JP3024181B2 - Method for manufacturing glass body - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing a metal organic compound as a starting material by hydrolysis and condensation polymerization to form a gel, and heating the obtained gel body by a sol-gel method. The present invention relates to a method for producing a glass body containing a crystalline component of a product.

Conventional technology Conventionally, a method for producing a glass body containing a crystalline component by a sol-gel method includes heating an amorphous gel body obtained by hydrolysis and polycondensation of a metal organic compound to a high temperature to obtain a crystalline phase. Such a method is disclosed in Glass Handbook, published by Asakura Shoten (published in 1982), pp. 1013 to 1017, edited by Saio Sakuhana et al.

[Problems to be Solved by the Invention] However, in the above-mentioned conventional method, heating at a high temperature of 400 ° C. or more is required in order to precipitate a crystal phase in a glass body. When the amount is small, heating at a high temperature and for a long time is required for crystal precipitation. Therefore, for example, when a glass body film is formed on a substrate, the heating temperature and time are limited for a substrate having low heat resistance, and it is difficult to form a glass body having a crystalline phase by the conventional method. There was a problem.

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the conventional method, that is, to provide a method for producing a glass body containing a crystal phase at a lower heating temperature.

"Means for solving the problem" The present invention forms a gel from a solution containing a hydrolyzable metal organic compound and an organic polymer, and then removes the organic polymer in the gel. This is a method for producing a glass body containing crystals of a metal oxide by treating the gel body as a porous body and thereafter treating the porous body with water vapor.

The metal organic compound used in the present invention is not particularly limited as long as it hydrolyzes and further performs a polycondensation reaction to form an oxide.Metal methoxide, ethoxide, propoxide, metal alkoxide such as butoxide, -Cl, -COOH, -COOR, organometallic compound containing a functional group capable of performing condensation polymerization or crosslinking reaction such as -NH _2, is β- diketone metal chelate complexes such as acetylacetonate can be exemplified. The metal organic compound used in the present invention may be a single metal organic compound or a mixture of two or more metal organic compounds. For example, a mixture of a titanium organic compound and one of metal organic compounds such as zirconium, aluminum, germanium, and tantalum may be used.
Further, a mixture of a metal organic compound and one or more of hydrolyzable organic compounds such as silicon, boron, and phosphorus can also be used. The compounds of silicon, boron, and phosphorus include silicon methoxide, silicon ethoxide, silicon propoxide, silicon butoxide, boron methoxide, boron ethoxide, boron propoxide, boron butoxide, boric acid, phosphoric acid, trimethyl phosphate, and phosphoric acid. Triethyl, tripropyryl phosphate and the like.

As the organic polymer compound contained in the solution according to the present invention, polyethylene glycol, polypropylene glycol, polyalkyl ether compounds such as polytetramethylene glycol, cellulose acetate, cellulose nitrate,
Cellulose compounds such as hydroxypropyl cellulose,
Compounds such as polyvinyl compounds such as polyvinyl alcohol, polyvinyl acetate, and polyvinyl chloride, which are easily burned by heating and hardly cause residues, or compounds which are easily removed from the gel by elution with an organic solvent are preferable.
The amount of the polymer compound added is related to the porosity when the gel body is made porous, and is preferably in the range of 0.1 to 10 in terms of weight ratio to the metal oxide finally contained in the glass body. .

To the solution of the present invention, if necessary, a catalyst such as water, hydrochloric acid, nitric acid, acetic acid, sulfuric acid or the like, or a base such as ammonia, caustic soda, caustic potash or the like can be added as a catalyst for promoting the hydrolysis and the condensation polymerization reaction.

In the present invention, as a method for making the gel body porous,
A method of heating the gel body to a temperature higher than the temperature at which the organic polymer compound contained in the gel body is decomposed by combustion can be used.
Further, the organic polymer in the gel body is treated with an organic solvent such as ethanol, isopropyl alcohol, butanol, acetone, butyl acetate, tetrahydrofuran, hexane, xylene, benzene, acetylacetone, 4-methyl-2-pentanone, 2-ethoxyethyl acetate. It may be made porous using a selective elution method.

In order to rapidly perform the steam treatment of the porous gel body in the present invention, the steam pressure is preferably 10 kPa (kilopascal) or more. As a result, the metal oxide can be crystallized near and inside the surface of the gel body. If the water vapor pressure is lower than 10 kPa, it takes a long time to crystallize the metal oxide in the gel body. Although the upper limit of the steam pressure is not particularly limited for crystallization, performing steam treatment at a steam pressure higher than 1000 kPa is not economically preferable because it requires expensive pressure-resistant equipment. In order to carry out steam treatment in a short time and economically and to generate crystals uniformly in the glass body, it is preferable to carry out steam pressure at 10 to 1000 kPa. And it is preferable to carry out at a temperature of 105 to 200 ° C.

The object of the present invention can be achieved by a treatment with high-pressure water instead of the above-described treatment of steam. Also,
The shape of the gel body subjected to the steam treatment is not limited to a bulk, a fiber, a thin film coated on a substrate, or the like.

"Action" The organic polymer compound contained in the gel body of the present invention is a glass body or a gel formed by heating and decomposing and burning the gel body, or by dissolving in an organic solvent and eluted from the gel body. It forms many continuous fine pores that are uniformly distributed throughout the body. Further, when the glass body or the gel body having the continuous pores and the inner surface area of which is increased is treated with steam, the water vapor rapidly penetrates into the inside, so that the metal oxide is uniformly and rapidly introduced into the glass body or the gel body. The nucleation of the crystal is caused to promote the crystal growth.

"Example" The present invention will be described below based on examples. FIG. 1 is a partial cross-sectional view of one embodiment of the present invention, in which a glass body 1 is coated on a glass substrate 4, and the glass body 1 has a metal oxide in an amorphous matrix 2. Are uniformly distributed.

Example 1 23.97 g of a solution consisting of 5 mol of ethyl alcohol per 1 mol of silicon tetraethoxide was prepared. Hydrolysis was performed by adding 4.06 g of dilute hydrochloric acid (3% by weight) to the solution and stirring the mixture at room temperature for 30 minutes. Furthermore, titanium tetranormal butoxide was dissolved in this solution so that the molar ratio of the oxide of titanium dioxide to silicon dioxide became 9:91, and the mixture was stirred for 30 minutes to carry out hydrolysis. The obtained liquid was colorless and transparent, and was further diluted with ethyl alcohol in order to adjust the thickness of a film formed by coating the liquid on a substrate. In this solution, polyethylene glycol (PEG) having an average molecular weight of 600 was added in a weight ratio to the final oxides of titanium dioxide and silicon dioxide (PEG).
/ (TiO ₂ + SiO ₂ ) = 1.0 and uniformly dissolved to obtain a coating solution.

A silicon wafer substrate and a quartz glass substrate were immersed in the above solution, and a gel film composed of polyethylene glycol and a hydrolysis-polycondensation product of a titanium organic compound and a silicon organic compound was coated on each of the substrates. These were heated at 350 ° C. for 15 minutes, and the polyethylene glycol was completely pyrolyzed and disappeared.
An amorphous film of m was obtained. Thereafter, the substrate is kept at 135 ° C and 90% relative humidity.
%, At a steam pressure of 240 kPa for 50 hours. Both films coated on silicon wafers and quartz glass substrates were examined by transmission electron microscopy and electron beam diffraction.The transmissivity was that anatase crystals of 10 to 30 nm in size were uniformly dispersed and deposited inside the films. It was found that a film was obtained. Was. In addition, the ratio of silicon dioxide and titanium dioxide in the film was not changed by the steam treatment. The hardness of the obtained film was increased 1.5 times by the steam treatment.

Example 2 23.97 g of a solution composed of 5 mol of ethyl alcohol per 1 mol of silicon tetraethoxide was prepared. Hydrolysis was performed by adding 4.06 g of dilute hydrochloric acid (3% by weight) to the solution and stirring the mixture at room temperature for 30 minutes. Further, titanium tetranormal butoxide was dissolved in this solution so that the molar ratio of the oxide of titanium dioxide to silicon dioxide was finally 50:50, and the mixture was stirred for 30 minutes to carry out hydrolysis. The obtained liquid was colorless and transparent, and was further diluted with ethyl alcohol in order to adjust the thickness of a film formed by coating the liquid on a substrate. In this solution, polyethylene glycol (PEG) having an average molecular weight of 600 was added in a weight ratio to the final oxides of titanium dioxide and silicon dioxide (PEG).
/ (TiO ₂ + SiO ₂ ) = 1.0 and uniformly dissolved to give a coating solution.

A silicon wafer substrate and a quartz glass substrate were immersed in the above solution, and each substrate was coated with a polyethylene glycol and a gel film composed of a hydrolysis-polycondensation compound of a titanium organic compound and a silicon organic compound. These are heated at 350 ° C. for 15 minutes, and the polyethylene glycol is completely decomposed by pyrolysis and has a thickness of about porous.
A 250 nm amorphous film was obtained. Then the substrate is put at 135 ° C, relative humidity
It was subjected to a steam treatment at 90% at a steam pressure of 240 kPa for 50 hours. In each of the films coated on the silicon wafer and the quartz glass substrate, a translucent film in which anatase crystals having a size of 10 to 30 nm were uniformly dispersed and deposited inside the film was obtained. In addition, the ratio of silicon dioxide and titanium dioxide in the film was not changed by the steam treatment. The hardness of the obtained film was increased by 1.4 times by the steam treatment.

Example 3 23.97 g of a solution composed of 5 mol of ethyl alcohol per 1 mol of silicon tetraethoxide was prepared. Hydrolysis was performed by adding 4.06 g of dilute hydrochloric acid (3% by weight) to the solution and stirring the mixture at room temperature for 30 minutes. Furthermore, titanium tetranormal butoxide was dissolved in this solution so that the molar ratio of the oxide of titanium dioxide to silicon dioxide became 9:91, and the mixture was stirred for 30 minutes to carry out hydrolysis. The obtained liquid was transparent and colorless, and was further diluted with ethyl alcohol in order to adjust the thickness of the coating film by coating on a substrate. To this solution was added polyethylene glycol (PEG) having an average molecular weight of 600 in a weight ratio to the final oxides of titanium dioxide and silicon dioxide, (PEG) / (TiO ₂ + S
iO ₂ ) = 1.5 and uniformly dissolved to obtain a coating solution.

A silicon wafer substrate and a quartz glass substrate were immersed in the above solution, and a gel film composed of polyethylene glycol and a hydrolysis-polycondensation product of a titanium organic compound and a silicon organic compound was coated on each of the substrates. These are heated at 350 ° C for 15 minutes, and the polyethylene glycol is completely pyrolyzed and disappears, and the thickness is about 350 nm.
Was obtained. Thereafter, the substrate is kept at 135 ° C and 90% relative humidity.
%, At a steam pressure of 240 kPa for 50 hours. In each of the films coated on the silicon wafer and the quartz glass substrate, a translucent film in which anatase crystals having a size of 10 to 30 nm were uniformly dispersed and deposited inside the film was obtained. In addition, the ratio of silicon dioxide and titanium dioxide in the film was not changed by the steam treatment. The hardness of the obtained film was increased 1.8 times by the steam treatment.

Example 4 23.97 g of a solution comprising 5 mol of ethyl alcohol per 1 mol of silicon tetraethoxide was prepared. Hydrolysis was performed by adding 4.06 g of dilute hydrochloric acid (3% by weight) to the solution and stirring the mixture at room temperature for 30 minutes. Furthermore, titanium tetranormal butoxide was dissolved in this solution so that the molar ratio of the oxide of titanium dioxide to silicon dioxide became 9:91, and the mixture was stirred for 30 minutes to carry out hydrolysis. The obtained liquid was colorless and transparent, and was further diluted with ethyl alcohol in order to adjust the thickness of a film formed by coating the liquid on a substrate. In this solution, polyethylene glycol (PEG) having an average molecular weight of 200 was added in a weight ratio to the final oxides of titanium dioxide and silicon dioxide (PEG).
/ (TiO ₂ + SiO ₂ ) = 1.0 and uniformly dissolved to obtain a coating solution.

A silicon wafer substrate and a quartz glass substrate were immersed in the above solution, and a gel film composed of polyethylene glycol and a hydrolysis-polycondensation product of a titanium organic compound and a silicon organic compound was coated on each of the substrates. These were heated at 350 ° C. for 15 minutes, and the polyethylene glycol was completely pyrolyzed and disappeared.
An amorphous film of m was obtained. Thereafter, the substrate is kept at 135 ° C and 90% relative humidity.
%, At a steam pressure of 240 kPa for 50 hours. In each of the films coated on the silicon wafer and the quartz glass substrate, a translucent film in which anatase crystals having a size of 10 to 30 nm were uniformly dispersed and deposited inside the film was obtained. In addition, the ratio of silicon dioxide and titanium dioxide in the film was not changed by the steam treatment. The hardness of the obtained film was increased by 1.3 times by the steam treatment.

Example 5 23.97 g of a solution composed of 5 mol of ethyl alcohol per 1 mol of silicon tetraethoxide was prepared. Hydrolysis was performed by adding 4.06 g of dilute hydrochloric acid (3% by weight) to the solution and stirring the mixture at room temperature for 30 minutes. Furthermore, titanium tetranormal butoxide was dissolved in this solution so that the molar ratio of the oxide of titanium dioxide to silicon dioxide became 9:91, and the mixture was stirred for 30 minutes to carry out hydrolysis. The obtained liquid was colorless and transparent, and was further diluted with ethyl alcohol in order to adjust the thickness of a film formed by coating the liquid on a substrate. In this solution, polyethylene glycol (PEG) having an average molecular weight of 10,000 was added in a weight ratio to the final oxides of titanium dioxide and silicon dioxide (PE
G) / (TiO ₂ + SiO ₂ ) = 1.0 and uniformly dissolved to obtain a coating solution.

A silicon wafer substrate and a quartz glass substrate were immersed in the above solution, and each of the substrates was coated with a polyethylene glycol and a gel film composed of a hydrolysis-polycondensation product of a titanium organic compound and a silicon organic compound. These were heated at 350 ° C for 15 minutes, and the polyethylene glycol was completely pyrolyzed and disappeared.
Was obtained. Thereafter, the substrate is kept at 135 ° C and 90% relative humidity.
%, At a steam pressure of 240 kPa for 50 hours. In each of the films coated on the silicon wafer and the quartz glass substrate, a translucent film in which anatase crystals having a size of 10 to 30 nm were uniformly dispersed and deposited inside the film was obtained. In addition, the ratio of silicon dioxide and titanium dioxide in the film was not changed by the steam treatment. The hardness of the obtained film was increased 2.1 times by the steam treatment.

Example 6 In the same manner as in Example 1, titanium dioxide 1 was added in a molar ratio.
A solution containing 83.5% of 6.5% silicon dioxide was prepared. Without dilution with ethyl alcohol for adjusting the thickness of the coating, polyethylene glycol having an average molecular weight of 10,000 was used to obtain a weight ratio of (PEG) / (TiO ₂ + SiO ₂ ) to titanium dioxide and silicon dioxide as final oxides = 1.0 was added to make a uniform solution. The resulting solution was left at room temperature to form a bulk gel. This gel body was immersed in a mixed solution of ethanol and water to elute the polyethylene glycol in the gel body into the solution to obtain an amorphous and porous bulk gel body. Thereafter, the amorphous gel was subjected to a steam treatment at 135 ° C., a relative humidity of 90% and a steam pressure of 240 kPa for 400 hours. By this steam treatment, a glass body in which fine crystals of anatase of 15 to 50 nm were uniformly dispersed and deposited inside the bulk was obtained.

Comparative Example 1 Using the solution prepared in Example 1, a polyethylene glycol-containing gel film was formed on a silicon substrate and a quartz glass substrate. These substrates were heated in a heating furnace at 700 ° C. for 5 hours. However, both the silicon substrate and the quartz glass substrate were hard baked, but titanium dioxide was not crystallized and was an amorphous film.

Comparative Example 2 A gel film was formed on a silicon substrate and a quartz glass substrate in the same manner as in Example 1 except that polyethylene glycol was not added to the solution. These boards
By heating at 350 ° C. for 15 minutes, an amorphous film having a thickness of about 200 nm was obtained. Thereafter, these substrates were subjected to a steam treatment at 135 ° C., a relative humidity of 90% and a steam pressure of 240 kPa for 50 hours. In both substrates, microcrystals of titanium dioxide were found to be deposited only on the film surface, and almost no crystals were formed inside the film. As shown in the above examples, it can be seen that in the example of the present invention, a glass body in which titanium dioxide microcrystals are uniformly dispersed can be obtained.

The samples obtained in Examples 1 to 6 have a photocatalytic effect, and include alkene (having a double-bonded alkyl group in the molecule) compound and alkyne (having a triple-bonded alkyl group in the molecule) compound Can be used as a catalyst when reacting with water to form an alkane compound.

According to the present invention, a glass body in which metal oxide microcrystals are uniformly dispersed can be obtained without using a crystal nucleating agent. Further, this glass body can be obtained in any shape such as bulk, fiber, and thin film. Further, according to the present invention, since a glass body containing crystals can be obtained at a relatively low heating temperature, a film can be formed on a substrate having low heat resistance, for example.

[Brief description of the drawings]

FIG. 1 is a partial sectional view of one embodiment of the present invention. 1 ... glass body, 2 ... amorphous matrix, 3 ... metal oxide crystal, 4 ... substrate

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Shinya Katayama 3-1-1, Doshumachi, Chuo-ku, Osaka-shi, Osaka Inside Nippon Sheet Glass Co., Ltd. (72) Inventor Toshio Kado 3-chome, Doshucho, Chuo-ku, Osaka-shi, Osaka No. 5-11 Inside Nippon Sheet Glass Co., Ltd. (56) References JP-A-3-159925 (JP, A) JP-A-48-913 (JP, A) Noboru TOHGE et al. , Journal of Non-Crystalline Solids, (Holland), 1988, Vol. 100, p. 501-505 (58) Field surveyed (Int. Cl. ⁷ , DB name) C03C 3/00-4/20 C03C 11/00 C03C 14/00 C03B 8/02 JICST file (JOIS)

Claims (3)

(57) [Claims] 1. A gel body is formed from a solution containing a hydrolyzable metal organic compound and an organic polymer compound, and then the organic polymer compound in the gel body is removed to make the gel body a porous body. And a method of producing a glass body containing crystals of the metal oxide by treating the porous body with steam thereafter. 2. The method according to claim 1, wherein said organic high molecular compound is polyethylene glycol having a molecular weight of from 200 to 10,000. 3. The method according to claim 1, wherein said hydrolyzable metal-organic compound includes a titanium compound.