JP3094852B2 - Heat ray shielding glass for vehicles - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat shielding glass suitable for use in a window of a vehicle such as an automobile.

[0002]

2. Description of the Related Art In recent years, heat ray reflective glass has been used not only for buildings but also for windows of vehicles such as automobiles for the purpose of reducing the cooling load or the heat and heat of the sun.

[0003] Here, the heat ray reflective glass is formed by forming a tin oxide, a metal chromium multilayer, a titanium oxide, a nitride multilayer, etc. on the surface of a glass plate having an ordinary soda lime composition. By using the interference effect to increase the surface reflectance and reflect solar energy, the inflow of solar radiation energy into automobiles and the like is suppressed.

On the other hand, heat-absorbing glass, which suppresses the inflow of solar radiation energy by adding a small amount of coloring components to a normal soda-lime glass plate to increase the absorption capacity of solar energy, is also widely used in vehicles such as automobiles. I have.

[0005]

However, the conventional heat-reflective glass or heat-absorbing glass has been designed for coatings or trace components with the window of the building used as a part to be used. It did not always satisfy the specific performance required for use in vehicles.

An object of the present invention is to provide a heat ray shielding glass particularly suitable for vehicles such as automobiles.

[0007]

SUMMARY OF THE INVENTION In a vehicle such as an automobile, the value of the solar transmittance of the glass used for the window is determined by the fact that the ratio of the opening (window) to the indoor space is relatively large. Is particularly desired to be not more than a certain value. On the other hand, considering the demand for weight reduction of vehicles such as automobiles, as in architectural glass, increasing the glass thickness increases the solar absorption effect of trace coloring components in the glass to reduce the solar transmittance. Is not appropriate. In general, the visible light transmittance also decreases as the solar transmittance decreases, but it is desirable that the visible light transmittance is equal to or more than a certain value in order to secure a view and a view from inside the vehicle. Further, it is important to satisfy the above-mentioned characteristics and at the same time provide a color tone (especially a reflection color tone) suitable for a vehicle.

The present invention has been completed as a result of applying the above requirements to an actual vehicle space and conducting various studies. The structure of the present invention is one of the main surfaces of a glass plate having a thickness of 3 to 5 mm. A visible light reflectance of the surface opposite to the surface on which this coating is formed is in the range of 10 to 30%, and the visible light transmittance is 15%. ５５55% and the solar radiation transmittance is 1
0-50% and less than or equal to the visible light transmittance, the reflection color tone on the opposite side is green, and the glass plate is expressed in weight%, and is essentially 65-80%. SiO ₂ 0 to 5% of Al ₂ O _{3 0~5%} of B ₂ O ₃ 0~10% 5~15% of MgO in CaO 10 to 18% of Na ₂ O 0 to 5% of K ₂ O. 5 to 15% MgO + CaO 10-20% Na ₂ O + K ₂ O Basic glass composition and 0.40 in terms of Fe ₂ O ₃ as a coloring component
1.0% of iron oxide, from 0 to 0.85% of TiO _2, 0 to
0.001% of CoO, and consist from 0 to 1.4% of CeO _2, the ratio of FeO / total iron oxide is made of a vehicle heat-reflecting glass, which is a 0.18 to 0.37.

The coating comprising the above oxide is preferably
It contains an oxide of at least one metal of iron, chromium and nickel and a cobalt oxide, and more preferably has a coating surface resistance value of more than 10 ⁴ Ω / square.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS As a method for forming an oxide film constituting the present invention on a glass substrate, a film can be formed by a vacuum deposition method, a sputtering method, a coating method or the like. A so-called thermal film formation method such as a chemical vapor deposition method (CVD method) is preferable. In the thermal film formation method, a spray method such as a solution spray method, a dispersion liquid spray method, or a powder spray method is preferred. Preferred from the point.

Among the above-mentioned methods, a solution containing a compound of a desired metal may be sprayed onto a high-temperature glass substrate in the solution spraying method. Instead, a dispersion in which fine particles of a metal compound are dispersed in a solution or a solvent may be used as powder of a metal compound. In addition, as these spraying methods, a liquid in which each component is mixed in advance may be sprayed as fine droplets or powder, or each component may be separately sprayed and reacted simultaneously as droplets or powder. Further, in the chemical vapor deposition method, a film-forming vapor containing the above compound may be used.

Raw materials that can be used for such a so-called spray method are exemplified below. That is,
Cobalt compounds include acetylacetone cobalt (both divalent and trivalent salts are acceptable), cobalt acetate, cobalt chloride, cobalt benzoate, cobalt borate, cobalt bromide, cobalt nitrate, cobalt fluoride, cobalt iodide, and cobalt oxalate. , Cobalt phosphate, cobalt phosphite, cobalt stearate, cobalt sulfate and the like, and nickel compounds include nickel acetylacetone, nickel bromide, nickel fluoborate, nickel fluoride, nickel fluosilicate, nickel formate, nickel hydroxide, Examples include nickel iodide, dipropionylmethane nickel, nickel nitrate, nickel acetate, nickel chloride, nickel stearate, nickel sulfamate, nickel sulfate, and the like.
As the chromium compound, acetylacetone chromium, chromium acetate, chromium chloride, chromium chloride, chromium formate, chromium fluoride, chromium ammonium sulfate,
Chromic hydroxide, chromic nitrate, chromic phosphate,
Potassium chromium sulfate, ferric chromium sulfate and the like, and iron compounds include iron acetylacetone, ferrous chloride, ferric chloride, ferric citrate, ferric ammonium oxalate, ammonium ferric sulfate, and fluoro Iron borate, ferric fluoride, iron fluosilicate, ferrous lactate, ferric nitrate, ferrous oxalate, ferrous phosphate, ferric phosphate, ferrous sulfate, ferric sulfate, tartaric acid One iron can be used.

A film formed by a thermal film forming method has excellent durability against heat treatment and can be subjected to a strengthening treatment or the like after the film is formed, and thus is suitable as a heat ray shielding glass for vehicles. That is, the heat ray shielding glass according to the present invention is obtained by melting and molding a glass plate so as to have the above-mentioned predetermined composition, and coating an oxide film on one of the main surfaces of the glass plate so as to have the above-mentioned predetermined optical characteristics and the like. It is formed by a thermal film forming method such as a spraying method, the coated glass sheet is cut into a predetermined size and shape, and the cut glass sheet is heated to a temperature from a strain point to a softening point to form and / or By performing the strengthening treatment, it is possible to manufacture efficiently. Furthermore, if the spray method is performed on a glass ribbon by the float method, the film can be continuously formed while utilizing the residual heat during glass production, so that the production efficiency can be further increased.

The coloring components of the glass plate constituting the present invention will be described below. Iron oxide in the glass exists in a state of Fe ₂ O ₃ and FeO. If the total iron oxide is less than 0.40% in terms of Fe ₂ O ₃ , the effect of absorbing infrared light is small and the visible light transmittance is high. On the other hand, if it exceeds 1.5%, the decrease in the visible light transmittance is extremely undesirable.

In order to obtain a desired solar radiation transmittance under such a total iron content, the lower limit of the ratio of FeO / total Fe ₂ O ₃ is set to 0.18 or more and the upper limit is set to 0.37 or less. It is important to.

In the case where it is necessary to shield ultraviolet rays of a certain value or more in addition to the heat ray shielding ability, TiO.sub.
₂ , CeO ₂ can be added. However, the concentration of these components is too high, the glass becomes too large absorption of the shorter wavelength side of visible light can not be obtained a desired color tone yellowish, 0.85% for the TiO ₂ or less, C
The content of eO ₂ is preferably 1.4% or less.

CoO in the glass plate is appropriately added up to 0.001% in order to obtain a green color tone when TiO ₂ is present and to reduce the visible light transmittance. The change of the glass to a yellowish color tone due to the addition of TiO ₂ as described above can be suppressed by the addition of CoO.

By setting the surface resistance of the coating constituting the present invention to a value exceeding 10 ⁴ Ω / square, the adhesion of dust due to electrostatic attraction can be suppressed. Further, by setting the surface resistance of the coating to a value exceeding 100 kΩ / square, the influence on the impedance of the antenna element provided on the coating can be reduced. From such a viewpoint, it is more preferable that the surface resistance value of the coating be 1 MΩ / square or more.

The thickness of the coating is preferably 10 to 100 nm. By adjusting the thickness in accordance with the composition of the coating, not only the reflection tone on the opposite side of the coating can be made green, but also the transmission tone. Can be made green.

[0020]

The present invention will be described in more detail with reference to the following examples.

To a typical soda-lime-silica glass batch component, ferric oxide, titanium oxide, cobalt oxide, cerium oxide and a carbon-based reducing agent are appropriately mixed, and the raw material is heated to 1500 ° C. in an electric furnace and melted. did. After melting for 4 hours, the glass substrate was poured out onto a stainless steel plate, gradually cooled to room temperature, and further polished to form a glass plate having a thickness shown in Table 1. Table 1 shows the content of each coloring component in the glass plate.

Next, the glass was washed and dried to obtain a substrate. The substrate was fixed by a hanging tool, held in an electric furnace set at 650 ° C. for 5 minutes, and then taken out. Toluene was used as a component shown in Table 1 with acetylacetonate of a metal shown in Table 1 such as trivalent cobalt. The raw material liquid adjusted and dissolved so as to be as described above was sprayed on the substrate using a commercially available spray gun to form an oxide film.

For these glasses, the visible light transmittance,
Visible light reflectance, solar radiation transmittance, surface resistance and a ^* , b ^*
(Chromaticness Index) was measured. Table 2 shows each characteristic value of the obtained glass.

[0024]

[Table 1]

[0025]

[Table 2]

[0026]

According to the present invention, it is possible to provide a heat ray shielding glass satisfying various conditions suitable for a vehicle (particularly for an automobile). That is, while reducing the solar radiation transmittance without increasing the glass thickness, while securing a certain visible light transmittance determined to be necessary in consideration of the relative relationship between the brightness inside and outside the vehicle, Since the transmission is not controlled only by the reflection of the coating film, the visible light reflectance is also controlled to a certain value or less to suppress the glare and the adverse effects due to the light reflection to the surrounding vehicles.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of a heat ray shielding glass according to the present invention.

[Explanation of symbols]

 1: glass plate, 2: oxide coating

────────────────────────────────────────────────── ─── Continuation of front page (56) References JP-A-6-321577 (JP, A) JP-A-6-234544 (JP, A) JP-A-6-234543 (JP, A) JP-A-6-234543 40741 (JP, A) Table 7-508971 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C03C 3/078 B60J 1/00 C03C 3/091 C03C 17/23

Claims (3)

(57) [Claims] 1. A heat ray reflective glass having a coating made of an oxide formed on one of the main surfaces of a glass plate having a thickness of 3 to 5 mm, the visible surface being opposite to the surface on which the coating is formed. The light reflectance is in the range of 10 to 30%, the visible light transmittance is in the range of 15 to 55%, and the solar transmittance is 10 to 30%.
50% and less than or equal to the visible light transmittance, the reflection color tone on the opposite surface is green, and the glass plate is essentially expressed by 65% to 80% by weight. SiO ₂ 0 to 5% of Al ₂ O _{3 0~5%} of B ₂ O ₃ 0~10% 5~15% of MgO in CaO 10 to 18% of Na ₂ O 0 to 5% of K ₂ O. 5 to 15% MgO + CaO 10-20% Na ₂ O + K ₂ O Basic glass composition and 0.40 in terms of Fe ₂ O ₃ as a coloring component
1.0% of iron oxide, from 0 to 0.85% of TiO _2, 0 to
0.001% of CoO, and 0 to 1.4% of consists CeO _2, FeO / total ratio of iron oxide vehicular heat ray shielding glass, which is a 0.18 to 0.37. 2. The heat ray shielding for a vehicle according to claim 1, wherein the coating made of the oxide contains an oxide of at least one metal of iron, chromium and nickel and cobalt oxide. Glass. 3. The resistance value of the oxide film is 10 ^4.
The heat ray shielding glass for a vehicle according to claim 1, wherein the heat ray shielding glass is larger than Ω / square.