JPH03275533A - Heat ray shielding glass - Google Patents

Abstract

PURPOSE:To provide the glass having a high visible light transmissivity and a neutral color tone and capable of being used as a single sheet by coating a transparent base glass successively with a layer of the nitrides of Ti, Zr, etc., a TiO2 layer and a transparent layer with its refractive index specified. CONSTITUTION:This heat ray shielding glass is obtained by coating a transparent base glass successively with the first layer consisting of >=1 kind among the nitrides of Ti, Zr, Hf or Cr, the second layer of TiO2 and the third transparent layer having <=1.8 refractive index. The first-layer film capable of shielding a heat ray exhibits high heat ray shielding performance by the optical interference produced by the combination with the second-layer film having a high refractive index. A glass having a neutral color tone and without the transmitted color and reflected color being loud is obtained. When the refractive index of the third layer exceeds 1.8, the glass color tone is not neutralized.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a hot-ray minted glass having a high visible light transmittance (and a low solar transmittance), which can be used as a single glass particularly suitable for automobile window glass. Regarding hot wire minted glass.

[Conventional technology] Heat-ray minted glass can be used in window glass for the purpose of converting the energy of sunlight that flows into the interior of a car through the window glass, preventing a rise in temperature inside the car, and reducing the cooling load. It is increasing.

However, in order to ensure safety and high visibility, the visible light transmittance of automobile window glass is 70.
% or more.

As a hot-wire minted glass that satisfies such requirements, Ag as disclosed in U.S. Pat. No. 4,337,990 is available.
There is glass that is coated with a transparent oxide film with a thin structure. Furthermore, a hot ray mint film in which a metal nitride film such as TIN is sandwiched between a film of a transparent oxide with a high refractive index such as titanium dioxide, is 5PIE Vol.
, 324. p52~5/7, 1982 (Optic
al Coatings for Energy
riciency and 5olar Applic
ations).

[Problems to be Solved by the Invention] However, the heat-wire minted glass using the above-mentioned Ag film has poor chemical durability and abrasion resistance, so unlike laminated glass, the film cannot be exposed to the outside. must be used. However, since the rear glass and side glass of automobiles are used as single glass, there is a problem in that the above-mentioned hot wire minted glass using an Ag film cannot be used.

Further, in the hot wire minting glass using the metal nitride film described above, there is a problem in that the reflected color tone becomes red or purple when the combination of film thicknesses provides good hot wire minting performance.

The present invention provides a hot wire minting glass that has good hot wire minting performance, high visible light transmittance, and neutral color tone, and is durable enough to be used as a veneer.

[Means for Solving the Problems] The present invention has been made to achieve the above object, and the first layer coated on the transparent substrate is made of Ti nitride, Zr nitride, Nitride of Hf.

The second layer coated on the first layer is made of titanium dioxide, and the third layer coated on the second layer has a refractive index of 17 or less. It is hot-wire minting glass, which is a transparent layer with a transparent layer.

The most significant feature of the present invention is that a titanium dioxide film having a high refractive index is coated on the above-mentioned metal nitride layer having hot wire minting properties/ability, and a titanium dioxide film having a high refractive index is further formed as the outermost layer. This means that a transparent layer of 8 or less is coated. The refractive index of the outermost transparent layer must be 1.8 or less; if the refractive index exceeds 1.8, the color tone of the hot-wire minted glass cannot be made neutral. Here, a neutral color tone means that the color difference △x1 △y between the heat ray shielding glass and the glass used, expressed in xy chromaticity coordinates, is 0.005 or less in the case of a transmitted color, and in the case of a reflective color. △X, △y
are both 0.02 or less.

Materials that can be used as the outermost transparent layer are not particularly limited as long as the refractive index is 1.8 or less, but include silicon dioxide, aluminum oxide, a compound consisting of silicone aluminum and oxygen, silicon, tantalum, and oxygen. A compound consisting of silicon, niobium and oxygen,
A compound consisting of silicon, aluminum, oxygen, and nitrogen is preferred because it is resistant to external mechanical forces such as scratches and abrasion. In particular, silicon dioxide has a refractive index of 1.46.
Because of its small refractive index, it is possible to increase the difference in refractive index by laminating it on top of the second layer titanium dioxide film, which has a refractive index thicker than 2.2, resulting in excellent hot wire minting performance and new properties.

- It is preferable because a neutral color tone can be obtained. In order to ensure sufficient chemical stability of the film against acids, alkalis, etc., a film of a compound of silicon, tantalum, and oxygen or a film of a compound of silicon, niobium, and oxygen is preferable.

Furthermore, in terms of production stability (when coating a film), a film of a compound consisting of silicon, aluminum, and oxygen or a compound consisting of silicon, aluminum, oxygen, and nitrogen is preferred. The outermost transparent layer of the present invention does not necessarily have to be completely transparent, and may have oxygen vacancies that cause light absorption to an extent that does not significantly impair the transparency of the coating.

In order to increase the hot wire minting performance, the thickness of the first layer of the final metal nitride is preferably thicker, and in order to increase the visible light transmittance, it is preferably thinner.

In the present invention, the thickness of the metal nitride is considered in combination with the thickness of titanium dioxide in the second layer and the thickness of the transparent layer in the third layer, so that the thickness of the metal nitride is taken into consideration in combination with the thickness of the titanium dioxide layer as the second layer and the thickness of the transparent layer as the third layer. is set to be 70% or more. In particular, in order to suitably use it as a window glass for an automobile, the thickness of the metal nitride is preferably 2 to 15 nm, and 3 to 10 nm.
m is most preferred.

In addition, in order to improve the adhesion between the substrate and the first layer metal nitride film, a transparent layer having a refractive index of 2 to 2.5 is formed between the first layer and the metal nitride film to the extent that the optical properties do not change significantly. It can be provided between two layers. For example, tin oxide, titanium oxide,
Tantalum oxide, zirconium oxide film with a thickness of 30 to 60 nm
It can be coated with a thickness of

As the transparent substrate of the heat-ray minted glass of the present invention, colorless transparent float glass, heat-absorbing float glass having a color such as bronze or gray-green (for example, Nippon Sheet Glass Co., Ltd. trade name Bronze Vane, Gray Vane, etc.) can be used. can.

In particular, when bronze-toned glass is used, the glass does not change the color tone of the glass itself, matches the appearance of the car body, and has good hot-wire minting performance. The transparent layer described above can be coated by direct current reactive sputtering using silicon, aluminum, an alloy of silicon and aluminum, an alloy of silicon and tantalum, and an alloy of silicon and niobium as targets.

Further, known vacuum evaporation methods and arc evaporation methods can be used. Similarly, metal nitride layers and titanium dioxide layers can be formed using direct current reactive sputtering, vacuum evaporation,
Arc evaporation methods can be used.

[Function] According to the present invention, the first layer of a film with thermal minting performance coated on a transparent substrate is combined with the second layer of high/refractive index titanium dioxide film to provide optical interference. Due to its action, it exhibits great hot wire minting performance. Furthermore, by coating the second layer with a transparent layer with a refractive index of 1.8 or less as the top layer, the visible light transmittance is not reduced and the transmitted color and reflected color are inconspicuous and neutral. A glass with a unique color tone can be obtained. Further, the top layer film of the present invention protects the first and second layers having a heat ray shielding function.

[Examples] The present invention will be described below based on Examples. Figure 1 shows
This is a partial cross-sectional view of the heat-shielding glass of the present invention, in which a metal nitride layer 2 is coated on a glass 1, and a layer 3 of titanium dioxide and a transparent layer with a refractive index of 1.8 or less are sequentially formed on top of the metal nitride layer 2. 4 is coated.

Example 1 Metallic titanium and quartz glass were set as targets in a magnetron sputtering device. Place the cleaned bronze-colored heat-absorbing float glass with a thickness of 4 mm into the vacuum chamber of the sputtering device, and reduce the pressure inside the chamber to 0.0 using a vacuum pump.
04 Pa or less.

Then, a mixed gas of 94% argon and 6% nitrogen was introduced into the tank, and the pressure was adjusted to 0.04 Pa. A current of 3 A was applied to the metal titanium target and sputtering was performed for a predetermined period of time to form a 6 nm T+ nitride film, and the sputtering was completed. Next, put 40 argon in the vacuum chamber.
A mixed gas consisting of 60% oxygen is introduced and the pressure is reduced to 0.0.
It was adjusted to 4Pa.

A current of 8 A was applied to the metallic titanium target 7) and sputtering was performed for a predetermined period of time to coat the nitride film of T1 with a titanium dioxide film having a thickness of +1101 nm, and the sputtering was completed. Finally, a mixed gas consisting of 80% argon and 20% oxygen was introduced into the vacuum chamber, and the pressure was set to 0.04 Pa.
Adjusted to. By applying 3KW of high frequency power to a quartz glass target and sputtering for a predetermined time, 9
A 3 nm silicon dioxide film was formed and sputtering was completed. Table 1 shows the optical properties of the sample I obtained. 1st
From the table, it can be seen that sample 1 transmits visible light well and blocks solar transmittance well.

In addition, when the color difference between the obtained sample 1 and the bronze heat-absorbing glass used itself was evaluated using xy chromaticity coordinates, the color difference ΔX of X in the transmitted color was 0.0005, y
The color difference Δy was as small as 0.0019. The difference in reflected color when light enters from the glass side is ΔX is 0.
0056, △y is 00017, and △X is o, o o a o, △y is 0.0 regarding the difference in reflected color when viewed from a direction tilted 30 degrees from the direction perpendicular to the glass surface.
The color difference was extremely small at 0.050. There was almost no difference in appearance color tone between Sample 1 and the glass used.0 The type and thickness of the metal nitride in the first layer, the thickness of titanium dioxide in the second layer, and the refractive index of the third layer were 18 or less. Heat-shielding glass samples 2 to 7 were obtained in the same manner as sample 1, except that the material and thickness of the transparent layer were changed. To prepare the sample, the first layer of metal nitride film was coated by reactive sputtering using a mixed gas of argon and nitrogen using metal as a target, and the third transparent layer was coated with aluminum silicide and tantalum silicide, respectively. , a mixed gas of argon and oxygen targeting zirconium diboride,
Alternatively, the coating was performed by reactive sputtering using a mixed gas of argon, oxygen, and nitrogen.

The film composition of the heat ray shielding film of each sample, the visible light transmittance of the obtained sample, and the fNX! ! The i pass rates are summarized in Table 1. Samples 2 to 7 all have a high visible light transmittance of 70% or more (and a solar transmittance of 60% or less, indicating that they have good shielding properties against solar energy. Also, samples 2 to 7 have a high visible light transmittance of 70% or more). In both cases, like the sample Otori, there was almost no discernible difference in color from the glass used.

Comparative Example Using the sputtering apparatus used in the example, a 4 mm thick bronze heat-absorbing float glass was sequentially coated with a first titanium dioxide film, a titanium nitride (TIN) film, and a second titanium dioxide film. The thickness of each film was selected so that the color difference with the glass used was small, and the thickness of the first titanium dioxide was 27 nm, the thickness of the titanium nitride was 7 nm, and the thickness of the first titanium dioxide was 27 nm.
The thickness of the second titanium dioxide was 76 nm. When the optical properties of the obtained comparative sample were measured, the visible light transmittance was 70.5% and the solar transmittance was 56.1%.

However, the color difference due to transmitted light with the glass used is ΔX of 0.0091. Δy was 0.0011, and the color difference due to reflected light was ΔX of 0.0562 and Δy of 00024, and both the transmitted color and the reflected color were reddish-purple. The color difference in reflection was greater when the sample was viewed from an angle.

As mentioned above, samples 1 to 7 according to the present invention are
It has an appearance that does not differ in color from the glass used, and
It can be seen that it has good heat ray shielding properties as expressed by visible light transmittance of 0% or more and solar radiation transmittance of 60% or less.

[Effects of the Invention] The heat ray shielding glass of the present invention has good heat ray shielding performance against sunlight, and the color tone due to transmitted light and reflected light has a small difference from that of the glass used, giving it a glare appearance. Therefore, when used for automobile window glass, it is possible to reduce the indoor cooling load without impairing the color harmony with the car body and interior materials.In addition, the heat ray shielding glass of the present invention can reduce visible light rays. The high transmittance ensures visibility to objects outside the vehicle.Also, the top layer of the coating is durable against mechanical external forces such as scratches and abrasion, so it can be used as a single plate. I can do it.

Therefore, without increasing the flfffi of the car (,
The load on air conditioning inside the vehicle can be reduced.

[Brief explanation of drawings]

FIG. 1 is a partial cross-sectional view of the heat ray shielding glass of the present invention. l...Transparent substrate, 2...Metal nitride layer, 3...
A layer of titanium dioxide, 4...a transparent layer with a refractive index of less than 1.8 Figure 1! , Indication of the case Japanese Patent Application No. 2-74190 2, Name of the invention Hot ray minting glass 3, Person making the amendment Relationship to the case Patent applicant address 3-5-11 Doshomachi, Chuo-ku, Osaka-shi, Osaka Name (400 ) Nippon Sheet Glass Co., Ltd. Representative: Iji Nakajima 4, Agent address: Shinbashi Sumitomo Building, 5-11-3 Shinbashi, Minato-ku, Tokyo Japan Patent Department 6, Subject of amendment, Contents of amendment) Name of the invention in the application Correct the column as shown in the attached sheet. ) Column for detailed description of the invention in the specification (1) Correct "minting" to "shielding" in lines 13, 15, 18, and 719 on page 2 of the specification. (2) Line 4, line 1O, line 15 on page 3 of the specification,
Correct "mint" in line 20 to "shield". (Corrected to ``good heat shielding glass''). (4) "Minting" in lines 6, 8, 17, and 19 on page 4 of the specification is corrected to "shielding." (5) “17” from line 16 to line 17 on page 4 of the specification
" is corrected to rl, 8J. (6) “Minute” in the 5th line of the 5th page of the specification is 1! ! "cover"
Correct. 7) r on page 6, line 2, line 15, and line 20 of the specification
Correct each word ``l note'' to ``shield.'' 8) Correct "Minute J" in lines 13 and 20 on page 7 of the specification to "shield" respectively. 9) Correct "Minute" in lines 13 and 15 on page 8 of the specification to "shield" respectively.

Claims (4)

[Claims] (1) Ti nitride, Z
At least one of r nitride, Hf nitride, and Cr nitride is coated, titanium dioxide is coated as a second layer on the first layer, and titanium dioxide is coated as a third layer on the second layer.
．． Heat-shielding glass coated with a transparent layer having a refractive index of 8 or less. (2) The thickness of the first layer is 2 to 15 nm, the thickness of the second layer is 90 to 110 nm, and the thickness of the third layer is 80 nm.
The heat ray-shielding glass according to claim 1, characterized in that the wavelength is 110 nm to 110 nm. (3) The transparent layer is made of silicon dioxide, aluminum oxide,
A compound consisting of silicon, aluminum and oxygen, a compound consisting of silicon, tantalum and oxygen, a compound consisting of silicon, niobium and oxygen, a compound consisting of silicon, aluminum, oxygen and nitrogen, a compound consisting of zirconium, boron and oxygen The heat ray shielding glass according to claim 1 or 2, which is any one of the compounds. (4) Visible light transmittance is 70% or more, solar transmittance is 60%
The heat ray shielding according to any one of claims 1 to 3, wherein the thicknesses of the first, second, and third layers are each adjusted so that glass.