JP2002087845A - Luminescent frosted glass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide luminescent frosted glass which is capable of suppressing glare due to sunlight or illumination and has sufficient daylighting properties and also, is capable of effectively visual-recognized even when the field of view is obstructed (e.g. at night) and moreover, hazard such as earthquake or fire, occurs to cause functional insufficiency of illumination lamps or emergency lamps, due to lamp breakage or power failure, and provided with decorative properties. SOLUTION: This glass is produced by forming a luminescent frosted coating film consisting of a low-melting glass matrix and an inorganic luminescent fine powder dispersed in the glass matrix, on at least one surface of a transparent glass sheet, wherein the glass sheet provided with the luminescent frosted coating film has visible-light transmissivity adjusted to >=50% and a haze value adjusted to >=50%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a frosted glass which reduces glare of sunlight and lighting, and has a lighting property and a privacy property.

[0002]

2. Description of the Related Art A frosted glass itself is known, and is obtained by grinding the surface of a glass plate, or after the grinding, by hydrofluoric acid treatment, or a paste containing a low-melting glass frit and an inorganic powder on the glass surface. And baking to form a film. The present invention relates to the frosted glass formed with the film.

As an example of applying a luminous material to glass or the like, Japanese Patent Application Laid-Open No. Hei 5-193998 discloses a laminated colored decorative portion provided on the surface of a plate glass or a mirror plate constituting windows, walls, partitions and the like. The structure of a colored decorative portion in which the portion is formed of a layer including a thermosensitive color changing material, a photosensitive color changing material, a light storage material, and the like, and is rich in change of decoration and interest is disclosed.

JP-A-8-165140, JP-A-9-9-1
Japanese Patent No. 42882 discloses a glaze (ceramic color) containing a low-melting glass powder and a phosphorescent material, and a product obtained by applying the same to a glass material or the like, which can emit light for a long time at night or has a decorative effect. Is disclosed.

[0005] Japanese Patent Application Laid-Open No. 9-220577 discloses that a layer of a phosphorescent ultraviolet radiating material is provided on the surface of a substrate, and a layer of a photocatalytic semiconductor is further provided on the surface. Is disclosed.

The present invention provides a frosted glass having a decorative property and a light absorbing property, which is different from those which impart a decorative property or emits excitation light of a photocatalytic substance, and has a light absorbing property. It is an object of the present invention to provide a luminous frosted glass that can effectively visually recognize glass when an illumination light and an emergency light are damaged due to an earthquake or a fire, and malfunctions due to a power outage or the like.

[0007]

According to the present invention, there is provided a glass having a frost-like coating formed on at least one surface of a transparent glass plate by dispersing an inorganic luminous fine powder in a low-melting glass matrix. Has a visible light transmittance of 5
This is a luminous frosted glass with 0% or more and a haze value of 50% or more.

The luminous frost-like coating is composed of 100% by weight of a low-melting glass matrix and 100% by weight of an inorganic luminous fine powder.
It is preferable that about 30% by weight is dispersed.

Further, it is preferable that the luminous frost-like coating is formed by dispersing 25% by weight or less of inorganic light-scattering fine powder in 100% by weight of a low-melting glass matrix.

[0010] In addition, another transparent glass plate is disposed on the glass on which the luminous frost-like coating has been formed so as to face the film-coated surface side, and the pair of transparent glass plate peripheral portions are integrally formed via a spacer. It may be converted to a double glazing.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Transparent glass plates include various transparent glasses such as ordinary soda-lime glass, borosilicate glass, and aluminosilicate glass. Soda-lime glass used widely and widely is particularly preferred. Is preferred. Further, heat strengthened glass of those glasses may be used.

[0012] The frost-like coating applied to the transparent glass plate is formed by applying a paste containing a low melting point glass frit, an inorganic luminous fine powder, an inorganic light-scattering fine powder, and an organic dispersion medium to the transparent glass plate. The film is formed by heating and baking in a range and at a temperature not lower than the temperature at which the low melting point glass frit melts.

A good baking temperature for the low melting point glass frit to appropriately melt and adhere to the transparent glass plate is determined by considering the heat softening property of the transparent glass sheet, especially the heat softening property of the soda-lime glass sheet. 700 ° C or less, preferably 600 to
It is about 650 ° C., and the softening point of the low melting glass frit is about 600 ° C. or less, preferably about 550 ° C. or less.
If the softening point of the low-melting glass frit is higher than 600 ° C., the baking will be insufficient, or if the baking temperature is increased to make the baking sufficient, deformation such as warpage and bending of the transparent glass plate will easily occur. On the other hand, among the low melting point glass frit, some have a softening point lower than 400 ° C., but they can also be employed.

The low-melting glass frit has a coefficient of thermal expansion (at room temperature to 300 ° C.) of about 50 to 95 (× 10 ⁻⁷ / ° C.). In the case of the expansion coefficient, the glass with the frost-like coating is easily strengthened by heat.

The basic composition of the low melting glass frit is limited.
Not specified, PbO-ZnO system, P_TwoO_Five-B_Two
O_ThreeSystem, B_TwoO_Three-ZnO-based, P_TwoO_Five-ZnO-based, Bi_TwoO
_Three-B _TwoO_Three-ZnO series, alkali metal oxidation as appropriate
Various objects such as those containing objects can be applied. Those moths
Lath crushed to 10 μm or less to several tens μm or less
Is used as a frit.

[0016] Inorganic phosphorescent fine high-energy radiation, for example, is excited by irradiation of ultraviolet rays is also contained in sunlight or a fluorescent lamp, which also itself emission after stopping the high-energy ray irradiation, Y ₂ O ₂ S (activator Eu), ZnS (activator Mn), MeAl ₂ O ₄ (Me: at least one of Ca, Sr, Ba or Mg) (activator Eu, co-activator La, Ce,
Pr, Nd, Mn, Sn, Bi, or the like, such as BaMg ₂ Al ₁₆ O ₂₇ (activator E
u) and the like can be appropriately employed, but the above MeAl ₂
O ₄ -based materials have relatively good heat resistance and are unlikely to react with low-melting glass frit.

The inorganic phosphorescent fine powder is a low melting point glass frit 1
If the amount is less than the above range, light emission is insufficient, and it is difficult to visually recognize the glass at night or the like. Exceeding the above range causes the visible light transmittance to be too small and the haze value to be too large to deteriorate the daylighting property. Also, the film quality tends to be brittle.

The particle size of the inorganic luminous fine powder is 10 μm or less to several tens μm or less as in the case of the low melting point glass frit. The inorganic phosphorescent fine powder itself has a different refractive index from the low-melting glass matrix, and by forming the roughened surface on the coating surface by dispersing the fine powder in the glass matrix, it is possible to provide an antiglare property to the glass. Also, a haze, that is, a light scattering property, and a frost-like appearance can be provided.

The inorganic light-scattering fine powder is a well-known light-scattering and non-light-storing fine powder of silica, alumina, titania, zirconia, or the like. By forming a rough surface on the surface of the coating and the surface of the coating, the glass is given a light-scattering property and a frost-like appearance. Inorganic light scattering fine powder is 0 to 25% by weight based on 100% by weight of low melting glass frit
Is appropriately added within the range described above. If it exceeds 25% by weight, the visible light transmittance is remarkably reduced, and the light collecting property is deteriorated. In order to effectively provide the light-scattering property and the frost-like appearance, the inorganic light-scattering fine powder is preferably used in an amount of 2% by weight or more. The particle size of the inorganic light-scattering fine powder is the same as that of the low-melting glass frit and the inorganic light-storing fine powder.

As the organic dispersion medium, a resin such as acrylic, silicone, epoxy, urethane, alkyd, or cellulose is used in a solvent such as aromatic hydrocarbon, alcohol, ketone, cellosolve, or chlorinated hydrocarbon. Use the dissolved one. Note that a leveling agent, a deterioration preventing agent, and other known additives can be added to the dispersion medium.

The total solid content of the paste including the low melting point glass frit, the inorganic luminous fine powder, and the inorganic scatterable fine powder is about 3 to 30% by weight. The amount of the dispersion medium becomes excessive and the paste viscosity is lowered, so that it is difficult to obtain a coating layer having a desired thickness, the solid content exceeding the above-mentioned range becomes excessive, the paste viscosity is increased and the application becomes difficult.

The preferred viscosity of the paste varies depending on the application means and method, but is generally preferably in the range of 0.05 to 2 Pa · s. If the viscosity is lower, the amount of the dispersion medium becomes excessive and the desired thickness of the paste is reduced. It is difficult to obtain a coating layer, and if the viscosity is higher, uniform coating tends to be difficult.

The paste is prepared by adding a low-melting glass frit, an inorganic light-storing fine powder, and an inorganic light-scattering fine powder into a dispersion medium comprising the above-mentioned resin and solvent, and forcibly stirring with a ball mill or a stirrer equipped with stirring blades to reduce the solid content. It is prepared by sufficiently dispersing in a liquid. The means for applying the prepared paste to the transparent glass plate is not specified, and any suitable means such as a curtain flow coating method, a roll coating method, a spin coating method, a screen printing method, and a flexographic printing method may be employed. The average thickness of the coating film is several μm to 10 μm in consideration of the surface unevenness of the luminous frost-like coating after baking.
It is adjusted in advance so as to be μm.

As described above, the preferred baking temperature for the low melting glass frit to be appropriately melted and adhered to the transparent glass plate is 600 to 650 ° C., and is maintained for several minutes to 10 minutes depending on the thickness of the glass plate. And baking to form a luminous frost-like coating. The film thickness after baking is as described above. If it is 1 μm or less, the absolute amount of the inorganic luminous fine powder is insufficient, and light emission at night or the like is not sufficient.
It is not necessary to form a thick film exceeding 10 μm, and in that case, the haze becomes remarkable, and the lighting property is impaired.
In particular, a phenomenon in which the coating peels off during baking tends to occur.

When heated for a predetermined time at the time of baking, the surface of the coating and the entire surface of the glass including the surface of the transparent glass plate are rapidly cooled by blowing a cooling medium, for example, cool air, to obtain a thermally strengthened transparent glass with a luminous frost-like coating. A plate is obtained.

The transparent glass plate having a luminous frost-like coating has a visible light transmittance of 50% or more, and if it is less than 50%, the light-collecting property is insufficient. In addition, the haze value is set to 50% or more, and if it is less than 50%, the transparency becomes excessive, the effect of alleviating the glare of sunlight and illumination is small, and the privacy property is easily impaired, especially the film surface is wet. In this case, privacy is greatly impaired.

The luminous frost-like coating may be applied to one surface of the transparent glass plate, but it is not necessary to apply it to the entire surface of the transparent glass plate. If you indicate the direction of guidance or if it is tempered glass,
It is also possible to display that effect or to show various designs in consideration of other decorative features. The pattern is formed by masking the pattern at the time of applying the paste, by screen printing, or by coating and drying the film, and then cutting the pattern into a desired pattern.

There are many cases where the low melting point glass frit, which is the main compounding material of the frosted coating, contains PbO, P ₂ O ₅ , B ₂ O ₃ , or an alkali metal oxide in an excessive amount and has poor weather resistance and durability. In such a case, another transparent glass plate is disposed opposite to the film-coated side of the glass on which the frost-like coating is formed, and the pair of glass plate peripheral portions are integrated via a spacer. Glass, that is, a double glazing having a frost-like coating on the inner space side may be used. In this case, as in the case of ordinary double-glazed glass, a moisture absorbing agent is built into the spacer, and the air in the double-glazed glass internal space,
Keep the gas dry. In addition, the spacer and the periphery of the transparent glass plate facing surface are bonded with a moisture-impermeable or water-impermeable adhesive such as polyisobutylene or a butyl-based adhesive. Or with a silicone sealant.

The distance between the transparent glass plates in the above-mentioned double-glazed glass is also several mm to several tens mm, for example, 3 to 60 mm, as in the case of ordinary double-glazed glass. And various gases for the purpose of heat insulation, for example, helium, argon, and hydrocarbon gases.

[0030]

[Example] [Sample preparation] As a low melting point glass frit for a low melting point glass matrix, composition (wt%) SiO ₂ 30.0 B ₂ O ₃ 20.0 PbO 50.0 Thermal expansion coefficient 60 × 10 ^-7 / ° C. (Room temperature to 300 ° C.) Glass having a softening point of 480 ° C. was adopted, the maximum particle size was set to 10 μm, and the particles were sized to less than 10 μm.

Strontium aluminate (adding europium as an activator) was used as the inorganic light-storing fine powder, and silica powder was used as the inorganic light-scattering fine powder.

90 parts by weight of the low melting point glass frit: 10 parts by weight of silica powder, 10% by weight of the total of the solid content described above, 20% by weight of a cellulose resin, and 70% by weight of an alcoholic solvent + inorganic. A dispersion (1) of a light-scattering fine powder was prepared.

Separately, a dispersion (2) of a luminous fine powder containing 40% by weight of the strontium aluminate in an alcohol solvent was prepared.

The dispersion liquid (2) was added to the dispersion liquid (1) at various ratios, mixed, and then mixed with a bar coater.
It was applied on one side of a transparent glass plate of 0 mm × 400 mm × 5 mm (thickness).

After drying, the transparent glass plate with the coating film was set in an electric heating furnace and baked under the conditions of a glass plate temperature of 630 ° C. for 5 minutes to obtain a glass sample having a luminous frost-controlling film. The average thickness of the luminous frost control film is about 4 μm for each glass sample.

[Appearance (light-collecting, light-scattering, anti-glare) test]
Each glass sample with a film has a slightly greenish color tone due to inorganic luminous fine powder. JIS K
Based on the test method of 7105, the light transmittance was measured with a haze meter (HGM-2DP: C light source, manufactured by Suga Test Instruments Co., Ltd.), and the average transmittance and haze value in the visible region were calculated.
In addition, a visible light transmittance of 50% or more is good (○),
A value less than the above value was evaluated as unacceptable (x), a haze value of 50% or more was evaluated as good (o), and a value less than the above value was evaluated as unacceptable (x). Further, when a fluorescent lamp 2 m away was seen through a glass sample with a film, the antiglare property was evaluated as good (○) if the outline of the fluorescent lamp was unclear and unacceptable (×) if the outline could be confirmed.

[Emission test] Each film-coated glass sample was placed flat on a 2.5 m table directly below an indoor fluorescent lamp (20 W x 2 parallel) and irradiated with light. Was observed. Those with clear yellow-green luminescence were evaluated as good (O), and those with insufficient or no luminescence were evaluated as unacceptable (X).

[Results] Table 1 shows the mixing conditions and results. As shown, within the scope of the present invention, good results are obtained in both appearance (light-collecting, light-scattering, and anti-glare properties) and light emission. On the other hand, those outside the scope of the present invention are not satisfactory in appearance or luminous situation.

[Table 1] ─────────────────────────────────── Sample Mixing ratio (wt%) Mixing Percentage (wt%) Result NO. ----------- ) Visible light Haze value Anti-glare Luminous state: Dispersion (2): Luminescent fine powder Transmittance (%): Light scattering fine powder (%) ────────────────── ───────────────── 1 100: 0 100: 0:11 ○ (85) × (30) × × 2 99.5: 0.5 100: 2.2: 11 ○ (79) ○ (60) ○ ○ 3 99.0: 1.0 100: 4.5: 11 ○ (72) ○ (78) ○ ○ 4 98.0: 2.0 100: 9.1: 11 ○ (65) ○ (88) ○ ○ 5 97.5: 2.5 100: 11.4 : 11 ○ (62) ○ (90) ○ ○ 6 95.0: 5.0 100: 23.4: 11 ○ (52) ○ (93) ○ ○ 7 92.5: 7.5 100: 36.0: 11 × (44) ○ (94) − ○ 8 90.0: 10: 0 100: 49.4: 11 × (33) ○ (95) − ○ ───────────────── ─────────────────

[0040]

According to the present invention, in a frosted glass which reduces glare of sunlight and lighting and has a daylighting property, visibility at night or the like is obstructed, and an illuminating lamp can be used for disasters such as earthquakes and fires. Even when the lamp is malfunctioned due to damage, power failure, etc., the glass can be visually recognized effectively, and the decorative effect can be provided.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4G059 AA01 AC02 AC30 CA03 CA08 CB09 4G061 AA20 BA01 CB02 CD02 CD21 DA01 DA09

Claims (4)

[Claims] 1. A luminous frost-like coating formed by dispersing an inorganic luminous fine powder in a low-melting glass matrix on at least one side of a transparent glass plate, and the visible light transmittance of the glass with the frost-like coating is 50%. Above, the haze value is 50%
A luminous frosted glass characterized by the above. 2. A luminous frost-like coating comprising 100% by weight of a low melting glass matrix and 2 to 3 inorganic luminous fine powders.
The luminous frosted glass according to claim 1, wherein 0% by weight is dispersed. 3. The luminous phosphor according to claim 1, wherein the luminous frost-like coating is obtained by dispersing 25% by weight or less of inorganic light-scattering fine particles in 100% by weight of a low-melting glass matrix. Frosted glass. 4. A glass plate having a luminous frost-like coating formed thereon, another transparent glass plate is disposed opposite to the film-coated surface side, and the pair of transparent glass plate peripheral edges are integrated via a spacer. 4. The luminous frosted glass according to claim 1, 2 or 3, wherein the frosted glass is double-glazed.