | generation of an aggregate. A method, metal oxide particles obtained by the method, and a resin composition containing the metal oxide particles can be provided.

Claims (9)

Formula (I)
M ¹ _x O _y (I)
(Wherein M ¹ represents a metal atom selected from silicon, titanium, zirconium and aluminum;
When M ¹ is silicon, titanium, or zirconium, x = 1 and y = 2, and when M ¹ is aluminum, x = 2 and y = 3. A mother particle containing at least one selected from metal oxides represented by
Formula (II)
R ² _n M ² (OR ³ ) _m−n (II)
Wherein R ² is a non-hydrolyzable group, R ³ is an alkyl group having 1 to 6 carbon atoms, M ² is a metal atom selected from silicon, titanium, zirconium and aluminum, and m is M ² Is 4 when M is silicon, titanium or zirconium, n is 3 when M ² is aluminum, n is an integer of 1 to 3 when m is 4 and an integer of 1 to 2 when m is 3 And
When R ² are a plurality, each R ² may be different from one another identical, if the OR ³ there are a plurality, each OR ³ may be different even identical to each other. )
A method for producing metal oxide particles, comprising: surface-treating with a metal alkoxide compound represented by the formula: The metal oxide represented by the general formula (I) is represented by the general formula (III)
M ¹ (OR ¹ ) _z (III)
(Wherein R ¹ represents an alkyl group having 1 to 10 carbon atoms,
M ¹ represents a metal atom selected from silicon, titanium, zirconium and aluminum;
z is 4 when M ¹ is silicon, titanium or zirconium, and 3 when M ¹ is aluminum;
When there are a plurality of OR ¹ , each OR ¹ may be the same or different. The method for producing metal oxide particles according to claim 1, wherein the metal alkoxide compound or a partially hydrolyzed product thereof is obtained by hydrolysis and condensation.   The method for producing metal oxide particles according to claim 1 or 2, wherein the metal oxide represented by the general formula (I) is silica.   The method for producing metal oxide particles according to any one of claims 1 to 3, wherein the metal alkoxide compound represented by the general formula (II) is a monoalkyltrialkoxysilane or a dialkyl dialkoxysilane.   After the surface treatment is performed to synthesize mother particles composed of the metal oxide represented by the general formula (I), the metal alkoxide compound represented by the general formula (II) or a partial hydrolyzate thereof is added to the synthesis solution containing the mother particles. The manufacturing method of the metal oxide particle in any one of Claims 1-4 performed by adding a decomposition product. The method for producing metal oxide particles according to any one of claims 1 to 5, wherein the calcination is performed under a condition that the R ² group in the metal alkoxide compound represented by the general formula (II) can be eliminated.   The average particle diameter of the metal oxide particle obtained is 0.01-5 micrometers, The manufacturing method of the metal oxide particle in any one of Claims 1-6.   Metal oxide particles obtained by the method according to any one of claims 1 to 7.   A resin composition comprising the metal oxide particles according to claim 8.