JPH0238324A - Production of silica glass - Google Patents

Abstract

PURPOSE:To obtain a silica glass prevented from crack or fissure development by gelling a sol solution prepared by hydrolyzing a silicon alkoxide incorporated with (N-)morpholine and silica fine granules, followed by drying and calcination. CONSTITUTION:A silicon alkoxide or its polycondensate is incorporated with 0.1-5.0 molar times of morpholine and/or N-morpholine and silica fine granules and the resultant system is homogeneously dispersed in the presence of a solvent followed by addition of water in the presence of a catalyst to make a hydrolysis, thus preparing a sol solution. Thence, this solution is gelled at >=0 deg.C and the resultant gel is left to stand at 0-100 deg.C for several minutes to several tens days to effect drying followed by calcination by heating at a rate of 50-200 deg.C to 1000-1300 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for producing silica glass used for optics, semiconductor industry, electronic industry, physics and chemistry, etc.

(Prior Art) In recent years, the sol-gel method has been attracting attention as a new method for producing silica glass.

The method for producing silica glass using the sol-gel method is as follows.

General formula 5t(OR)= (where R represents an alkyl group)
Silicon alkoxides and/or polycondensates thereof, such as (RO)ssi(O5i(OR))nO5i(OR)i
(n = O~8) with water (acid as a catalyst in advance,
(Optionally, an alkali may be added in advance) and hydrolyze it to form silica hydrosil. At this time, an appropriate alcohol may be added as a solvent so that the silicon alkoxide and water form a homogeneous system. Let this silica sol solution stand still, raise the temperature,
It is gelled by adding a gelling agent or the like.

Thereafter, the gel is dried to obtain silica gel.

Silica glass is obtained by sintering this dried gel in a suitable atmosphere.

This sol-gel method has the following features.

Since it can be produced at a lower temperature than the conventional vapor phase chemical vapor deposition method in which the soot produced by flame hydrolysis or the like using fil 5iC1, etc. as a raw material is sintered and vitrified, it can save energy and reduce costs.

(2) Since it can be used as a raw material in a liquid state, it can be easily purified and highly purified.

(3) Since liquid phase mixing is possible at room temperature, homogeneous glass can be produced even when mixed with other components.

There are still unresolved problems in the production of silica glass by the sol-gel method, which has various advantages as described above.

In particular, the problem is that the gel tends to crack or crack during the drying process, making it difficult to produce a large, monolithic dried gel with a high yield. One of the causes of cracks and cracks is that stress is generated in the gel as water, alcohol, etc. evaporate during gel drying, and if this stress is greater than the strength of the gel, it is thought that the gel will crack or break. There is. In addition, this stress is expressed by the following formula % formula % (P = stress, γ = surface tension, θ = wetting angle, r = pore diameter), and the larger the surface tension is, the smaller the pore diameter is, the larger it becomes. .

Therefore, as a method to prevent such cracks and cranks, measures have been taken such as increasing the amount of water in the sol solution to increase the gel strength, and increasing the hydrolysis temperature to increase the pore diameter. There is.

Furthermore, Japanese Patent Application Laid-open No. 183129/1983 discloses that solvents with a boiling point higher than water, such as 1-
A method has been proposed in which butanol, 1-pentanol, 1-hexanol, and toluene are added to silicon alkoxide.

(Problems to be Solved by the Invention) However, in all of the above methods, it was difficult to obtain a sufficiently large dry gel body, and it was not possible to obtain a silica glass body whose dimensions were very large.

The present invention provides the production of silica glass without cracking or cracking.

(Means for Solving the Problems) The present invention considers that stress generated due to evaporation of water, alcohol, etc. during gel drying is a cause of cracks and cracks, and the present invention aims to prevent the generation of such large stress. In order to avoid this, morpholine and/or N-morpholine is used as a solvent for silicon alkoxide, and silica fine particles are further added to the gel.

As the silicon alkoxide used in the present invention, not only silicon alkoxide monomers but also polycondensates may be used. For example, (CHzO on asi(05N(QC)Is)
i(QC)lx)z(n-0~8). One or more of these can be used. The alkyl group of silicon alkoxide is
A methyl group, an ethyl group, a propyl group, a butyl group, etc. are preferred.

To the water added for hydrolysis, mineral acids such as hydrochloric acid and nitric acid, organic acids such as formic acid and acetic acid as catalysts, and not only ammonia but also organic bases such as ethylenediamine as bases may be added in advance.

The amount of morpholine and/or N-morpholine added to the silicon alkoxide is preferably 0.1 to 5.0 times (molar ratio) to the silicon alkoxide, and commonly used alcohols such as ethanol may also be used together. can. Furthermore, ketones and esters can also be used in combination.

Silica fine particles are uniformly dispersed in a solvent or a mixed solution of a solvent and silicon alkoxide before being hydrolyzed by adding water. At this time, it is effective to use a surfactant to improve dispersibility.

The silicon alkoxide, morpholine and/or N-morpholine, silica fine particles, and water are thoroughly mixed using a starrer or the like in order to make the resulting sol as uniform as possible. Alternatively, ultrasonic waves may be irradiated.

The generated sol solution is quickly transferred to another container and allowed to gel. During gelation, it is preferable to seal the container to prevent the solvent from escaping from the generated gel, and the temperature during gelation is preferably 0° C. or higher.

In the drying process, instead of using a lid with holes, the gel is dried and shrunk and solidified in an appropriate atmosphere to form a dry gel.

Thereafter, silica glass is manufactured by sintering using a gel-sol method.

Generally used conditions are used for the gelling step, drying step, and sintering step. For example, each
Leave at 100℃ for a few minutes to several 10 days, leave at room temperature to 100℃ for several hours to several 10 days, 1000 to 130 in an appropriate atmosphere
50~b at 0°C (Action) Although the details of the action of morpholine and/or N-morpholine and silica fine particles are unknown, the formation of silica fine particles in the gel, the bonding between these silica fine particles in the gel,
It is thought that this contributes to the relaxation of stress generated in the gel during the drying process, making it possible to increase the size of the gel.

Example 1 Fine silica particles having a particle size of approximately 7 On+s were added to morpholine in a weight ratio of 2 to 0.1 times the weight of the morpholine, and after uniformly dispersing the mixture, tetramethoxysilane was added in an amount of 0.9 times the weight of the morpholine. A homogeneous solution was prepared by mixing, and a 0.01 mol/It aqueous solution of choline was added at a weight ratio of 0.64 times that of tetramethoxysilane, and the mixture was sufficiently mixed to obtain a silica sol. The obtained sol was made into a diameter of 200 mm.
The mixture was placed in a stainless steel petri dish to a depth of 10 m, sealed, and allowed to gel at room temperature for 5 days. Thereafter, it was dried at 60°C for 7 days and further dried at 120°C for 1 day to obtain a dried gel with a diameter of about 170 nm. The bulk density of the dry gel thus obtained was 0.65 g/-, with no cracks or cracks. This dried gel was heated in air to 1250° C. at a rate of 60° C./hour to obtain a silica glass having a diameter of about 110° without cracks or foaming. This silica glass has no devitrification or bubbles and is of high quality. Further, as a result of analysis, the properties of this silica glass matched those of commercially available silica glass.

Example 2 A dry gel having a diameter of about 170 m was obtained in the same manner as in Example 1, except that a mixed solvent having a volume ratio of methanol:morpholine of 7:3 was used.

The dried gel thus obtained was free of cracks and cracks. This dried gel was heated in the same manner as in Example 1 to obtain silica glass having a diameter of about 110 m without cracks or foaming. This silica glass has no devitrification or bubbles and is of high quality.

Further, as a result of analysis, the properties of this silica glass matched those of commercially available silica glass.

(Effects of the Invention) According to the present invention, large-sized silica glass can be easily manufactured by the sol-gel method without causing cracks or cracks. There are basically no restrictions on its size (its shape is not limited to plate-like ones, but rod-like and tubular ones can also be manufactured, and it can be manufactured at a lower cost than before).

In addition, since silica glass can be manufactured at a lower cost than before with the present invention, it can be used not only in fields such as photomask substrates for IC manufacturing, which have traditionally been used, but also in fields where it has not been used due to its high price. It will also be possible to expand demand for.

Agent Patent Attorney Akira Hirose

Claims (1)

[Claims] 1. In the production of silica glass, which consists of the steps of hydrolyzing silicon alkoxide to form a sol solution, gelling the sol, drying the gel, and firing, morpholine and/or A method for producing silica glass, characterized by adding N-morpholine and silica fine particles.