JPH09194230A - Opal glass and glass block for building material produced from the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain opal glass transmitting sunbeams as faint light and excellent in UV shielding ability and chemical durability and to provide a glass block for building material produced from the same. SOLUTION: This opal glass has a compsn. consisting of, by weight, 50-75% SiO2 , 5-12% Al2 O3 , 0.5-13% B2 O3 , 1-7% BaO+SrO+ZrO, 13-22% Na2 O+K2 O, 0.1-1% SO3 and 0.05-1% MoO3 , contains fine sodium sulfate particles deposited and dispersed in the glass matrix and has 10-60% average transmissivity in the wavelength region of 400-700nm in the case of 10mm thickness.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to opalescent glass and a glass block for building materials produced by using it.

[0002]

2. Description of the Related Art Hitherto, as opalescent glass, opalescent glass having various compositions has been proposed. For example, JP-A-50-40610, JP-A-50-51513 and JP-A-53-125418 are proposed. JP-A-56-9
No. 6746 discloses that SiO ₂ —RO—R ₂ O (R is
It is disclosed that a glass such as Mg, Ca, Ba and the like, R ₂ is made of Li, Na, K, etc.) by adding a fluoride to make the milk white.

[0003] These milky glasses have a large milky white color because a large amount of fluoride crystals are precipitated in the glass, and are limited to use as tableware and decorative articles.

In recent years, attempts have been made to develop glass blocks for building materials made of opalescent glass.
No. 315534.

[0005] The opalescent glass disclosed in JP-A-63-315534 has a higher light transmittance and is more excellent in chemical durability than the opalescent glass used for tableware and decorative articles. Therefore, the glass blocks made from this will not be glare when exposed to the sun's rays, and soft and faint light will enter the room, and will be exposed to acid rain due to water droplets and soot when used on the outer walls of the building or veranda etc. Even
The appearance is not impaired due to whitening.

[0006]

However, the above-mentioned glass block for building materials made of opalescent glass has a large particle size of sodium sulfate precipitated and dispersed in the glass, so that it easily transmits ultraviolet rays, and articles in the room may be discolored. However, there is a problem that the color is easily discolored.

It is an object of the present invention to provide opal glass which is excellent in ultraviolet ray shielding ability and chemical durability while allowing sunlight to be transmitted as soft and pale light, and a glass block for building materials made from the opal glass. The purpose is to do.

[0008]

SUMMARY OF THE INVENTION The milky glass of the present invention comprises:
By weight percentage, SiO ₂ 50-75%, Al ₂ O ₃ 5
_{~12%, B 2 O 3 0.5~13} %, BaO + SrO
+ ZnO 1 to 7%, Na ₂ O + K ₂ O 13 to 22
%, SO ₃ 0.1-1%, MoO ₃ 0.05-1%
Wherein sodium sulfate fine particles are precipitated and dispersed in the glass, and the average transmittance at a wavelength of 400 to 700 nm is 10 to 60% at a thickness of 10 mm.

Further building materials glass block of the present invention, in% by _{weight, SiO 2 50~75%, Al 2} O 3 5
_{~12%, B 2 O 3 0.5~13} %, BaO + SrO
+ ZnO 1 to 7%, Na ₂ O + K ₂ O 13 to 22
%, SO ₃ 0.1-1%, MoO ₃ 0.05-1%
Wherein sodium sulfate fine particles are precipitated and dispersed in the glass, and the average transmittance at a wavelength of 400 to 700 nm is 10 mm in thickness and 10 to 60% made of opalescent glass. I do.

[0010]

Since the opalescent glass of the present invention contains a large amount of Na ₂ O and SO ₃ , white sodium sulfate [Na ₂ SO ₄ ] fine particles are deposited during the vitrification reaction of both components, and this precipitates in the glass. Since it precipitates in a state of being uniformly dispersed in the above, it will allow sunlight to pass through appropriately and will have a pale white color tone.

Further, even when it is directly exposed to sunlight, the transmitted light is weakened by the diffuse reflection and light scattering action among the sodium sulfate fine particles, so that there is no glare and a unique Japanese-style shoji tone is produced.

Next, the reason for limiting the composition of the opal glass of the present invention as described above will be explained.

SiO ₂ is a component forming a glass former, and if it is less than 50%, the chemical durability will be poor, and if it is more than 75%, the viscosity of the glass will be high and melting will be difficult. .

If Al ₂ O ₃ is less than 5%, the chemical durability will be poor, and if it is more than 12%, the high temperature viscosity of the glass will be increased and the meltability of the glass will be poor.

B ₂ O ₃ is a component which acts as a flux for glass and has the effect of improving chemical durability, but if it is less than 0.5%, the effect cannot be obtained.
If it exceeds 13%, volatilization increases from the surface of the glass melt, and appearance defects such as striae and color stripes occur.

BaO, SrO and ZnO are components that lower the viscosity of the glass in the high temperature range and improve the chemical durability, but if it is less than 1%, its effect is not obtained and it is exposed to rainwater. When it exceeds 7%, the glass becomes devitrified and molding becomes difficult.

Na ₂ O is a component necessary for improving the meltability of glass and precipitating fine particles of sodium sulfate in glass. K ₂ O is also a component that improves the meltability of the glass, and can be substituted for part of Na ₂ O. However, if the total amount of these components is less than 13%, the viscosity of the glass increases, Molding becomes difficult. On the other hand, if it is more than 22%, the chemical durability becomes poor, which is not preferable.

SO ₃ is a component necessary for precipitating fine particles of sodium sulfate in the glass to make the glass pale white. If it is less than 0.1%, its effect cannot be obtained, and if it is less than 1%. If the amount is large, the glass becomes streaky and the appearance becomes poor.

MoO ₃ has an appropriate size of sodium sulfate fine particles precipitated in glass, specifically 0.5 to 10
It is a component for controlling the size to 0 micron and improving the devitrification tendency of the glass. If it is less than 0.05%, its effect is not obtained, and if it is more than 1%, the glass becomes opaque and permeates. The rate drops.

The opalescent glass of the present invention has a wavelength of 400 to 70.
The average transmittance at 0 nm is 10 to 60 for a thickness of 10 mm.
%, The average transmittance is less than 10%, the amount of light passing through the glass is reduced, and the daylighting property is deteriorated. On the other hand, when the average transmittance is more than 60%, the light diffusion property is weak. And it is difficult to obtain a uniform lighting, which is not preferable.

Further, in the present invention, in addition to the above components, SnO ₂ , WO ₃ , P ₂ O ₅ , TiO ₂ , V ₂ O.
₅ , ZrO ₂ , MgO, CaO, As ₂ O ₃ , Sb ₂ O
_3. It can contain chlorides and fluorides.

That is, SnO ₂ , WO ₃ and P ₂ O ₅
Is a component having the same action and effect as MoO _3, and in order to enhance the action of controlling the size of sodium sulfate fine particles, at least one of these components should be contained in an amount of 0.05% or more. Just go. However, if each of these components exceeds 1%, the glass is emulsified and the transmittance is undesirably reduced.

Further, TiO ₂ and V ₂ O ₅ have an effect of absorbing ultraviolet rays, and when it is desired to further enhance the ultraviolet ray shielding ability of the glass, one or two of these components are added by 0.01% each. It is sufficient to contain the above. However, when the content of each of these components exceeds 1%, the absorption edge reaches the visible range,
The thick portion of the glass is colored yellow, which is not preferable in appearance.

Further, ZrO ₂ is effective in improving the chemical durability of glass, and if it is desired to further enhance such effect, it may be contained at 0.1% or more. However, if ZrO ₂ is more than 3%, the glass is devitrified, which is not preferable.

Further, MgO and CaO are components having the same action as BaO and the like, but when each exceeds 5%,
It is not preferable because the glass is devitrified. As ₂ O ₃ , Sb
₂ O ₃ , chloride compounds, and fluorides are components that act as a fining agent, and can be contained up to 1%.

Further, in the present invention, for design reasons, C
It is also possible to contain up to 1% of a coloring agent such as oO or NiO.

[0027]

Next, the present invention will be described in detail with reference to examples.

Tables 1 and 2 show the opal glass of the present invention (Sample N).
o. 1-8) and the milky glass of Comparative Example (Sample No. 9)
It shows. In addition, sample No. The glass No. 9 is opal glass for glass blocks disclosed in JP-A-63-315534.

[0029]

[Table 1]

[0030]

[Table 2]

Each sample in Tables 1 and 2 was prepared as follows.

First, glass raw materials were prepared so as to have the composition shown in the table, which was placed in a platinum crucible, and 145
After melting at 0 ° C. for 4 hours, the temperature is lowered to 1200 ° C. to uniformly precipitate the white fine particles of sodium sulfate, and then poured out onto a carbon plate to form a plate having a thickness of 20 mm. This was placed in a lehr and slowly cooled.

As is apparent from the table, N which is the product of the present invention.
o. Each of the samples 1 to 8 has a transmittance of 2 at a wavelength of 400 nm.
It was 1.2% or less, and was excellent in ultraviolet shielding ability. The average transmittance at a wavelength of 400 to 700 nm is 26.0 to 5
5.0% and the amount of alkali elution is 0.3 mg
Below, it was also excellent in chemical durability.

On the other hand, No. Sample No. 9 has a wavelength of 40
The average transmittance from 0 to 700 nm was 60.0% and the chemical durability was also excellent, but the transmittance at the wavelength of 400 nm was as high as 55.3% and the ultraviolet shielding ability was poor.

No. When the fine particles deposited on each sample of Nos. 8 and 9 were observed with a microscope, No. The fine particles deposited on the sample No. 8 had a diameter of 0.5 to 70 μm. The diameter of the fine particles deposited on the sample No. 9 was 50
It was as large as ~ 800 microns.

Further, No. 145x from each of samples 8 and 9
An exposure test in which a glass block having a size of 145 × 95 is manufactured and sunlight is applied to the article (red, blue, green, yellow, and violet color pigment printed paper) through the glass block (total 500)
Time), No. In the glass block produced from the sample No. 8, no fading or discoloration of the article due to ultraviolet rays was observed at all, but No. In the case of the glass block made from sample No. 9, the article faded slightly.

The transmittance at a wavelength of 400 nm in the table was measured by optically polishing both sides of each sample glass to a thickness of 10 mm and then measuring a wavelength of 40 with a spectrophotometer with a large integrating sphere of 150φ.
The transmittance at 0 nm was measured.

The average transmittance for wavelengths 400 to 700 nm is 400 to 70 for each sample glass under the same conditions as above.
The transmittance at 0 nm was measured every 1 nm, and the average value was determined.

The amount of alkali elution is JIS R-35.
It is measured based on No. 02, and it is desirable that this value be 0.5 mg or less in order to prevent whitening of the glass block.

[0040]

As described above, the opal glass of the present invention has an average transmittance of 10 to 60 at a wavelength of 400 to 700 nm.
%, And the particle size of the sodium sulfate precipitated inside the glass is uniform and fine. Therefore, the glass block for building materials made from this opalescent glass can receive soft and faint light when it receives sunlight. And has excellent ability to block ultraviolet rays.

Further, since the opal glass of the present invention is excellent in chemical durability, even if the glass block produced from the opal glass is used for an outer wall of a building or a veranda, no whitening occurs.

Claims (2)

[Claims] 1. The composition according to claim 1, wherein the weight percentage of SiO _{2 is} 50-75.
_{%, Al 2 O 3 5~12%} , B 2 O 3 0.5~13
%, BaO + SrO + ZnO 1~7 %, Na 2 O + K
₂ O 13-22%, SO ₃ 0.1-1%, MoO ₃
It has a composition of 0.05 to 1% and is composed of fine particles of sodium sulfate deposited and dispersed in glass and has a wavelength of 400 to 700 n.
The average transmittance at m is 10 to 60% at a thickness of 10 mm.
Milky glass characterized by the following. 2. The composition of claim 2, wherein the weight percentage of SiO _{2 is} 50-75.
_{%, Al 2 O 3 5~12%} , B 2 O 3 0.5~13
%, BaO + SrO + ZnO 1~7 %, Na 2 O + K
₂ O 13-22%, SO ₃ 0.1-1%, MoO ₃
It has a composition of 0.05 to 1% and is composed of fine particles of sodium sulfate deposited and dispersed in glass and has a wavelength of 400 to 700 n.
The average transmittance at m is 10 to 60% at a thickness of 10 mm.
A glass block for building materials characterized by being made from milky glass.