JPH06263484A - Water-and oil-repellent heat ray shielding glass - Google Patents

Abstract

PURPOSE:To provide a water- and oil-repellent heat ray shielding glass excellent in durability. CONSTITUTION:When a heat ray shielding coating film 2 is formed on a transparent glass substrate 1 and a carbon- or carbide-based coating film 3 is further formed on the heat ray shielding coating film 2 to obtain a heat ray shielding glass, at least the surface 3a of the carbon- or carbide-based coating film 3 is fluorinated by plasma treatment so as to impart water and oil repellency and the objective heat ray shielding glass is obtd. A single-layered film of titanium dioxide, cobalt oxide, etc., or a multilayered film consisting of a metallic film and a titanium nitride film is used as the heat ray shielding coating film 2.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat ray-shielding glass having excellent durability and water and oil repellency.

[0002]

2. Description of the Related Art As a heat ray shielding glass, a transparent glass substrate coated with titanium oxide by a so-called thermal decomposition solution spraying method, a mixture of cobalt oxide, iron oxide and chromium oxide formed (all manufactured by Nippon Sheet Glass Co., Ltd. Product name Reflight ^R ) or a transparent glass substrate on which a metal nitride film such as titanium nitride, a metal film such as a stainless film, or a metal nitride film, a metal film and a metal oxide film are laminated by a sputtering method. (Nippon Sheet Glass Co., Ltd. product name Lefshine ^R ) has been widely used. On the other hand, Teflon (trade name of DuPont) coated with polytetrafluoroethylene is well known as an article whose surface is rendered water and oil repellent. To coat Teflon, a dispersion in water usually containing 50-60% solids is made, applied to the surface of metals or ceramics, dried and then about 35
The method of heating to 0 degreeC is taken. Recently, application of silicone oil containing polysiloxane as a main component to the surface has started to be used as a water and oil repellent treatment for automobile glass and clothes.

[0003]

Among the conventional heat ray-shielding glasses described above, the one in which the metal oxide film is formed by the solution spray method (Relight ^R ) has a chemical durability because the film is a metal oxide film. It is also excellent in mechanical durability because it forms a coating on a glass ribbon at high temperature. Therefore, when the film is used by being exposed to the external environment, that is, when it is used as a window glass, it is possible to use the film on the outdoor side. However, since the metal oxide film has a high affinity for water, it has a drawback that it is easily wetted by water and solid matter adheres as dirt during the drying process of the water. Regular cleaning is required. The coating had to be used indoors if dirt was to be avoided. However, since it is originally a single-layer metal oxide film, it does not have sufficient heat-ray shielding properties, but when the film is placed on the indoor side, the heat-ray shielding performance is further reduced, and also the outdoor reflectance is reduced by design. Therefore, there is a disadvantage that the beautiful mirror effect is lost.

On the other hand, a metal nitride film such as titanium nitride, a metal film such as a stainless steel film, or a metal nitride film, a metal film, and a metal oxide film are laminated on a transparent glass substrate by a sputtering method. Since the heat ray shielding glass (Lefshine ^R ) has excellent heat ray shielding properties,
It has begun to spread widely from the viewpoint of energy saving. However, since the chemical and mechanical durability is not sufficient, there is a restriction that the coating surface should be used as the indoor side when used as a window glass. Therefore, the problem of soiling due to moisture is less important than Relight ^R, as the coating is not exposed to the external environment. However, conversely, there is a problem that stains caused by the indoor environment, for example, oil stains such as fingerprints are noticeable. Since this is a high-performance heat-shielding glass with high reflectance, the portion where such oil stains adhere ( (Reflectance changes) and the difference between the reflectance of the surroundings and becomes noticeable, it is easy to notice. Next, among the conventional water and oil repellent treatments for preventing such stains, the water repellent and oil repellent treatment of the inner surface of frying pans and electronic jars is utilized by utilizing the characteristic that Teflon coating has excellent lubricity. Although it is applied as a treatment, it cannot be effectively used as a surface treatment of glass because of its insufficient adhesion to glass. There is also a problem that the surface is easily damaged mechanically. The coating of silicone oil has an advantage that it can be easily used as a post-treatment, but it has a serious problem that the effect of water and oil repellency does not last because the durability is not sufficient.

[0005]

The present invention has been made in order to solve the above-mentioned conventional problems, and a heat ray shielding film is formed on a transparent glass substrate, and the heat ray shielding film is formed on the heat ray shielding film. A heat ray-shielding glass having a coating containing carbon or carbide as a main component, wherein at least the surface of the coating containing carbon or carbide as a main component is fluorinated by plasma treatment. It is a heat ray shielding glass.

The heat ray-shielding coating used in the present invention is a titanium oxide coating formed by the thermal decomposition solution spray method used for producing the reflight ^R or a mixture of cobalt oxide, iron oxide and chromium oxide. Coating,
A laminated film composed of one or more of a metal film formed by a sputtering method, a metal nitride film, a metal oxynitride film, and a metal oxide film, which is used to manufacture the Lefshine ^R , is practical. It can be mentioned as a thing. However, the heat ray shielding film is not limited to these, and it is an interference filter type in which a high refractive index transparent dielectric film and a low refractive index transparent dielectric film are alternately formed, or a transparent conductive film such as an ITO film. It may be one that utilizes the heat ray shielding performance of the flexible film.

As the coating mainly composed of carbon or carbide provided on the heat ray shielding coating, SiC, TiC, Cr ₃ C ₂ , ZrC, NbC, Ta having excellent durability is used.
It is possible to exemplify one containing one or more of C and WC as a main component. All of these carbide films have excellent chemical and mechanical durability, and can be easily fluorinated by plasma (generation of C—F bond). The uppermost film is carbon or a film of these carbides, and the surface thereof is fluorinated. By forming a C—F bond on the surface of the uppermost film, a surface having a surface energy smaller than that of water or hydrocarbon (oil) can be obtained, and water and oil can be repelled. Then, this uppermost layer is partially oxidized for the purpose of, for example, increasing the adhesion with the heat ray-shielding coating of the lower layer, improving the durability, enhancing the heat ray-shielding ability, or adjusting the color tone. Alternatively, a metal or a nitride may be mixed as an accessory component. The thickness of the uppermost layer is 5 to 100 nm, and further 10 to
50 nm is desirable. When the film thickness is less than 5 nm, the fluorinated water- and oil-repellent surface is more likely to disappear due to abrasion or the like, and even when the film thickness is 100 nm or more, the water- and oil-repellent effect is improved. Instead, problems such as film peeling will occur. 5-100 for the uppermost membrane
By setting an appropriate thickness in the range of nm, it becomes possible to improve the heat ray shielding performance. This is particularly effective when the Reflight ^R described above is used as a heat ray shielding coating. That is, not only can the reflight ^{R be provided} with a water / oil repellent function, but also the heat ray shielding performance can be improved to the same level as the above-mentioned Lefshine ^R. In addition, when using the Lefshine ^R as a heat ray shielding film, while increasing the variation of color tone by appropriately selecting the type and thickness of the carbon film or the carbide film,
The advantage of being able to impart water / oil repellency is produced.

When the heat ray-shielding coating according to the present invention is a titanium oxide coating coated by a thermal decomposition solution spray method or a coating containing cobalt oxide, a float bath for plate manufacturing in a float plate glass manufacturing process is used. About 500 that have passed
It can be formed by a method of spraying a solution containing an organometallic salt which is thermally decomposed to form an oxide film on a glass plate having a high temperature of ˜650 ° C. After that, the glass coated with the heat ray-shielding film is introduced into a vacuum chamber, a film containing carbon or carbide as the main component is formed by a sputtering method in the vacuum chamber, and then the surface of the film containing carbon or carbide as the main component is formed. A water- and oil-repellent heat ray-shielding glass can be obtained by fluorinating by exposing it to plasma containing fluorinated carbon. Forming a titanium oxide coating or a coating composed of a mixture of cobalt oxide, iron oxide and chromium oxide on a high temperature glass ribbon by a solution spraying method is a process that has already been put into practical use as a method for producing heat ray reflective glass. The titanium oxide film having a thickness of about 50 nm is a silver-colored heat ray reflective glass corresponding to the product name Relight S manufactured by Nippon Sheet Glass Co., Ltd., and can be used as it is. Further, since a mixture of cobalt oxide, iron oxide and chromium oxide having a film thickness of about 50 nm is a bronze color heat ray reflective glass corresponding to Reflight Bronze, a trade name manufactured by Nippon Sheet Glass Co., Ltd., it should be used as it is. You can As the carbide film formed on the titanium oxide film or the cobalt oxide, iron oxide and chromium oxide film, SiC, TiC, Cr ₃ C ₂ , Zr
It is desirable to use one or more of C, NbC, TaC, and WC as a main component. All of these carbide films have excellent chemical and mechanical durability, and can be easily fluorinated by plasma (generation of C—F bond). The fluorination of the surface can be performed by exposing it to plasma containing fluorinated carbon, and the fluorinated carbon may be CF ₄
Alternatively, the fluorination can be most effectively performed by using any of the mixed gas of CF ₄ and oxygen.
A fluorinated surface can also be obtained using hydrogenated fluorinated carbon such as CHF ₃ . The fluorination of the surface by the plasma containing the fluorinated carbon is performed by using a parallel plate type reactive ion etching apparatus (RIE) or a cylindrical plasma etching apparatus (PR) which are known plasma processing apparatuses. It can be easily carried out by exposing to glow discharge plasma generated by applying high frequency power under a reduced pressure condition containing. PR
When using the apparatus, it is effective to attach an etching tunnel to exclude etching by ions in order to dominate fluorination rather than etching of the film.

As a heat ray shielding film according to the present invention,
A single layer film formed of one kind selected from the group of a metal film, a metal nitride film, a metal oxynitride film, and a metal oxide film formed by sputtering, or a laminated film formed of two or more kinds can be used.

Examples of such heat ray-shielding film include a single-layer film of titanium nitride film, titanium oxynitride film, chromium nitride film, chromium oxynitride film, and stainless steel film, which has a heat-ray shielding ability by itself. Further, the one having a titanium dioxide film or a tin dioxide film in contact with the film having the heat ray-shielding ability is provided on the glass substrate side of the single-layer film having the heat ray-shielding ability or on the side opposite to the glass substrate. It can be used as a heat ray shielding film. Further, the one having a titanium dioxide film or a tin dioxide film in contact with the film having the heat ray blocking ability on the glass substrate side of the single-layer film having the heat ray blocking ability and on the side opposite to the glass substrate is also the heat ray of the present invention. It can be used as a shielding film. The heat ray shielding film according to the present invention can be formed by a known sputtering method, the metal nitride film is in an atmosphere containing nitrogen, and the metal oxynitride film is an atmosphere containing nitrogen and oxygen. In particular, it can be formed by a sputtering method using the metal as a target.

The titanium dioxide film or tin dioxide film is
It is used to adjust the optical properties of heat-shielding coatings.

Since a single layer film of titanium nitride having a film thickness of 20 to 100 nm is manufactured as the Lefshine T series, which is a high-performance heat ray reflective glass manufactured by Nippon Sheet Glass Co., Ltd., it can be used as it is. it can. Also,
A stainless steel film having a thickness of about 5 to 20 nm and a titanium nitride film having a thickness of about 30 nm formed on a glass substrate in this order is also a high-performance heat ray reflective glass made by Nippon Sheet Glass, Lefshine S.
Since it is manufactured as a series, it can be used as it is.

[0013]

The heat ray-shielding film according to the present invention is protected by a carbon film or a carbide film having excellent wear resistance, and the surface thereof is strongly bound with fluorine by plasma treatment.
Since the surface energy is small, it is possible to obtain a heat ray-shielding glass having high durability against water and oil repellency and abrasion resistance.

[0014]

EXAMPLES The present invention will be described in more detail below with reference to examples.

Example 1 At the float bath outlet for plate making of a float glass manufacturing facility,
A glass ribbon at about 600 ° C. was sprayed with an organic solution containing a chelating compound of titanium metal (solution spray method) to form a titanium oxide film with a thickness of about 50 nm on a float plate glass with a thickness of 6 mm (product of Nippon Sheet Glass Co., Ltd. Name Reflight Silver: Visible light transmittance 61.8%, Visible light reflectance 33.2%, Solar light transmittance 63.4
%). After cleaning the surface of the coating film, the coating film was set in a direct-current sputtering device equipped with tantalum carbide as a target and exhausted to 5 × 10 ⁻⁴ Pa. Then, argon gas was introduced at a flow rate of 100 sccm, the pressure inside the apparatus was set to 0.2 Pa, a current of 2 A was applied to the target, and the glass substrate was passed over the target at a predetermined speed to obtain titanium oxide. A tantalum carbide coating having a thickness of about 20 nm was formed on the coating. Then, this glass substrate was set in a cylindrical plasma etching apparatus with an etch tunnel, and after exhausting up to 6 Pa, CF ₄ gas at 70 P
Introduced to a, discharge with RF power of 300W for 2 minutes,
The surface of the tantalum carbide film was fluorinated. The glass thus obtained had a visible light transmittance of 35% and a visible light reflectance of 46.
%, And the solar radiation transmittance was 34%. The reflection color tone was bluish gray, and the vividness of the reflection color was increased to reflect the increase in visible light reflectance. Further, the solar radiation transmittance was reduced by about 13%, and the heat ray shielding performance was improved. In order to evaluate the water repellency of this heat ray-shielding glass, the contact angle of pure water was measured and found to be about 103 °, indicating that the glass exhibited excellent water repellency. next,
To evaluate the durability of this glass, Teledyne
Using a wear tester manufactured by Taber, a wear wheel of CS-10F was loaded with 500 g and subjected to 300 times of rotary wear. The change in the transmittance of the glass and the change in the haze ratio before and after the abrasion test were both less than 2%, and it was found that the durability of the film was excellent. Further, it was found that the contact angle to pure water after the abrasion test was about 90 °, and that excellent water repellency was maintained.

Example 2 At the exit of a float bath for plate making of a float glass manufacturing facility,
Cobalt oxide-iron oxide-with a thickness of about 50 nm is sprayed with an organic solution containing a chelate compound of metallic cobalt as a main component and a chelate compound of iron and chromium as a subcomponent on a glass ribbon at about 600 ° C (solution spray method). A film made of chromium oxide was formed on a float plate glass having a thickness of 6 mm (Nippon Sheet Glass Co., Ltd., trade name Reflight Bronze: visible light transmittance 42.6%, visible light reflectance 34.
0%, solar radiation transmittance 48.4%). After cleaning the surface of the coating film, the coating film was set in a DC sputtering device having silicon carbide as a target and evacuated to 5 × 10 ⁻⁴ Pa. Then, argon gas was introduced at a flow rate of 100 sccm, the pressure in the apparatus was adjusted to 0.2 Pa, a current of 1 A was applied to the target, and the glass substrate was passed over the target at a predetermined speed to obtain cobalt oxide. A silicon carbide coating having a thickness of about 20 nm was formed on the iron oxide-chromium oxide mixed coating. After that, this glass substrate was set in a cylindrical plasma etching apparatus with an etching tunnel, and after evacuation to 6 Pa, CF ₄ gas was introduced to 70 Pa and discharge was carried out at RF power of 200 W for 10 minutes to make the surface of the silicon carbide film fluorine. Processed. The obtained glass had a visible light transmittance of 37%, a visible light reflectance of 34%, and a solar light transmittance of 41%. The transmission color tone is a bronze color which is almost the same as that of relight bronze manufactured by Nippon Sheet Glass Co., Ltd. The reflection color tone was a relatively vivid bronze color, whereas the relight bronze was a gray color. The solar radiation transmittance was reduced by about 7%, and the heat ray shielding performance was improved. In order to evaluate the water repellency of this heat ray shielding glass, the contact angle of pure water was measured and found to be about 93 °.
It was found that it showed excellent water repellency. Next, in order to evaluate the durability of this glass, Teledyne T
Using a wear tester manufactured by Aber Co., Ltd., a wear wheel of CS-10F was applied with a load of 500 g and subjected to 300 times of rotary wear. The change in the transmittance of the glass and the change in the haze ratio before and after the abrasion test were both less than 2%, and it was found that the durability of the film was excellent. Further, it was found that the contact angle to pure water after the abrasion test was about 82 °, and the excellent water repellency was maintained.

Example 3 Metallic stainless steel was used for the first cathode of an in-line type DC sputtering apparatus having three sputtering cathodes.
Titanium metal was attached to the second cathode, and titanium carbide was attached to the third cathode.
A 6 mm-thick float glass plate that had been washed as a substrate was set in a sputtering device and evacuated to 5 × 10 ⁻⁴ Pa. Then, nitrogen gas was introduced at a flow rate of 100 sccm, the pressure in the apparatus was set to 0.2 Pa, a current of 2 A was applied to the metallic titanium target, and the glass substrate was passed over the target at a predetermined speed, A titanium nitride coating having a thickness of about 30 nm was formed (corresponding to high-performance heat ray reflective glass, Lefshine T series, TS30 manufactured by Nippon Sheet Glass Co., Ltd .: visible light transmittance 30%, visible light reflectance 16.3).
%, Solar radiation transmittance 23.5%). Next, after the inside of the sputtering apparatus was evacuated to 5 × 10 ⁻⁴ Pa again, argon gas was introduced at a flow rate of 100 sccm, and the pressure inside the apparatus was reduced to 0.
After the pressure was set to 2 Pa, a current of 2 A was applied to the titanium carbide target, and the glass substrate was passed over the target at a predetermined speed to give about 20 nm on the titanium nitride film.
A titanium carbide coating film having a thickness of 1 μm was formed. Then, this glass substrate was set in a cylindrical plasma etching apparatus with an etch tunnel, and after exhausting to 6 Pa, CF ₄ gas was added to 70
After introducing up to Pa, the surface of the titanium carbide film was fluorinated by discharging with RF power of 300 W for 4 minutes. The glass thus obtained had a visible light transmittance of 17%, a visible light reflectance of 24%, and a solar light transmittance of 12%. The transmission color tone was gray. The reflection color was pale green. In order to evaluate the water repellency of this heat ray-shielding glass, the contact angle of pure water was measured and found to be about 96 °, indicating excellent water repellency. next,
To evaluate the durability of this glass, Teledyne
Using a wear tester manufactured by Taber, a wear wheel of CS-10F was loaded with 500 g and subjected to 300 times of rotary wear. It was found that the change in the transmittance and the change in the haze ratio of the glass before and after the abrasion test were both less than 4%, and the durability of the film was excellent. Further, it was found that the contact angle to pure water after the abrasion test was about 85 °, and the excellent water repellency was maintained.

Example 4 Metallic stainless steel was used for the first cathode of an in-line type DC sputtering apparatus having three sputtering cathodes.
Titanium was attached to the second cathode, and silicon carbide was attached to the third cathode. A 6 mm-thick float glass plate that had been washed as a substrate was set in a sputtering device and evacuated to 5 × 10 ⁻⁴ Pa. Argon gas was introduced at a flow rate of 100 sccm, the pressure inside the apparatus was adjusted to 0.2 Pa, a current of 1 A was applied to the metallic stainless target, and the glass substrate was passed over the target at a predetermined speed. A stainless coating of about 6 nm was formed on the glass substrate. Then, the inside of the sputtering apparatus was again evacuated to 5 × 10 ⁻⁴ Pa, nitrogen gas was introduced at a flow rate of 100 sccm, the pressure inside the apparatus was adjusted to 0.2 Pa, and then a current of 2 A was applied to the metallic titanium target. , The glass substrate is passed over the target at a predetermined speed, so that about 2
A titanium nitride film with a thickness of 8 nm was formed (high-performance heat ray reflective glass, Lefshine S series, S manufactured by Nippon Sheet Glass Co., Ltd.
Equivalent to S20: visible light transmittance 20%, visible light reflectance 23.8%, solar light transmittance 15.8%). next,
After exhausting the inside of the sputtering apparatus to 5 × 10 ⁻⁴ Pa again,
Argon gas was introduced at a flow rate of 100 sccm, the pressure in the apparatus was adjusted to 0.2 Pa, a current of 1 A was applied to the target, and the glass substrate was passed over the target at a predetermined speed to remove the titanium nitride film. About 20n above
A silicon carbide coating having a thickness of m was formed. Then, this glass substrate was set in a cylindrical plasma etching apparatus with an etch tunnel, and after exhausting to 6 Pa, CF ₄ gas was added to 70
After introducing up to Pa, the surface of the silicon carbide film was fluorinated by discharging with RF power of 300 W for 10 minutes. The glass thus obtained had a visible light transmittance of 20%, a visible light reflectance of 34%, and a solar light transmittance of 16%.
The transmission color tone was bronze. The reflection tone was pale blue with a gray tinge. In order to evaluate the water repellency of this heat ray-shielding glass, the contact angle of pure water was measured, and it was found to be about 90 °, indicating excellent water repellency. Next, in order to evaluate the durability of this glass, Tel
Using an edyne Taber abrasion tester, CS
A load of 500 g was applied to a wear wheel of -10 F, and rotational wear was applied 300 times. It was found that the change in the transmittance and the change in the haze ratio of the glass before and after the abrasion test were both less than 4%, and the durability of the film was excellent. Further, it was found that the contact angle with pure water after the abrasion test was about 81 °, and the excellent water repellency was maintained. Furthermore, Example 1
It was confirmed that each of the glass samples obtained in ~ 4 had oil repellency.

Comparative Example The contact angle of pure water on the surface in the case of not forming a carbon or carbide coating and subsequent fluorination treatment according to the present invention was measured as a comparative example, and the results are shown below.

[0020] Comparative Sample Contact angle (°) · solution oxidation of 50nm thickness were formed by spraying the titanium coating surface 35 (manufactured by Nippon Sheet Glass Co., Ltd. Refuraito corresponding to ^R S) · solution cobalt oxide over iron oxide 50nm thickness were formed by spraying over 40 6 nm thickness was deposited by sputtering method (corresponding to Nippon Sheet Glass Co. reflex Shine ^R TS30) chromium oxide mixed film surface (Refuraito ^R B in equivalent) sputtering method a titanium nitride film formation was 30nm thickness by coating the surface 55 Stainless steel film and 28 nm 55-thick titanium nitride two-layer film surface (equivalent to Lefshine ^R SS20) -Sputtering-formed 7 nm-thick stainless steel film and 6 nm 50-thick titanium oxide two-layer film surface (Lefshine ^R Equivalent to SGY20)

According to the present invention, it is possible to obtain a heat ray-shielding glass having a water-repellent and oil-repellent coating having excellent durability on the outermost surface. Therefore, when it is used as a window glass, even if the coating is placed on the outdoor side, it is possible to prevent contamination caused by moisture or oil from the external environment. As a result, it is possible to effectively utilize the heat ray shielding performance and the designability of the heat ray shielding glass. In addition, a variety of color tones can be provided, and the heat ray shielding performance can be improved. Also, when the coating is used on the indoor side, it is caused by the indoor environment,
In particular, since it is possible to prevent oily stains from adhering, it is possible to avoid deterioration in the design of the high-performance heat-shielding glass.

[Brief description of drawings]

FIG. 1 is a partial cross-sectional view of the present invention.

[Explanation of symbols]

1 ... glass substrate, 2 ... heat ray shielding film, 3 ...
..Coatings mainly composed of carbon or carbide, 3a ...
Layers fluorinated by plasma treatment

Claims (5)

[Claims] 1. A heat ray shielding glass having a heat ray shielding coating formed on a transparent glass substrate, and a coating containing carbon or carbide as a main component formed on the heat ray shielding coating. A water and oil repellent heat ray shielding glass in which at least the surface of a coating film as a main component is fluorinated by plasma treatment. 2. The carbide is SiC, TiC, Cr.
_The water / oil repellent heat ray-shielding glass according to claim 1, which is at least one selected from the group consisting of ₃ C ₂ , ZrC, NbC, TaC, and WC. 3. The water- and oil-repellent heat ray-shielding glass according to claim 1, wherein the heat ray-shielding coating is a titanium dioxide coating coated by a thermal decomposition spray method. 4. The water- and oil-repellent heat ray-shielding glass according to claim 1, wherein the heat ray-shielding coating is a coating made of cobalt oxide, iron oxide and chromium oxide, which is coated by a thermal decomposition solution spray method. 5. The heat ray shielding coating is a single layer film formed of one kind selected from the group of metals, metal nitrides, metal oxynitrides and metal oxides, all of which are coated by a sputtering method, or the above group. The water- and oil-repellent heat ray-shielding glass according to claim 1 or 2, which is a laminated film composed of two or more kinds selected from the following.