JPS58156526A - Inorganic oxide and preparation thereof - Google Patents

Abstract

PURPOSE:To prepare inorganic oxide particles having improved various characteristics, by adding a solution containing a specific organosilicon compound and an organometallic compound to an alkaline solvent, and hydrolyzing both compounds. CONSTITUTION:A hydrolyzable organosilicon compound, e.g. an alkoxysilane, and a hydrolyzable organic compound of a metal selected from GroupIin the periodic table, e.g. K, Li or Na, are added to an alcoholic solution and mixed. The resultant solution is then added to an alkaline solvent, e.g. ammoniac alcohol, capable of dissolving both organic compounds, but incapable of dissolving the reaction product, to hydrolyze both organic compounds. Thus, the aimed fine particulate inorganic oxide, having 0.1-10mum particle diameter, <=1.30 standard deviation value of the particle diameter distribution and >= 100m<2>/g specific surface, consisting of silica containing 20mol% or less above- mentioned metallic oxide, and usable widely as a dental filler, etc. is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel spherical inorganic oxide whose main constituents are silica and a metal oxide of group Ⅰ of the synchronous table (hereinafter abbreviated as group Ⅰ), and its production. Regarding the method.

Conventionally, inorganic oxides containing silica and Group 1 metal oxides as main constituents have been known, but their shapes are amorphous, and spherical ones are not known. A known manufacturing method is to mix silica and the metal oxide of the first layer, melt the scissor mixture at a high temperature above the melting point to obtain a glassy material, and crush the glassy material. As a result, the shape is not only irregular as described above, but also the particle size distribution is extremely wide, so that it can only be used for limited purposes. In addition, as another manufacturing method, alkoxysilane and
It is known that an agar-like gel is obtained by mixing a group metal alcoholade and hydrolyzing this, and by calcining the agar-like substance, silica and the first layer of metal oxide are obtained. There is. This method is superior to the above-mentioned methods in that the agar-like gel can be changed into a limited shape by forming it into a plate or a fiber. however,
Even if such a production method is adopted, it has not been possible to obtain an inorganic oxide having a spherical shape and having a uniform particle size, particularly a small particle size, for example, 0.1 to 1.0 μm. Therefore, it has been a major technical challenge to obtain an inorganic oxide consisting of spherical silica with uniform particle diameter and a first layer of metal oxide.

Therefore, an object of the present invention is to provide a spherical inorganic oxide whose main constituents are silica and a first layer of metal oxide, and a method for producing the same.

Another object of the present invention is to provide an inorganic oxide having a particle size in the range of 0.1 to 1.0 μm and a very uniform particle size distribution, and a method for producing the same.

Yet another object of the present invention is to improve the mechanical strength of the composite material when used as a reinforcing material for the composite material.

Provided is a spherical inorganic oxide whose main constituents are silica and a Group 1 metal oxide, which not only increases surface hardness but also has good transparency and surface smoothness, and a method for producing the same. There is something to do.

In part, other objects of the invention will become apparent by themselves from the detailed description below.

As a result of intensive research to solve many technical problems, the inventors of the present invention have succeeded in producing an inorganic oxide with a spherical shape, the main constituents of which are silica and Group 1 metal oxides. We were successful in this and have come to propose it here.

The inorganic oxides of the present invention include silicon atoms of silica and Group 1 metal oxides such as potassium oxide.

Sodium oxide, lithium oxide, etc. are bonded via oxygen, and silica and Group 1 metal oxides are the main components. The composition ratio of the metal oxide in the first layer (hereinafter simply referred to as general 2M20 (however, pM is the metal in the first layer) has a large effect on the shape of the obtained inorganic oxide. . Of course, the type of M20, manufacturing method,
The influence of the composition ratio on the shape varies depending on the manufacturing conditions, etc., but in general, when trying to obtain a spherical inorganic oxide, it is preferable to keep the composition ratio of M2O to 20 molX or less, especially 0.01 Mho in the range of ~15 mol X
When selecting the composition ratio, the particles will be close to perfect spheres with uniform particle diameters. The composition ratio of M20 can be confirmed by chemical analysis, but depending on the type of M2O, it can also be confirmed by fluorescent X-ray analysis. However, it is usually not much different from what is calculated theoretically from the raw material ratio, so if the manufacturing raw material ratio is clear, it can also be calculated from the nuclear raw material ratio.

In the inorganic oxide of the present invention, the constituent components of silica and M2O generally exist chemically bonded, and these constituent components cannot be physically separated.

The shape of the inorganic oxide of the present invention can be determined using a scanning or transmission electron microscope.

It is possible to measure particle size, particle size distribution, etc. Generally, the inorganic oxide of the present invention has a small particle size, for example, in the range of 0.1 to 1.0 μm, and its particle size distribution is extremely uniform. For example, the standard deviation value of the particle diameter may be 1.60 or less.

The inorganic oxides mainly composed of silica and M2O provided by the present invention have a specific surface area of 100 d/ff or more, generally in the range of 100 to 200 j/f, and those with a specific surface area of 1
00 m'/f, generally in the range of 1 to 50 d/f. Although details will be described later, the inorganic oxide obtained by reacting and hydrolyzing the raw materials of both components in an alkaline solvent generally has a large specific surface area of 100 j/f or more.

Generally, inorganic oxides are heated at temperatures above 500°C.
If the inorganic oxide is fired at a temperature of about 1,300° C., the specific surface area of the inorganic oxide becomes small and becomes less than 100 d/f. However, all inorganic oxides have the same composition ratio and spherical shape.

The inorganic oxide of the present invention is mostly amorphous or a mixture of amorphous and partially crystalline, but depending on the type of M2O, it can be produced as a crystalline mixture. Generally, these determinations can be confirmed by analyzing the inorganic oxide of the present invention by means such as X-ray diffraction or refractive index measurement.

The inorganic oxide of the present invention has 10H groups bonded to its surface, and the amount of nuclear OH groups can be confirmed by measurement using an alkali neutralization method.

Generally, the specific surface area is large, that is, the one before firing is 1.0
~2.0 mmol/f, and those with a small specific surface area, that is, those after firing, are in the range of 0.01~0. I Qmmo
It often has an OH group in the l/f range.

Furthermore, the specific gravity and refractive index of the inorganic oxide of the present invention each differ depending on the type and composition ratio of M2'O, so they cannot be shown in part. Most commonly, the specific gravity is 1.
20 to 3.00, and many have a refractive index of 1.35 to 1.50.

As described above, the inorganic oxide of the present invention has the most characteristic use in that it is spherical in shape. For example, when the inorganic filler of the present invention is used as a dental filler, the powder filling rate can be significantly increased, and as a result, the mechanical strength and surface hardness of the dental filler can be increased.
In addition to the above, the inorganic oxide of the present invention can be used for catalysts, catalyst supports, sintering, etc. wood,
Suitable for a wide range of applications such as pigments, inorganic ion exchangers, and adsorbents.

Since the inorganic oxide of the present invention has the various properties described above, it can be used for various purposes, but the method for producing it is not particularly limited as long as it provides the above-mentioned properties. The most representative method will be described in detail below.

(b) A mixed solution containing a hydrolyzable organosilicon compound and a hydrolyzable group (III) metal organic compound is dissolved, but the reaction product is substantially not dissolved. There is a method in which the reaction product is precipitated by adding it to an alkaline solvent that does not dissolve in the water, hydrolyzing it, and precipitating the reaction product.

There are various types of hydrolyzable organosilicon compounds mentioned above, and one that is industrially easily available is, for example, the general formula St (OR
) The alkoxysilane represented by a or the low condensate obtained by partially hydrolyzing the alkoxysilane is used without particular limitation. R in the general formula for coughing is an alkyl group, and lower alkyl groups such as methyl, ethyl, inglovir, and butyl are preferably used. These alkoxysilanes and their low condensates may be used as commercially available products as they are or after being purified by distillation.

Another raw material, a hydrolyzable organic compound of Group 1 metal, is a metal alkoxide compound represented by the general formula M(OR') (where R' is an alkyl group) or an alkoxide group (OR ') is preferably substituted with a cardaxyl group or a β-dicarbonyl group.

Here, M is a Group 1 metal, and specifically, for example, lithium, potassium, or sodium is preferably used. Specific examples of the above-mentioned compounds that are generally preferably used in the present invention include organic alkali metal compounds such as Na0CHx, Na0c2Hs, Naoc5ay, and Na0OCCHs.

In the present invention, the alkoxysilane or its low condensate and the organometallic compound are mixed in advance to prepare a mixed solution. The solvent for the above mixed solution is not particularly limited and can be used as long as it dissolves the raw materials, but methanol, ethanol, impropatol, Phthanol, ethylene glycol.

Alcohol solvents such as propylene glycol are preferably used. Further, organic solvents such as ether solvents such as dioxane and diethyl ether, and ester solvents such as ethyl acetate may be used by partially mixing them with the above alcoholic solvent. In addition, although it is common to dissolve each of the raw materials separately in a solvent and then mix the solvent with scissors, it is also possible to add and dissolve one raw material in the solvent to form a mixed solution. . Furthermore, it is generally preferable that the concentration of the solution in which the raw materials are dissolved is low, but if it is too low, the amount of solvent used will increase significantly, and if the concentration is too high, it will be difficult to control the reaction and it will be inconvenient to handle. It may be determined appropriately by taking these into consideration. In general, it is most preferable to use the raw material at a concentration of 50% by weight or less, preferably from 5 to 50% by weight.

In order to make the inorganic oxide of the present invention into a spherical shape, it is generally preferable to control the mixing ratio of silicon (sl) and group (I) metal (M) in the raw material mixture solution. If the amount of the Group (I) metal (M) is too large, it is generally difficult to form the inorganic oxide into a spherical shape, and the shape of the obtained inorganic oxide tends to be amorphous.

Therefore, it is preferable to control the mixing ratio of Sl and M.

The abundance ratio of M and 81 in the raw material mixture solution influences the refractive index of the obtained inorganic oxide. Therefore, if it is necessary to change the refractive index, the above ratio may be controlled.

It is believed that the raw material mixture reacts with the organic silicon compound and the organic compound of the Group Ⅰ metal by stirring or allowing it to stand still. This is because even if a solution of an organosilicon compound dissolved in an alkaline solvent and a solution of an organic compound of a Group Ⅰ metal are added and reacted separately without mixing and preparing them in advance, inorganic oxides, especially spherical You can't get anything. Therefore, in producing the inorganic oxide of the present invention, it is necessary to prepare a solution in which both raw materials are mixed in advance. The conditions for preparing the mixed solution are not particularly limited, but are generally 0-80 in order to uniformly disperse and react both raw materials.
Preferably, the preparation is carried out under stirring or left standing at a temperature of several minutes to several hours.

The raw material mixture solution prepared as described above is then added to an alkaline solvent that dissolves the wrinkled raw materials but does not substantially dissolve the inorganic oxides, so that silica and Group 1 metal oxides are the main constituents. This is to precipitate the inorganic oxide. The solvent that dissolves both raw materials but does not substantially dissolve the produced inorganic oxide is not particularly limited, and known organic solvents may be used. Generally preferred solvents are the same alcoholic solvents or ether solvents as described in the book as solvents for the organosilicon compounds and organic compounds of Group 1 metals.

It is a water-containing solvent consisting of water and a mixed solvent obtained by adding a portion of an organic solvent such as an ester solvent to the alcoholic solvent. As mentioned above, the water-containing solvent needs to be alkaline.

Although known compounds can be used to make the mixture alkaline, ammonia is generally most preferably used.

The shape of the inorganic oxide of the present invention, particularly the particle size of spherical particles, is affected by factors such as the type of organic solvent, the amount of water, and the alkali concentration, so it is important to determine these conditions appropriately in advance. . Generally, it is preferable to select the alkali concentration of the alkaline solvent in the range of 1.0 to 10 mol θ/l, and the higher the alkali concentration, the larger the particle size of the obtained inorganic oxide tends to be. The amount of water in the alkaline solvent is required to further promote hydrolysis and generate inorganic oxides, and is generally 0.5 to 5.
It is preferable to select from the range of 0 mole/l.

In general, the higher the concentration of the mixing water, the larger the particle size of the obtained inorganic oxide tends to be. Furthermore, another factor that affects the particle size of the inorganic oxide is the type of organic solvent,
Generally, as the number of carbon atoms increases, the particle size of the obtained inorganic oxide tends to increase.

The method of adding the raw material mixture solution to the alkaline solvent is not particularly limited, but it is generally preferable to add the raw material mixture solution in small amounts over a long period of time, and it may be generally carried out within a range of several minutes to several hours.

Although the reaction temperature varies depending on various conditions and cannot be limited to a particular temperature, it is usually carried out at about 0°C to 40°C, preferably about 10 to 30°C, under atmospheric pressure. The above reaction can also be carried out under reduced pressure or increased pressure, but since it proceeds satisfactorily under atmospheric pressure, it may be carried out at normal pressure.

The product precipitated by the above reaction operation can be separated and dried.10 The inorganic oxide thus obtained contains silica and M2O as the main components as described above, and has a specific surface area of 100 nl/f or more. It has the following. By selecting various conditions as described above, inorganic particles having a spherical shape and an excellent particle size distribution with a particle size generally in the range of 0.1 to 1.0 μm and a standard deviation value of particle size of 1.30 or less can be obtained. It is an oxide.

(2) In the method of (1) above, a seed consisting of a silica polymer serving as a nucleus for precipitation is preliminarily present in an alkaline solvent, and then a reaction similar to that in U) above is carried out to form an inorganic oxide. There is a way to get it.

, , fJe71F*“°ゝtt ll+u
Particles of y Q h 104''6 can be used without particular limitation.

The method of making such seeds exist is not particularly limited, but for example, it is preferable to disperse particles that have already been separated into particles into an alkaline solvent, or to generate them in an alkaline solvent and use them as seeds without separating them. will be adopted. Regarding the latter method,
To explain in more detail, seeds made of silica polymer are first generated by further hydrolyzing alkoxysilane or its low condensate, and then the same reaction as in (1) above is carried out in the presence of the silica polymer. This is a method to obtain inorganic oxides. The alkoxysilane or its low condensate is hydrolyzed into a silica polymer in a solvent in which the alkoxysilane dissolves but the resulting silica polymer does not. The silica polymer serves as the core of the inorganic oxide that will eventually be produced, and it does not necessarily have to be large enough to be visible to the naked eye as a precipitate in the above solvent. The particles may be so small that they cannot be detected. Further, method #: i for producing a silica polymer from alkoxysilane or its low condensate is not particularly limited, and any known hydrolysis method can be employed.

For example, a specific amount of water as explained in (1) above is present in the same alkaline solvent as explained in (1) above,
Alkoxysilane or a low condensate thereof may be added.

Generally, the alkoxysilane or its low condensate is added as is, dissolved in a soluble solvent as explained in (1) above, and adjusted to #11 degree of 1 to 50 weight x before use. is suitable.゛After producing the silica polymer, the inorganic oxide may be precipitated by the same operation as in (1) above, and then separated and dried. The inorganic oxide thus obtained has silica as the core, silica and M2.
Since it is an inorganic oxide mainly composed of O, the resulting particle size distribution is particularly good. Also, the specific surface area of the obtained inorganic oxide is 100m? / or more, the particle size is 0.1 to 1.0 μffi' viscosity.

(3) A mixed solution containing a hydrolyzable organosilicon compound and a hydrolyzable organic compound of a Group 1 metal of the Periodic Table, in which the organosilicon compound and the organic compound of a Group 1 metal of the Periodic Table are dissolved. However, there is a method in which the reaction product is added to an alkaline solvent in which it does not dissolve, hydrolysis is performed to precipitate the reaction product, and then a hydrolyzable organosilicon compound is added to the reaction system and hydrolyzed.

The method (3) above is the same as (1) above up to the step of precipitating an inorganic oxide whose main components are silica and M2O, but in this method, a precipitate of the inorganic oxide is generated. After that, an organic silicon compound is added and reacted. The organosilicon compound to be reacted after the amount of iron has the general formula Si(OR)4 (where R is an alkyl group) used as the raw material.
The alkoxysilane or sonolow condensate represented by can be used without particular limitation. The method of reacting the precipitate with the alkoxysilane or its low condensation i is not particularly limited and can be carried out by any known method. For example, if a solution in which alkoxysilane or its low condensate is dissolved is added to an alkaline solvent containing the precipitate, or to a slurry solution prepared by redispersing the precipitate in an insoluble solvent after separation, and the reaction is caused. good. As the solution for dissolving the insoluble solvent for the precipitate and the alkoxysilane, the same type of solvent as the solvent used for dissolving the raw materials is preferably used. In addition, in order to cause the alkoxysilane or its low condensate to react with the precipitate, the alkoxysilane needs to undergo hydrolysis, so the presence of water is necessary in the reaction solvent. The amount of iron water is the same as the conditions for precipitating the reaction product whose main constituents are silica and M2O in ←) above. In addition, when the solvent in which the alkoxysilane or its low condensate is dissolved is added to the solution in which the precipitate is present, the alkoxysilane concentration should be lower, generally 5.
It is good to use 0 weight x or less, preferably 1 to 30 weight x weight. (9) The addition time of the alkoxysilane solution described above varies depending on the amount of solvent added, but generally it may be selected from a range of several minutes to several hours. Of course, when adding the alkoxysilane, it is also possible to directly add the alkoxysilane to the solvent in which the precipitate is present without dissolving it in the solvent, but such a method is difficult to control the reaction industrially. It is better to avoid it if possible.

The precipitated inorganic oxide obtained by the above method may be separated and then dried. Further, the inorganic oxide has silica and M2O as main constituents, and has a specific surface area of 100//f or more. However, due to the manufacturing method, it is presumed that the particle surface layer of the inorganic oxide is covered with only silica or a layer with a high silica content, and the inside of the particle has a structure in which silica and M2O are combined. The inorganic oxide obtained as described above has chemical properties similar to silica.

(4) In the method (3) above, seeds made of silica polymer are pre-existing in an alkaline solvent as in the method (2) above, and then an external reaction is carried out in the same manner as in (3) above. This is a method for obtaining inorganic oxides.

The method (4) above is a combination of the methods (1), (2) and (2) above, and the conditions explained for these reactions are adopted as they are.The inorganic oxide obtained by this method is There is a layer mainly composed of silica and Group I metal oxide around the coalescent seeds, and on the surface there is an inorganic oxide covered with a layer mainly composed of silica.

In addition, the specific surface area of the scissors inorganic oxide is large, 100-72 or more, and the particle size of the spherical body is 0.1 to 1.
The standard deviation value of the particle size is 1.5 for books in the 0 μm range.
You can get 4 less than 0.

The inorganic oxides obtained by the above methods (1), (2), (3), and (4) are mainly composed of white to yellowish white amorphous powder, especially spherical particles. What is obtained is useful. As mentioned above, inorganic oxides obtained in this way generally have a specific surface area of 100
W? Since it is a large book with /f or more, the catalyst, catalyst carrier,
Suitable for use in fields requiring specific surface area such as adsorbents.

Some of the inorganic oxides provided by the present invention have a reduced specific surface area by firing the products obtained by the methods (1) to (4) above. The wrinkle firing method is not particularly limited, and firing may be performed at a temperature of 200 to 1300°C or higher using a known method.

Furthermore, depending on the content of the metal oxide in Group 1 of the periodic table, the inorganic oxide may melt within the temperature range and lose its spherical shape and become amorphous. Preferably, the firing temperature is selected depending on the oxide content.

For example, when the Na2O content is 9.1 mol% of the total, the spherical shape is maintained when the firing temperature is 750°C or lower, but the spherical shape starts to collapse from 800°C, and spherical objects are difficult to remain at 850°C or higher. In this case, it is amorphous at a firing temperature of 800°C or lower, but becomes crystalline with cristobalite and α-quartz as main components at a firing temperature of 850 to 1000°C. By firing, the specific surface area of the inorganic oxide becomes smaller, and when fired at a temperature of 500°C or higher, the inorganic oxide can be fired at a temperature of 100 W? The specific surface area is less than /f. Furthermore, when a spherical inorganic oxide is fired at a temperature of about 500° C. or higher, the specific surface area is often the same as that theoretically calculated from the particle size as a true sphere.

The above firing temperature may change the structure of the powder. For example, when the amorphous inorganic oxide is fired, it becomes amorphous.
In some cases, amorphous materials are mixed with some crystalline materials, or even in some cases, crystalline materials are mixed in.

The inorganic oxidizing agent obtained after the above-mentioned calcination has excellent properties and is excellent as a powder component of dental fillers, for example.

The composite material used as a powder component of a dental filler will be described below.

7 For example, it exhibits excellent properties when made into a composite material consisting of a polymerizable vinyl monomer and the fired spherical particles having a particle size in the range of 0.1 to 1.0 μm.

One component of the composite is a polymerizable vinyl monomer. The vinyl monomer is not particularly limited, and known ones that are generally used as dental composite materials can be used. The most typical vinyl monomer is a polymerizable vinyl monomer having an acrylic group and/or a methacrylic group. Specific examples of vinyl monomers having an acrylic group and/or methacrylic group include 2,2-bisC4(2-hydroxy-3-methacryloxypropoxy)phenyl]furopane.

Methyl methacrylate, bismethacryloethoxyphenylpropane, triethylene glycol dimethacrylate, diethylene glycol dimethacrylate, tetramethylol triacrylate, tetramethylolmethane trimethacrylate, trimethylolethane trimethacrylate and the like are preferred. Also preferably used is a vinyl monomer having a urethane structure represented by the following structural formula.

c-.

Dark ↓ ) J'LT However, in the above formula, R1, R2, Rs and R4 are the same or different H or CH3, and MoA+ is fcHz + 6° These vinyl monomers are necessary as they are known as dental materials. Depending on the situation, they may be used alone or in combination.

Another component of the composite material is the inorganic oxide. It is preferable to use spherical particles having a particle diameter in the range of 0.1 to 1.0 μm and a standard deviation value of the particle diameter distribution within 1.50 as the inorganic oxide. The above particle size 2 Particle shape and particle size distribution are both very important factors as long as they are used in dental composite materials. For example, if the above particle size is 0
．． If it is smaller than 1 μm, the viscosity will increase significantly when it is kneaded with a polymerizable vinyl monomer to form a paste mixture, and if you try to prevent the increase in viscosity by increasing the blending ratio, the operability will deteriorate. It cannot be used as a material for practical use. In addition, if the particle size is larger than 1.0 μm, it is preferable because the abrasion resistance or surface smoothness of the resin after polymerization and curing of the vinyl monomer decreases, and the surface hardness also decreases. do not have. Furthermore, if the standard deviation value of the particle size distribution is greater than 1.30, the operability of the composite material will be lowered, so that the composite material cannot be used for practical use. Furthermore, even if the attached inorganic oxide is a particle with a particle size in the range of 0.1 to 1.0 μm and a standard deviation value of the particle size distribution within 1.30, the shape of the particle is spherical. Otherwise, the wear resistance, surface smoothness, surface hardness, etc. will not be satisfactory. For example, when using the above composite material as a dental restorative material, not only is operability an important factor, but also the mechanical strength and abrasion resistance of the resulting composite resin after curing. must be kept in good condition. For this purpose, the amount of the inorganic oxide added is generally 70
It is preferable to select it so that it becomes a range of 90 weight X.

When used as the above-mentioned dental composite restorative material, a paste-like mixture consisting of the inorganic oxide, a polymerizable vinyl monomer, and a polymerization accelerator (for example, a tertiary amine compound), an inorganic oxide, a vinyl monomer, and a polymerization promoter is generally used. A method is preferably used in which a paste-like mixture consisting of an initiator (for example, an organic peroxide such as benzoyl peroxide) is prepared in advance, and the two are kneaded and cured immediately before the repair operation. Composite resin made by curing the above composite materials has no inferiority in mechanical strength such as compressive strength compared to conventional ones, and has excellent wear resistance and surface smoothness, as well as high surface hardness and surface polishing. It has many excellent features such as being very easy to finish and improving transparency. However, although the reason for this characteristic is not necessarily clear at present, the present inventors believe as follows. That is, first, the shape of the particles is spherical, and the standard deviation value of the particle size distribution is 1.
By using an inorganic oxide with a uniform surface particle size of 30% or less, inorganic oxide can be contained in the composite resin obtained by curing, compared to the case of using conventional fillers with a wide particle size distribution and irregular shapes. The particles are packed more uniformly and densely, and secondly, the particle size range is from 1 to 1.
By using a material with a particle size within the range of 0 μm, the polished surface of the composite resin after curing becomes smoother than when using conventional inorganic fillers with a particle size of several tens of μm. This is because the total specific surface area of the filler is smaller than when using an ultrafine particle filler whose main component is microparticles, and therefore a large amount of filler can be filled under conditions with appropriate operability. Conceivable.

In addition to the characteristics due to the shape as described above, the filler according to the present invention can easily match the refractive index of the filler itself with that of the vinyl monomer polymer, so that by matching the refractive index, the filler can be extremely A composite resin with excellent transparency can be obtained.

By blending the specific inorganic oxide and a polymerizable vinyl monomer, the above-mentioned composite material exhibits a number of previously unanticipated advantages as described above. The above-mentioned composite material exhibits the above-mentioned advantages by blending two components, a polymerizable vinyl monomer component and a specific inorganic oxide component, but in addition to these components, there is also a compound that is generally used as a dental restorative material. It is also possible to add additional components as necessary. Typical of these additive ingredients are as follows. For example, radical polymerization inhibitors,
There are colored pigments for color matching, ultraviolet absorbers, etc.

The present invention will be described in more detail with reference to Examples below. Unless otherwise specified, measurements of various properties used in the Examples below were carried out as follows.

(1) Refractive index A solvent having the same refractive index as the inorganic oxide of the sample was prepared, and the refractive index of the solvent was taken as the refractive index of the sample. The solvent was prepared by suspending the sample in a solvent and preparing the composition of the solvent at a constant temperature so that it appeared transparent when observed with the naked eye. The solvents used were pentane, hexane, cyclohexane, toluene, styrene, and methylene iodide.
The refractive index of the solvent was measured with an Abe refractometer.

(2) Weigh several samples of inorganic oxides with surface OH groups by 2.00 Wg) 10
Place in a 0- Erlenmeyer flask and add 0.05 N NaOH.
Eighty-ounces of the aqueous solution was added, the mixture was sealed with a rubber stopper, and the mixture was left stirring for 12 hours. After that, the inorganic oxide and the solution were separated using a centrifuge, and 10-bibebut was taken from this solution, and 0.05
Nf) HC1 aqueous solution is designated as A-.

The same procedure was carried out in the pot without adding the sample, and the HCA aqueous solution required for neutralization was designated as B-. The amount of -0H groups on the surface per unit weight of the inorganic oxide (Xmmole/f) is calculated by the following formula.

(3) Specific gravity Specific gravity was measured according to the vicinometer method.

(4) Standard deviation value of particle size and particle size distribution Take a scanning electron micrograph of the powder, and calculate the number of particles observed within the unit field of view of the photograph, (n), and the particle size (diameter xl). It is calculated using the following formula.

X+n-1 Standard deviation value=□: (5) Specific surface area Shibata Kagaku Kiki Kogyo ■ Rapid surface measuring device 8A-1000 was used. The measurement principle is the BET method.

(6) Composite paste preparation and curing method
, amorphous silica whose surface had been treated with r-methacryloxypropyltrimethoxysilane and a vinyl monomer were placed in a predetermined ratio in an agate mortar and sufficiently kneaded to form a uniform paste. Next, the paste was divided into three equal parts, and a polymerization accelerator was further added to one paste and thoroughly mixed (this was referred to as paste A). In addition, an organic peroxide catalyst was added to the other paste and thoroughly mixed (this will be referred to as base B). Next, equal amounts of Pase) A and Base) H were kneaded for about 30 seconds, filled into a mold, and cured.

(1) Compressive strength Paste A and paste) B were mixed and polymerized at room temperature for 30 minutes, and then immersed in water at 67° C. for 24 hours to prepare test pieces.

Its size and shape are cylindrical with a diameter of 6 cm and a height of 12 cm. This test piece was tested using a testing machine (Toyo Baudouin U).
TM-57), crosshead speed 10 m
The compressive strength was measured in m/min.

(8) Bending strength Base) A and pace) B were mixed and polymerized at room temperature for 30 minutes, and then immersed in water at 67°C for 24 hours to prepare a test piece. Its size and shape are 2x2x25 prismatic. The bending test was carried out using a bending test device with a distance between fulcrums of 20 cm mounted on a UTM-5T manufactured by Toyo Baudwin, and a crosshead speed of 0.5 cm/min.

(9) Toothbrush wear depth and surface roughness Base) A and paste) B were mixed and polymerized at room temperature for 50 minutes, and then immersed in water at 57°C for 24 hours to prepare test pieces.

Its size and shape are plate-like with dimensions of 1.5 x 10 x 10 cm. The test piece was brushed with a toothbrush under a load of 400f.
500? After Fl wears out, use a surface roughness meter (Surfcom A-
100) to determine the ten-average roughness. The wear source was determined by dividing the wear weight by the density of the composite resin.

(10) Surface hardness Pace) A and base) B were mixed and polymerized at room temperature for 30 minutes, and then immersed in water at 37° C. for 24 hours to prepare a test piece. Its size and shape are 2.5 x 10 square discs. The measurement used a micropurinelle hardness test.

Furthermore, the abbreviations used in the examples are as follows unless otherwise specified.

Note that the firing time for the inorganic oxides in Tables 1 to 20 was 4 hours unless otherwise specified.

AM: amorphous, gtoH: ethanol, IPA: inpropatol, MeOH: methanol.

BuOH: Methanol -0 wise? ″″0 −0 H −0 ■ −0 Example 1 Tetraethyl silicate (5i (OC2Hs) 4-Nippon Coat Chemical Co., Ltd., trade name: ethyl silicate) 28 ) 20
8f and 5.4t of sodium methylate were mixed with 1.8t of methanol. After dissolving OL and heating this solution under reflux for 50 minutes,
A mixed solution was prepared by cooling to room temperature. Next, 2.5 methanol was added to a glass reaction vessel with an internal volume of 10 tons equipped with a stirrer.
t, and add 500 t of ammonia aqueous solution (light L2
5 wt*) to prepare an ammoniacal methanol solution, and to this solution was added the previously prepared mixed solution of tetraethyl silicate and sodium methylate at a temperature of 2.
The addition took about 2 hours while maintaining the temperature at 0C. A few minutes after the addition started, the reaction solution turned milky white. After the addition was completed, stirring was continued for one hour, the solvent was removed from the milky white reaction liquid using an evaporator, and the mixture was further dried under reduced pressure at 80C to obtain a milky white powder.

As a result of observation using a scanning electron microscope with four lenses, the shape of the powder was spherical, the particle size was in the range of 0.20 to 0.35 μm, and the standard deviation value of the particle size was 1.07. BE again
The specific surface area determined by the T method was 120 wt/l.

According to X-ray analysis, a gentle mountain-shaped absorption centered around 2θ=25° was observed, and it was confirmed that the material had an amorphous structure.

Furthermore, thermal changes and weight changes were measured using a differential thermal analyzer and a thermobalance. As a result, there was an endotherm around 100°C, which was thought to be due to dehydration.

A decrease in weight was observed, and further a decrease in exothermic weight was observed at around 500 to 600°C. Thereafter, no thermal change9 weight change was observed up to 1000°C.

The surface area of the powder after firing at 700℃ for 4 hours is 14
d/f, specific gravity is 2.20 and refractive index is 1.45-1.
46, and in the xs analysis, a gentle mountain-shaped absorption centered at 2#=21.5° was observed, and it was predicted that it was an amorphous material. Furthermore, the Na2O content determined by fluorescence xl1 analysis agreed with the value calculated from the amount of feed, and the yield also agreed with the value calculated from the amount of feed. The actual value of the content rate of Na2O in the powder is
9.1 mole! (The calculated value is 9.1 mole%),
The actual value of powder yield was 65. Ot (calculated value is 66.5
F).

Examples 2 to 4 All experiments were carried out under the same conditions as in Example 1, except that the raw material composition of the mixed solution in Table 1 was used. The results are shown in Table 1.

The obtained inorganic oxide was found to have a spherical shape when observed using a scanning electron microscope.

Examples 5 to 7 All experiments were carried out under the same conditions as in Example 1, except that the raw material composition of the mixed solution in Table 2 was used. The results are shown in Table 2.

All of the obtained inorganic oxides had a spherical shape as a result of observation using a scanning electron microscope (η).

Examples 8 to 10 All experiments were carried out under the same conditions as in Example 1, except for the composition of the ammoniacal alcohol shown in Table 3. The results are shown in Table 3.

All of the obtained inorganic oxides had a spherical shape when observed using a scanning electron microscope.

Examples 11 to 16 All experiments were carried out under the same conditions as in Example 1, except that the raw material composition of the mixed solution in Table 4 was used. The results are shown in Table 4.

All of the obtained inorganic oxides had a spherical shape when observed using a scanning electron microscope.

Example 17 An ammoniacal methanol solution having the same composition as that used in Example 1 was prepared in a 10 L glass reaction vessel equipped with a stirrer. Then, tetraethyl silica is added as an organosilicon compound solution to make silica seeds in this ammoniacal methanol solution,)4. (A solution dissolved in lt-methanol 100- was added over about 5 minutes, and when the reaction liquid became slightly milky 5 minutes after the addition was completed, a mixed solution having the same composition as that used in Example 1 was added.) was added to the reaction vessel over 2 hours while keeping the temperature of the reaction vessel at 20C.As the mixed solution was added, it became a milky white suspension.After the addition was completed, stirring was continued for 1 hour, and a milky white suspension was formed. Remove the solvent from the reaction solution using an evaporator,
A milky white powder was obtained by further drying under reduced pressure at 80°C. As a result of observation using a scanning electron micrograph, the shape of the powder was spherical, the particle size was in the range of 0.20 to 0.33 μm, and the standard deviation value of the particle size was 1.06. MataBII
Is the specific surface area by CT method 11ON? /f. According to X-ray analysis, a gentle mountain-shaped absorption was observed around 2#=25°, and it was confirmed that the material had an amorphous structure. Thermal changes and weight changes measured by a differential thermal analyzer and thermobalance showed similar trends to those of the powder of Example 1.

The specific surface area of the powder after firing at 700°C for 4 hours is I
Sd/f, specific gravity is 2.20. and refractive index is 1.45~
1.46, and XII analysis showed a gentle mountain-shaped absorption centered at 2#=21.5', confirming that it was an amorphous substance. In addition, Na2Q by fluorescent X-ray analysis
The content of #8iQ2 was consistent with the calculated value from the charging amount, and the yield was also consistent with the calculated value from the charging amount. Powder 1 (a20
Actual value of content of 8.9 moleX (calculated value f3
．． 9 mole N) Actual value of yield of e powder 66,
Of (calculated value 67.4 F).

Examples 18 to 20 All experiments were carried out under the same conditions as in Example 17, except that the composition of the organic silicon compound solution for producing silica seeds was as shown in Table 5.

The results are shown in Table 5. All of the obtained inorganic oxides had a spherical shape as a result of observation using scanning electron micrographs.

-2 (Examples 21 to 26 The raw material composition of the mixed solution in Table 6 is Example 17 except for 9.
It was carried out under the same conditions. The results are shown in Table 6. All of the obtained inorganic oxides had a spherical shape as a result of observation using a scanning electron microscope with four lenses.

Examples 27 to 29 Solid lines were obtained under the same conditions as in Example 17, except that the composition of the ammoniacal alcohol shown in Table 7 was used. The results are shown in Table 7.

All of the obtained inorganic oxides had a spherical shape as a result of observation using a scanning electron microscope with four lenses.

203- Examples 60 to 35 All the same as Example 17 except that the raw material composition of the mixed solution in Table 8 was used.
It was carried out under the same conditions. The results are shown in Table 8.

All of the obtained inorganic oxides had a spherical shape as a result of observation using a four-lens scanning electron microscope.

Example 36 An ammoniacal methanol solution having the same composition as that used in Example 1 was prepared in a glass reaction vessel with an internal volume of 10 L equipped with a stirrer. Next, a mixed solution having the same composition as that used in Example 1 was added to this ammoniacal methanol over a period of 2 hours while maintaining the temperature of the reaction vessel at 20° C. to precipitate a reaction product. After the addition is complete, add 0.5 t of methanol containing 104 f of tetraethyl silicate.
A solution consisting of was added over about 2 hours to the system in which the reaction product had precipitated. After addition, stir for 1 hour and continue after death.
The solvent was removed from the milky white reaction solution using an evaporator, and the mixture was further dried under reduced pressure at 80C to obtain a milky white powder.

As a result of observation using a scanning electron microscope, the shape of the powder was spherical, the particle size was in the range of 0.22 to 0.34 μm, and the standard deviation value of the particle size was 1.05. . X
According to line analysis, a gentle mountain-shaped absorption was observed centered at 21=25°, indicating that the material had an amorphous structure. Also, the specific surface area by BET method is 110w? /f. Furthermore, thermal changes and weight changes were measured using a differential thermal analyzer and a thermobalance.

The results showed the same tendency as in Example 1.

The specific surface area of the powder after firing at 700℃ for 2 hours is 13
m'/f, the number of 10H on the surface is 0, 10 mmol/f
*Specific gravity is 2.20. and refractive index is 1.45-1.46
-t', and X-ray analysis showed a gentle mountain-shaped absorption centered at 20=22°, indicating that it had an amorphous structure.

The amount ratio of Sl and lJa by Fluorescence X@ matched the amount ratio of the preparation, and the yield also almost agreed with the value calculated from the amount of preparation. 810293.8 mo1%.

It was confirmed that it was a spherical inorganic oxide having an amorphous structure with a composition of 1% by mole of N1206.5.

Examples 37 to '59 All experiments were carried out under the same conditions as in Example 36, except that the composition of the organosilicon compound solution added after the reaction product shown in Table 9 was precipitated. The results are shown in Table 9. The obtained inorganic oxide was found to have a spherical shape when observed using a scanning electron microscope.

Examples 40 to 45 All Example 3 except for the raw material composition of the mixed solution shown in Table 10
It was carried out under the same conditions as in 6. The results are shown in Table 10. All of the obtained inorganic oxides had a spherical shape as a result of observation using scanning electron micrographs.

Examples 46 to 48 All experiments were carried out under the same conditions as in Example 66, except that the composition of the ammoniacal alcohol shown in Table 11 was used. The results are shown in Table 11.

The obtained inorganic oxide was found to have a spherical shape when observed using a scanning electron microscope.

Example 49-, :54 All the same as Example 5 except that the raw material composition of the mixed solution was as shown in Table 12.
It was carried out under the same conditions as in 6. The results are shown in Table 12. The obtained inorganic oxide was found to have a spherical shape when observed using a scanning electron microscope.

Example 55 An ammoniacal methanol solution having the same composition as that used in Practical Example 1 was prepared in a glass reaction vessel with an internal volume of 10 L equipped with a stirrer. Then, tetraethyl silica is added to the ammoniacal methanol solution of the kernels as an organosilicon compound solution for making silica seeds)4. Of methanol 10
A solution dissolved in 0 mg was added over about 5 minutes, and 5 minutes after the addition was completed, when the reaction liquid became slightly milky,
Further, a mixed solution having the same composition as that used in Example 1 was added to the reaction solution for about 20 minutes while keeping the temperature of the reaction vessel at 20C.
It was added over time to precipitate the reaction product. Continuing on from the next page, a solution consisting of 0.5 t of methanol containing 104F (tetraethyl silicate) was added over about 2 hours to the system in which the axillary reaction product had precipitated. After the addition was completed, stirring was continued for 1 hour, the solvent was removed from the milky white reaction solution using an evaporator, and the temperature was further heated to 80°C.

A milky white ring was obtained by drying under reduced pressure.

As a result of observation using a scanning electron microscope, the shape of the powder was spherical, the particle size was in the range of 0.23 to Q, 35 μm, and the standard deviation value of the particle size was 1.04. According to X@ analysis, gentle mountain-shaped absorption was observed around 20=25°, indicating that the material had an amorphous structure. Also B
The specific surface area determined by the ET method was 108tt//f. Furthermore, thermal changes and weight changes were measured using a differential thermal analyzer and a thermobalance. The results showed the same tendency as in Example 1.The specific surface area of the powder after firing at 700C for 4 hours was 12
Lol? /f, the number of 10H on the surface is 0-09 mmole
/f, specific gravity is 2.20. and the refractive index is 1.45-1
．． 46, and X-ray analysis showed a gentle mountain-shaped absorption centered at 2 # = 22°, indicating that it had an amorphous structure. The amount ratio of Sl and Na determined by fluorescent X-ray analysis matched the amount ratio of the ingredients, and the yield also almost agreed with the value calculated from the amount of ingredients. 5i02 93.8moleX
*Na2O6,2moleX.

Examples 56 to 58 All experiments were carried out under the same conditions as in Example 55, except that the composition of the organic silicon compound solution for producing silica seeds was as shown in Table 13. The results are shown in Table 1'3. All of the obtained inorganic oxides had a spherical shape as a result of observation using scanning electron micrographs.

Practical Examples 59 to 64 All Example 5 except for the raw material composition of the mixed solution in Table 14
It was carried out under the same conditions as in 5. The results are shown in Table 14. All of the obtained inorganic oxides had a spherical shape when observed using a scanning electron microscope.

Actual Examples 65 to 67 All experiments were carried out under the same conditions as in Example 55, except that the composition of the ammoniacal alcohol shown in Table 15 was changed. The results are shown in Table 15.

The obtained inorganic oxide was observed to have a spherical shape using a scanning electron microscope.

Examples 68 to 73 All Example 5 except for the raw material composition of the mixed solution in Table 16
It was carried out under the same conditions as in 5. The results are shown in Table 16. Observation of the obtained inorganic oxide with a transmission electron microscope revealed that it had a spherical shape.

Example 74 700°C synthesized in the same manner as in Example 1.

The inorganic oxide baked for 4 hours was further surface-treated with r-methacryloxypropyltrimethoxysilane. The treatment was performed by adding 6 wt% of r-methacryloxypropyltrimethoxysilane to the inorganic oxide, refluxing it in a water-ethanol solvent at 80C for 2 hours, removing the solvent with an evaporator, and drying in vacuum. .

Next, as a vinyl monomer, 2,2-bis[4(2-hydroxy-6-methacryloxypropoxy)phenyl]
A mixture of propane (hereinafter referred to as Bis-GMA) and triethylene glycol dimethacrylate (hereinafter referred to as TEGDMA) (the mixing ratio is Bis-GMA/Tg
GDMA=6/7 molar ratio. ) was blended with the above inorganic oxide and sufficiently kneaded to obtain a paste-like composite material. At this time, the filling amount of inorganic oxide in the composite material was 72.8 w
The viscosity of the paste at t% was operationally adequate. Next, the paste was divided into two parts, and one part was filled with N,N-dimethyl-P-toluidine as a polymerization accelerator, and the other part was filled with benzoyl peroxide as a polymerization initiator, each at 1w per vinyl monomer.
t% added pace) A (former) and base) B (latter)
was prepared.

Add the above paste A and paste B in equal numbers and hold for 30 seconds.
As a result of measuring the physical properties of the product kneaded and hardened at room temperature, the compressive strength was 3.580Kt/-, and the bending strength was 800Kt.
/cd, surface roughness 0.5 μm9 surface hardness 60.0. The toothbrush wear depth was 4.0 μm. Furthermore, when the surface was polished with Itehan Flex (manufactured by 3M), a smooth surface was easily obtained without excessively abrading the surface of the composite resin. Moreover, transparency was good.

Actual examples 75-77 Example 17. Using the inorganic oxides of Example 36 and Actual Example 55 (calcined at 700°C for 4 hours), Example 7
A paste was prepared in the same manner using the same vinyl monomer as in Example 4, and was further cured to measure the physical properties of the composite resin. The results are also summarized in Table 17.

Examples 78 to 80 Using the inorganic oxide used in Example 74, U-4HMA, U-4'rMA, U-4BM as vinyl monomer components
A, tetramethylolmethane triacrylate (hereinafter referred to as T
It's called MMT. ) and methyl methacrylate (hereinafter referred to as M
It's called MA. ) A paste-like composite material was prepared in the same manner as in Example 74, except that the following was used. The mixing proportions of the vinyl monomer components are shown in Table 18. The paste-like composite material was further cured in the same manner as in Example 74, and the physical properties of the composite resin were measured. The results are also shown in Table 18.

Example 81 PdCLz O0'56 f was dissolved in a 1N aqueous hydrochloric acid solution, and 1Of of an inorganic oxide synthesized in the same manner as in Example 1 (calcined at 200 C for 2 hours, surface area 120 d/f) was added to this aqueous solution. It was impregnated, evaporated to dryness at 80 to 85°C, and then dried at 110°C overnight to obtain a powder. After molding the powder using a pelletizer, it was filled into a Pyrex reaction tube with an inner diameter of 2B, and heated at 550° C. for about 3 hours in a hydrogen atmosphere. After that, the temperature of the reaction tube was lowered to 200℃, and hydrogen 1
．． 0 z, "h, - Carbon oxide was passed through the reaction tube at a flow rate of 0.5 t/hour, and after 20 hours, the composition at the outlet of the reaction tube was analyzed by gas chromatography. As a result, methanol was produced. The yield was - 0.06 for carbon oxide
It was molX. This was a high activity corresponding to about 1.10% of the equilibrium yield calculated from thermodynamic data.

Patent Applicant: Tokuyama Ichida Co., Ltd.　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　
λ indication of patent application 1983-35. '+(i,'+92,
Of invention? , Ladle 1 Muwan oxide and IF! Construction method: z, correction ζ ministry "Ii fl and σ gate (I f!! !+'! Out! I
Ir person f+ t′ili :l! rl+,'
;= b Tayama City Gosu 2-cho 1. Song number 1 name fu1
, (, jiU) Tokuyama Sotatsu Co., Ltd. (Before company representative)
7Iif! i first self 4 ti! i if's 1st inversion #1 diagonal t', 5 in clear m 舊1, correction details

Claims (1)

[Scope of Claims] (1) Main constituents are silica and a metal oxide of Group 1 of the periodic table that can be bonded to silica, and the specific surface area is 100.
An inorganic oxide having a ratio of j/f or more and a spherical shape. (2) Claim 1, in which the composition ratio of the metal oxide of Group Ⅰ on the surface of the crystalline surface that can be bonded is 20 mol X or less! (1) The inorganic oxide described. (3) The inorganic oxide according to claim a), which has a particle size in the range of 0.1 to 1.0/Jm. (4) The inorganic oxide according to claim 1t(1), which has a standard deviation value of particle diameter of 1.50 or less. (5) Claim I in which the bondable metal oxide of Group 1 of the periodic table is at least one metal oxide selected from the group consisting of lithium oxide, potassium oxide, and sodium oxide! (e) The inorganic oxide described. (6) The main constituents are metal oxides of group 1 of the periodic table that can bond with silica and silica, and the specific surface area is 100 d1.
An inorganic oxide having a particle size of less than 1 and having a spherical shape. ()) Claim (6) states that the bondable metal oxide of Group 1 of the periodic table is at least one metal oxide selected from the group consisting of lithium oxide, potassium oxide, and sodium oxide. inorganic oxides. (8) The inorganic oxide according to claim (6), wherein the composition ratio of the metal oxide of group '' of the periodic table that can be bonded is 20 moles or less. (9) The inorganic oxide according to claim 1!1(6), which has a particle size in the range of 0.1 to 1.0 μm. (10) The inorganic oxide according to claim (6), which has a standard deviation value of particle diameter of 1.30 or less. (U) A mixed solution containing a hydrolyzable organosilicon compound and a hydrolyzable organic compound of a metal of Group 1 of the Periodic Table (M) is mixed with the organic compound of the organosilicon compound and an organic compound of a Group Oxidation of silica and metals from group 1 of the single period table, characterized in that the compound dissolves but the reaction product does not substantially dissolve. A method for producing inorganic oxides whose main constituents are (12) The method according to claim 8(n), wherein the mixed solution is an alcohol solution. (13) The method according to claim (m), wherein the alkaline solvent is an ammoniacal alcohol containing water. (14) Claim (1) in which the inorganic oxide is spherical
1) The method described. (15) Claims (u) in which the metal (M) of group Ⅰ of the m-period table is potassium, lithium, or lithium.
Method described. ≦0.5. ≦0.2. (1B) The method according to claim (U), wherein the alkaline solvent contains silica seeds in advance. (19) Silica seeds are prepared by adding a hydrolyzable organosilicon compound to an alkaline solvent containing water that dissolves the organosilicon compound but does not dissolve the hydrolyzed silica. , the method according to claim (1B), wherein silica is precipitated. (20) A mixed solution containing a hydrolyzable organosilicon compound and a hydrolyzable organic compound of a metal (M) of group 1 of the periodic table is added to the organic compound of the organosilicon compound and an organic compound of a metal of group 1 of the periodic table. is added to an alkaline solvent in which is dissolved but the reaction product is not dissolved and hydrolyzed to precipitate the reaction product, and then a hydrolyzable organosilicon compound is added to the reaction system and hydrolyzed. A method for producing an inorganic oxide, the main components of which are silica and an oxide of a Group I metal of the periodic table. (21) Claim i in which the mixed solution is an alcohol solution! 1(20). (22) The method according to claim (20), wherein the alkaline solvent is an ammoniacal alcohol containing water. (23) Claim (2) in which the inorganic oxide is spherical
0) The method described. (24) Claim (20) in which the metal (M) in group Ⅰ of the m-period table is potassium, lithium, or sodium.
Claim (20) included so that the described method≦0.3
Method described. Claim (20) included so that ≦0.2
Method described. (27) The method according to claim (20), wherein the alkaline solvent contains silica seeds in advance. (28) When silica seeds are added to an alkaline solvent containing water, the organic silicon compound is dissolved, but the hydrolyzed silica is dissolved, and the organic silicon compound is added to an alkaline solvent containing water. The method according to claim (2), wherein the compound is hydrolyzed to precipitate silica. (2g) (1) A mixed solution containing a hydrolyzable organosilicon compound and a hydrolyzable organic compound of metal (M) of group 1 of the periodic table is mixed with the organosilicon compound and - The organic compound of group metal is dissolved, but the reaction product is not substantially dissolved, and it is added to an alkaline solvent and hydrolyzed to precipitate the reaction product, or (-) hydrolyzable organosilicon compound and hydrated. A mixed solution containing a decomposable organic compound of Group 1 metal of the Periodic Table (M) is prepared using an alkaline solvent that dissolves the organosilicon compound and the organic compound of Group 1 metal of the Periodic Table but does not dissolve the reaction product. and hydrolyze it to precipitate the reaction product,
A composite material according to claim 3B, wherein a hydrolyzable organosilicon compound is then added to the reaction system and hydrolyzed to precipitate a reaction product, and then the reaction product is precipitated. (44) The polymerizable vinyl monomer has an alkali group and/or
The composite material according to claim II (3B) is also a vinyl monomer having a methacrylic group. (45) A catalyst for alcohol production whose main component is a spherical inorganic oxide whose main components are silica and an oxide of a metal from group Ⅰ of the Pigeon Table. (46) Claim (45) in which the composition ratio of the oxide of Group Ⅰ metal of the periodic table in the inorganic oxide is 20 moles or less
Catalysts as described.