JP3386918B2 - Coating liquid for ultraviolet absorbing film and glass article - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention mainly relates to an ultraviolet absorbing film which is basically a single layer film having an ultraviolet absorbing property and suitably having various functions such as coloring, heat insulation and radio wave transmission, and a method for producing the same. The present invention relates to a glass article coated with an ultraviolet absorbing film.

The present invention provides a useful ultraviolet absorbing film which can be used not only as architectural glass but also as automotive glass at least as a single plate, a method for producing the same, and a glass article.

[0003]

2. Description of the Related Art In recent years, in addition to providing clearing, coloring, heat insulation, ultraviolet ray blocking, and radio wave transmitting functions to architectural glass, the vehicle glass also shields solar radiant energy entering the interior of the vehicle to increase the temperature inside the vehicle and cool it. For the purpose of reducing the load, heat ray-shielding glass is used for vehicles, as well as those that have added ultraviolet ray shielding to make it both human and physical and environmentally friendly. Recently, in particular, the glass for vehicles has come to be required to have high transmission performance of various radio waves in addition to high heat ray ultraviolet shielding performance and high visible light transmittance in a light green color tone. Alternatively, the following are known as those in which ultrafine particles are dispersed in the coating layer of single-plate glass and those related thereto.

For example, Japanese Patent Application Laid-Open No. 2-296726 describes an ultraviolet absorbing granular material, which comprises titanium dioxide particles having an average particle diameter of 0.01 to 0.15 μ and a dense amorphous silica coating. , And a method for producing the same are disclosed, and it is described that a plastic composition in which the granular material is dispersed in a polymer material absorbs ultraviolet rays (UV) and is transparent to visible light.

Further, for example, Japanese Patent Application Laid-Open No. 2-8260 discloses a colored UV absorbing pigment, which is semiconductor fine particles having a particle size of 0.1 μm or less, preferably 10 to 100 nm, such as TiO ₂ , Zn.
On the surface of O ₂ , WO ₃ , SyTiO ₂ , CdS, SnO ₂ , CdSe, etc.
It discloses that a cyano-iron complex film having a thickness of 30 nm is provided, and that it is described as a transparent colored ultraviolet absorbing film.

Further, for example, Japanese Patent Laid-Open No. 6-48777 discloses that
An ultraviolet absorbing film and its manufacturing method are described, for example, a cerium oxide colloid sol having a particle diameter of 1000 nm or less,
For example, a silicon compound of the formula SiR _m (OR ') _4m (where R and R'are alkyl; m is 0 to 3) and, for example, the formula TiL _m (OR) _4-m (where L is chelate coordination). Child, R = alkyl group, m = 1 to 2) represented by a chelate ligand, a complexed alkoxide, and a titanium compound selected from the polymer as a main component, for example, a polymerization ratio of TiO ₂ / SiO ₂ = 1.0 or more, TiO ₂ / CeO ₂ =
Dissolve in an organic solvent so that the concentration becomes 0.1 to 3.0, apply a coating solution having a total solid content concentration of oxide of 1.0 to 15.0% by weight, and then dry and / or heat to form an ultraviolet absorbing film. Is disclosed.

[0007]

As described above, for example, the ultraviolet absorbing granular material disclosed in Japanese Patent Laid-Open No. 2-296726 is a film material for covering substances such as food, and a plastic composition used for agricultural films. 50% of the tensile strength of the film can be obtained by adding 0.01-5.0 wt% of the above UV-absorbing granular material to a material, specifically a polyolefin, and mixing it.
Even if the time to reach the drop can be made much longer than in the past, it is not a method of coating titanium dioxide ultrafine particles coated with dense amorphous silica on the glass surface, but a pale coloring, especially a pale yellow type It is not a color tone.

Further, for example, the colored UV-absorbing pigment described in Japanese Patent Application Laid-Open No. 2-8260 requires the use of semiconductor fine particles, and a resin film containing bead-shaped spacers must be sandwiched between glass substrates to form a laminated glass. However, it does not form a Prussian blue, is not applied as a single film layer on the glass surface, and the color tone is not a light yellowish color tone.

Further, for example, the ultraviolet absorbing film and the method for producing the same disclosed in Japanese Patent Laid-Open No. 6-48777 have a single film layer but are merely an ultraviolet absorbing film and exhibit an accompanying antireflection property. However, it is not always a simple and inexpensive coating film means, not a film intended for coloring.

[0010]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and it is an ultraviolet absorbing film containing the specified titanium yellow ultrafine particles as a main component, and the specified titanium yellow ultrafine particles. Due to the manufacturing method of the ultraviolet absorbing film using the coating liquid consisting of fine particles and the specified oxide, and the glass article in which a single film layer made of these is formed on the glass substrate, the heat insulating performance, the ultraviolet blocking performance and the radio wave transmission are achieved. It is possible to impart functional properties such as performance, balance control of the color tone of coloring and transparency, prevent reflection and glare, and obtain excellent quality. It is cheap and easy to do, and it can be freely adapted to the size and shape of glass, and it can be coated on a blue glass substrate to obtain a light green color tone glass, etc. Built window material of course also be sufficiently applied to automotive window material, and provides a useful ultraviolet absorbing film and a manufacturing method and a glass article that an optimum recent needs.

That is, the present invention is characterized in that the main component is titanium yellow-ultrafine particles containing at least one or more of nickel oxide, barium oxide, and chromium oxide in a titanium oxide-antimony oxide system. Absorption film.

In addition, as the ultraviolet absorbing oxide ultrafine particles, the titanium yellow ultrafine particles having an average particle size of 100 nm or less are contained in an amount of 5% by weight or more in terms of oxide, and silicon oxide or titanium oxide is used as a binder of the ultrafine particles. The ultraviolet absorbing film described above, which is a film containing 95% by weight or less of an oxide composed of at least one of zirconium oxide and aluminum oxide.

Further, a coating solution containing titanium yellow ultrafine particles and an oxide composed of at least one selected from silicon oxide, titanium oxide, zirconium oxide and aluminum oxide as a main component is applied and heated. A method for producing an ultraviolet absorbing film, which comprises subjecting the film to a strengthening and / or bending treatment to form a film.

Further, the titanium yellow ultrafine particles are
Characterized by a titanium yellow-ultrafine particle containing at least one of nickel oxide, barium oxide, and chromium oxide in a titanium oxide-antimony oxide system as a main component, and the average particle diameter of the ultrafine particle is 100 nm or less. The method for producing the ultraviolet absorbing film described above.

Furthermore, the oxide is Si (OR) _m R
_n , Ti (OR) _m L _n , Zr (OR) _m L _n , Al (OR) _x L _y (however, m + n = 4, m = 1 to 4, n = 0 to 3, x + y = 3, x = 1 to 3,
y = 0 to 3, R = C _{1 to} C ₄ alkyl group, L = ligand) or a polymer containing at least one of these polymers, which is used for the above-mentioned ultraviolet absorption. Membrane manufacturing method.

Further, a glass article having the ultraviolet absorbing film described above applied on the surface of a glass substrate. Further, the above-mentioned glass article is characterized in that a light yellowish color ultraviolet ray absorbing film is provided on the surface of the glass substrate having a light blue color tone so as to exhibit a light green color tone.

Furthermore, the glass article described above is characterized in that the glass article has a heat insulating property. Furthermore, the glass substrate having a light blue color tone has a refractive index (n ₁ ) of 1.5.
A float glass having a blue-color tone of 0 to 1.53, in which the content of the titanium yellow ultrafine particles is 5 to 11% by weight on the surface of the glass, silicon oxide, titanium oxide, zirconium oxide, and oxidation. The refractive index (n ₂ ) is 1.47 to 1.80 when the film is prepared by adjusting the content of at least one oxide in aluminum to 95 to 89% by weight. The above-mentioned glass articles are provided, each of which is a glass for vehicles that is subjected to a film and exhibits a light green color tone.Here, as described above, the titanium oxide-antimony oxide-based oxide is oxidized. The main component of titanium yellow-ultrafine particles containing at least one of nickel, barium oxide and chromium oxide is titanium oxide-antimony oxide composite oxide system, nickel oxide, barium oxide. 3 or more containing at least one of chromium and chromium oxide.
By including the original composite oxide, it is possible to coat the glass surface with excellent ultraviolet absorption performance and pale yellowish color tone, as well as optical characteristics such as transparency and heat insulation of the coating, or radio wave transmission performance and durability. To secure various physical properties,
Further, it is possible to obtain a light greenish color tone by combining with blue glass.

For example, as titanium yellow-ultrafine particles,
Titanium oxide 60-70% by weight and antimony oxide 15-17% by weight
In the system of 5 to 7% by weight of at least one kind of nickel oxide, barium oxide and chromium oxide,
Specifically, for example, # 3120 (TiO ₂ 66.1wt% -Sb ₂ O ₃ 16.4-NiO6.5wt%) manufactured by Dainichiseika Kogyo Co., Ltd.
3150 (TiO ₂ 67.8 wt% -Sb ₂ O ₃ 16.3-Cr ₂ O ₃ 5.9 wt%) and the like.

The titanium yellow ultrafine particles have an average particle size of 100 nm or less. If the average particle size exceeds 100 nm, the transparency and film strength of the coating film will be reduced, and the dispersion liquid for coating may be optionally treated with alcohol or water. This is because it cannot be diluted and used, and is preferably about 50 nm or less, more preferably about 20 nm or less.

Further, a dispersion medium of titanium yellow-ultrafine particles,
The dispersion method is not particularly limited and various ones can be used, for example, titanium yellow-ultrafine particles are added to a solvent such as water or alcohol, and an acidic substance or a basic substance is added to adjust the pH. After that, the sand mill,
It can be obtained by dispersing with a commercially available powder disperser such as a colloid mill or a homogenizer or an ultrasonic disperser.

Further, the ultraviolet absorbing oxide ultrafine particles contain the titanium yellow ultrafine particles in an amount of 5% by weight or more in terms of oxide, and silicon oxide, titanium oxide, zirconium oxide or aluminum oxide is used as a binder for the ultrafine particles. Is a film containing 95% by weight or less of at least one kind of oxide, and the coating liquid for the film is at least one selected from the above-mentioned titanium yellow ultrafine particles and silicon compounds, titanium compounds, zirconium compounds, and aluminum compounds. Obtained by mixing with a solution containing seeds and diluting with an organic solvent such as alcohol to the required concentration.

Specifically, Si (OR) _m R _n , Ti (OR) _m L
_n , Zr (OR) _m L _n , Al (OR) _x L _y (however, m + n = 4, m =
1-4, n = 0-3, x + y = 3, x = 1-3, y = 0-3, R = C ₁
To C ₄ alkyl group, L = ligand) or at least one of these polymers, or a partial hydrolyzate thereof is preferably added to the titanium yellow ultrafine particle dispersion.

Furthermore, these organometallic compounds are
Not only does it act as a binder, but it also binds to the hydroxyl groups on the surface of the oxide particles in the coating liquid and covers the oxide particles, so that the dispersibility of the oxide particles in the liquid is significantly improved. Needless to say, the interference color due to the reflection of the coating can be reduced by making the refractive index of the coating similar to that of the base glass.

Further, a glass article in which the above-mentioned ultraviolet absorbing film is applied on the surface of a glass substrate, particularly a light green-based color tone obtained by applying an ultraviolet absorbing film in the light-yellowish tone on the surface of a glass substrate in the light-blue tone The glass article thus obtained has a heat insulating property.

Furthermore, the glass article is a float glass having a blue-tone color, and the glass substrate having a light-blue hue has a refractive index (n ₁ ) = 1.50 to 1.53. The content of the titanium yellow ultrafine particles is adjusted to 5 to 11% by weight, and the content of the oxide composed of at least one of silicon oxide, titanium oxide, zirconium oxide and aluminum oxide is adjusted to 95 to 89% by weight. The film is formed with a refractive index (n ₂ ) of 1.47.
It is a glass for vehicles which has a light yellowish color ultraviolet ray absorbing film of 1.80 to 1.80 and has a light green color tone.

Further, the glass substrate is a normal plate glass made of soda lime silicate glass, which is commonly used for automobile and architectural glass, a so-called float plate glass, and the like, tempered glass and similar glass, laminated glass and the like. Needless to say, it can be used as various kinds of flat glass products such as double glazing and flat plates or bent plates. The plate thickness is, for example, about 1.0 mm or more and about 12 mm or less, preferably about 2.0 mm or more and about 10 mm or less for construction, and about 1.
It is preferably about 5 mm or more and about 6.0 mm or less, and more preferably about 2.0 mm or more and about 4.0 mm or less.

The thickness of the ultraviolet absorbing film is as follows.
About 100-2000 nm, preferably about 200-1000 nm
It is a degree. For example, if the film thickness is less than 100 nm, the ultraviolet absorption performance tends to decrease, and if it exceeds about 2000 nm, the film strength decreases and the occurrence of fine cracks during firing is not preferable. Also, as the refractive index of the ultraviolet absorbing film
It is about 1.47 to 1.80, preferably about 1.50 to 1.77.

Further, a coating liquid prepared by adding a metal alkoxide as a binder component to the dispersion liquid of the titanium yellow ultrafine particles described above is heated and then heated to form a highly hard pale yellow color tone film having an ultraviolet absorbing property. Can be formed.

The method of coating the glass substrate is not particularly limited, and examples thereof include a dipping method, a spin coating method, a roll coating method, a spray method, a screen printing method and a flexographic printing method.

[0030]

As described above, the ultraviolet absorbing film, the method for producing the same, and the glass article of the present invention are provided with an ultraviolet absorbing film containing a specific titanium yellow-ultrafine particle as a main component, and an oxide specified with the titanium yellow-ultrafine particle. The main component is and
A specific titanium yellow-ultrafine particle is obtained by a method for producing an ultraviolet absorbing film which is formed by applying a coating solution, heat-strengthening and / or bending the film, and a glass article obtained by coating the ultraviolet absorbing film on a glass substrate. It is possible to take advantage of the light yellowish color tone and outstanding ultraviolet (UV) absorption performance of the above, and to make the sol-gel solution mainly composed of silica (SiO ₂ ) uniform with the specific titanium yellow-ultrafine particles as the main component. It has been found that it can be dispersed.

Further, the solution made of these can be coated as a single film by a general coating method such as a dipping method or a spin coating method, and the film can be finished by heat strengthening and / or heat bending treatment after precoating. Since it is possible to apply it more than once and to adjust the film thickness to prevent interference color, it is possible to simplify the process and improve the yield. Further, it has durability such as abrasion resistance and chemical resistance. Was also excellent.

Furthermore, since the transmitted color of the ultraviolet absorbing film of the present invention is a pale yellowish color tone, the so-called so-called glass component composition which produces a light greenish color tone by forming a film on a blue glass substrate. It was possible to obtain a glass that has the same color tone and performance as the ultraviolet or / and ultraviolet absorbing glass.

Further, it should have an excellent solar radiation transmittance that enhances the heating and cooling effect and improves the habitability, and a remarkable ultraviolet ray shielding that is kind to the environment and people, and also has a relatively high visible light transmittance. In addition, it is possible to eliminate the influence of reception obstacles in broadcasting such as AM radio waves, FM radio waves, TV radio wave bands, etc., and because it has the same radio wave transmission performance as ordinary float glass, it can be used for vehicle TVs and radios. ,
It is possible to reduce the radio wave interference such as ghost phenomenon without deteriorating the reception performance of the glass antenna for mobile phones and the like, and let the original glass antenna performance be exhibited to create a comfortable environment inside and outside the vehicle. It can be ensured that the blue glass can exhibit a commercially available light green color tone as a glass substrate, and as a building window material, in particular, an automobile window material, for example, a front window, a rear window or. It is intended to provide a useful ultraviolet absorbing film which can be sufficiently applied to side windows, sunroofs, etc. and which is most suitable for recent needs, a method for producing the same, and a glass article.

[0034]

EXAMPLES The present invention will be specifically described below with reference to examples. However, the present invention is not limited to the embodiment.

Example 1 First, a coating liquid is prepared as follows. DAI PILOXIDE TM # 3120 (Titanium Yellow; TiO ₂ 66.1wt% -Sb
₂ O ₃ 16.4 wt% -NiO 6.5 wt%: UV absorber) 20.0 wt%, TSL8
311 (Silane coupling agent) 1.0wt%, Ethocel 7CP
(Ethyl cellulose) 0.5 wt%, Isopropyl alcohol
78.5 wt% of the resin was dispersed and mixed in a SG mill (disperser) using 0.5 mm zircon beads for about 3 hours to prepare a dispersion solution of UV absorbing fine particles, which was designated as solution A.

Then, Si (OC ₂ H ₅ ) ₄ 17.3 wt%, nitric acid 1.0 wt
%, Water 1.0 wt%, solution A 25.0 wt%, and isopropyl alcohol 55.7 wt% were mixed by a propeller stirrer and allowed to stand at room temperature for about 1 day to mature the solution. Was used as the solution B), and then the uniform solution B was used as the coating solution.

A soda lime glass plate (blue-
Color system Float glass about 3.5 mm, Tr about 79.8%, Ts about 63.7%, Tuv about 37.3%, Pe about 3.4%), mask one side and apply it on the other side by dipping method, After drying at about 200 ℃ for about 30 minutes, about 3 at 650 ℃
It was heat strengthened for a minute. A titanium yellow-fine particle dispersed silica film having a thickness of about 340 nm was obtained.

The following items were evaluated for the obtained glass plate with a titanium yellow-fine particle dispersed silica film. [Optical characteristics]: Spectrophotometer (U4000 type, manufactured by Hitachi Ltd.)
Transmittance between wavelength 340 and 1800 nm is measured with JIS Z 8722.
And JIS R 3106 or JIS Z 8701, visible light transmittance Tv
(%) (380 to 780 nm), solar radiation transmittance Ts (%) (340 to 1800n
m), and UV transmittance according to ISO 9050 Tuv (%) (282.5 to 3
(77.5 nm), stimulation purity (%), color tone, etc. were determined. [Haze]: The haze value H was determined according to JIS K6714. 3% or less for construction, 1 for automobiles
% Or less was accepted. [Radio wave permeability]: Reflection loss value (d in the range of radio waves 10 to 1000MHz (d
Contrast B) with a normal clear glass (FL3t) single plate product with a plate thickness of 3 mm. The absolute value (ΔdB) of the difference was judged to be within 2 dB. [Chemical resistance]: Acid resistance: Immersed in 1N hydrochloric acid at room temperature for 2 days. Alkali resistance: Immersed in 1N caustic soda solution at room temperature for 2 days. Those with no abnormality were accepted. [Heat resistance]: After boiling in boiling water at 100 ° C. for about 6 hours, except for 10 mm around the periphery, there was no abnormality such as generation of bubbles, clouding, or cracking of glass, and the result was passed. [Also called boiling resistance] [Moisture resistance]: After leaving for 2 weeks in a controlled condition of 50 ± 2 ° C and relative humidity of 95 ± 4%, there should be no abnormalities such as foaming, clouding, and glass cracking. I passed. [Electrical characteristics]: Mitsubishi Yuka's surface high resistance meter (HIRESTA HT
-210).

(Sheet resistance value) (M Ω / port). 10 MΩ /
Passed more than mouth. [Abrasion resistance]: A taper-wear tester (wear wheel CS-10F, load 500gf, 1000 rotations) based on JIS R 3212 and JIS R 3221.

As a result, the spectral transmittance curve shown in FIG. 1 is obtained, the visible light transmittance Tv is about 78.0%, and the solar radiation transmittance is
Ts is about 61.0%, UV transmittance Tuv is about 13%, stimulation purity Pe is about 4.2%, color coordinates of transmitted color by D ₆₅ light source (x, y) = (0.308,0.333), glass Color coordinate of surface side reflection color (x, y) = (0.301, 0.335), color coordinate of film surface side reflection color (x, y
y) = (0.230,0.332) and neutral bluish green color tone, no glare due to reflection, and our green color tone glass (3.5 mm thickness)
Tv of about 79%, Ts of about 57%, ultraviolet transmittance of about 30%, compared to the color coordinates of the transmitted color (x, y) = (0.308, 0.334), except for the ultraviolet transmittance, it is almost the same. Yes, it was possible to significantly reduce the ultraviolet transmittance.

Further, the haze value H is about 0.5%, and the haze value by the Taber test is about ΔH 4.2%, and in addition to sufficiently excellent optical characteristics such as ultraviolet ray shielding property and heat ray shielding property, it is remarkably high. It has a high surface resistivity and is almost the same as single glass, for example 80MHz (FM radio wave band), about 520-1630KH
z (AM radio frequency band), etc., in particular, shows the same level of radio wave transmission as ordinary single-plate glass, and is sufficiently stable and has excellent adhesiveness, heat resistance, and moisture resistance. It is environmentally friendly and highly safe, and can comfortably receive various radio waves including the AM band. It can be fully adopted as a single glass plate for building window glass, etc., and can also be used for automobile window glass. It was something that could be done. The refractive index of the film was about 1.80.

In addition, when various other properties such as weather resistance (for example, about 1000 hours with a Sunshear weather meter: visible light transmittance does not substantially change) were evaluated, all of them passed. there were.

Example 2 First, as in Example 1, a coating liquid is prepared as follows. Example 1 of Dipiroxide TM # 3120 (titanium yellow; UV absorber) 20.0 wt%, TSL8123 (silane coupling agent) 1.0 wt%, ethanol 79.0 wt%
In the same manner as the above, using a 0.5 mm zircon bead on an SG mill (dispersing machine), the mixture was dispersed and mixed for about 4 hours to prepare a dispersion solution of UV absorbing fine particles, which was designated as solution C.

Then, CH ₃ Si (OCH ₃ ) ₃ 30.0 wt%, acetic acid 1.0
wt%, water 1.0 wt%, C liquid 47.7 wt%, isopropyl alcohol 20.3 wt% were mixed by a propeller stirrer and allowed to stand at room temperature for about 48 hours to age the solution (this Was used as the D liquid), and the uniform D liquid was used as the coating liquid.

This solution was applied to one surface of a soda lime glass plate (blu-color tint float glass about 3.5 mm) by the dipping method as in Example 1, dried at about 100 ° C. for about 15 minutes, and then dried. Baking at 500 ℃ for about 30 minutes, film thickness about 68
A 0 nm titanium yellow-fine particle dispersed silica film was obtained.
The glass plate with the titanium yellow-fine particle dispersed silica film was heat-cooled at about 670 ° C. for about 3 minutes for heat strengthening.

Each item was evaluated in the same manner as in Example 1 with respect to the obtained tempered glass plate with a titanium yellow-fine particle dispersed silica film. As a result, Tv is 74.0%, Ts is 58.0%, Tuv
Shows excellent optical characteristics as in Example 1 such as 15%, stimulation purity Pe is about 4.0%, and color coordinates (x, y) = (0.309,0.338) of the transmitted color by the D ₆₅ light source, Color coordinates (x, y) = (0.302,0.333) of the reflection color on the glass surface, color coordinates (x, y) = (0.295,0.337) of the reflection color on the film surface, and a light gray neutral tone, and glare due to reflection None, our green color glass (for example, Nomargreen) toned glass (3.5mm thickness)
Compared with, the UV transmittance was almost the same except the UV transmittance, and the UV transmittance could be significantly reduced.

Moreover, the haze value ΔH by the Taber test
Was 3.7%, which was expected to show a good balance of physical properties such as radio wave transmission and quality. The refractive index of the film is 1.
It was about 72.

In other words, it has excellent habitability, is highly safe for the driver, passengers and the environment, is highly safe, and can comfortably receive various radio waves including the AM band, and can be sufficiently used as a single glass plate, and is a window glass for construction. Needless to say, it could be sufficiently applied to automobile window glasses, especially automobile window glasses equipped with antenna conductors at the same time, and it was possible to sufficiently meet expectations.

Example 3 First, in the same manner as in Example 1, a coating liquid is prepared as follows. Dipyroxide TM # 3120 (Titanium yellow; UV absorber) 20.0 wt%, TSL8123 (Silane coupling agent) 1.0 wt%, Isopropyl alcohol 79.0 wt%
Was mixed with a SG mill (disperser) using 0.5 mm zircon beads for about 4 hours in the same manner as in Example 1 to prepare a dispersion solution of UV absorbing fine particles, which was designated as solution E.

Then, Si (OCH ₃ ) ₄ 23.4 wt% and hydrochloric acid 0.2 wt
%, Water 1.6 wt%, methanol 13.3 wt%, anhydrous zinc chloride 1
The composition of 5.9 wt%, trimethylboron 18.2 wt% and E solution 17.5 wt% was mixed by a propeller stirrer and allowed to stand at room temperature for about 2 days to age the solution (this was designated as solution F), and then homogenized. Liquid F was used as the coating liquid.

As in Example 1, this solution was coated on one side of a soda lime glass plate (blu-color tint float glass about 3.5 mm) by the dipping method, dried at about 100 ° C. for about 15 minutes, and then dried. Baking at 500 ℃ for about 30 minutes, film thickness about 88
A 0 nm titanium yellow-fine particle dispersed silica film was obtained.
The glass plate with the titanium yellow-fine particle dispersed silica film was heat-cooled at about 670 ° C. for about 3 minutes for heat strengthening.

Each item was evaluated in the same manner as in Example 1 for the obtained tempered glass plate with a titanium yellow-fine particle dispersed silica film. As a result, Tv is 73.0%, Ts is 56.0%, Tuv
13%, etc. show excellent optical characteristics as in Example 1, the stimulation purity Pe is about 3.8%, and the color coordinates (x, y) = (0.310,0.339) of the transmitted color by the D ₆₅ light source, Color coordinates (x, y) = (0.310,0.330) of the reflection color on the glass surface, color coordinates (x, y) = (0.306,0.336) of the reflection color on the film surface, and a light gray neutral tone, and glare due to reflection None, our green color glass (for example, Nomargreen) toned glass (3.5mm thickness)
Compared with, the UV transmittance was almost the same except the UV transmittance, and the UV transmittance could be significantly reduced.

Moreover, the haze value ΔH by the Taber test
Was excellent at 2.6%, and was expected to show a good balance of radio wave transmission and physical properties such as chemical resistance and boiling resistance. The refractive index of the film was about 1.77.

In other words, it has excellent habitability, is highly safe for the driver, passengers and the environment, and is highly safe, and can comfortably receive various radio waves including the AM band, and can be sufficiently used as a single plate glass, and is a window glass for construction. Needless to say, it could be sufficiently applied to automobile window glasses, especially automobile window glasses equipped with antenna conductors at the same time, and it was possible to sufficiently meet expectations.

[0055]

As described above, according to the present invention,
It has excellent heat insulation performance that enhances the heating and cooling effect and improves habitability, as well as exceptional UV protection that is kind to the environment and people, has an extremely low haze value, ensures excellent transparency, and has a reflective and glare sensation. It is possible to provide prevention in a well-balanced manner and reduce reception obstacles in various broadcasts, with the same radio wave transmission performance as that of ordinary float glass without degrading the reception performance of the glass antenna.
It is possible to reduce radio wave interference such as strike phenomenon, to ensure a comfortable environment inside and outside the vehicle, and to use green glass as a glass substrate of blue glass to provide a green color tone. As a material, it can be applied to window materials for automobiles, etc., and is a single-useful UV-absorbing film which is most suitable for recent needs. is there.

[Brief description of drawings]

FIG. 1 is a diagram showing a transmittance curve measured by a spectrophotometer and graphed in Example 1 of the present invention, where 1 is Example 1 of the present invention, 2 is commercially available blue glass, and 3 is commercially available pale It is green glass.

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Claims (5)

(57) [Claims] 1. Titanium yellow having an average particle size of 100 nm or less.
Si (OR) _m R _n of metal alkoxide in ultrafine particle dispersion ,
Ti (OR) _m L _n , Zr (OR) _m L _n , Al (OR) _x L _y (however, m + n
= 4, m = 1 to 4, n = 0 to 3, x + y = 3, x = 1 to 3, y = 0 to
3, R = C _{1 to} C ₄ alkyl group, L = ligand) or their weight
A coating containing at least one kind of coalescence
Liquid, and the titanium yellow is titanium oxide 60-
70% by weight, 15 to 17% by weight of antimony oxide,
In addition, in nickel oxide, barium oxide, chromium oxide
5 to 7% by weight of at least one kind
A coating liquid for forming an ultraviolet absorbing film. 2. The ultraviolet ray according to claim 1 on the surface of a glass substrate.
Purple obtained by applying the coating liquid for absorbing film and baking
A glass article having an external line absorbing film formed thereon. 3. The ultraviolet ray according to claim 1 on the surface of a glass substrate.
Apply the coating liquid for forming the absorption film and strengthen the glass substrate.
UV absorbing film was formed by denaturing and / or bending treatment
Glass articles . 4. A glass substrate having a light blue color tone, which is formed after film formation.
Is characterized by having a light green color tone
The glass article according to claim 2 or claim 3 . 5. A light blue glass substrate has a refractive index (n1) =
A float glass having a blue color tone of 1.50 to 1.53, wherein the content of titanium yellow ultrafine particles on the glass surface is 5 to 11% by weight, silicon oxide, titanium oxide, and oxide. The content of at least one oxide of zirconium and aluminum oxide is 95 to 89% by weight.
The refractive index (n2) adjusted to 1.47 to 1.80 is a glass for vehicles that has a light green color tone and is formed with an ultraviolet light absorbing film of a light yellow color tone that does not shine. The glass article according to claim 4, which is characterized in that: