JPH11302037A - Low reflectance and low transmittance glass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To ensure superior heat ray and UV shielding properties and a moderate light shielding property for a glass with a laminated film by specifying the visible light transmittance of the glass, the visible light reflectance of the film face and glass face sides of the glass and the solar radiation transmittance of the glass. SOLUTION: A heat ray shielding film and a transparent colorless film are successively formed on the surface of a glass substrate to obtain the objective glass with a laminated film having 10-30% visible light transmittance. The visible light reflectance of the film face and glass face sides of the glass is <=12% and the solar radiation transmittance of the glass is <=15%. The heat ray shielding film is preferably a film of nitride of at least one selected from the group consisting of Ti, stainless steel, Ni-Cr, Cr, Mo, W, Zr, Hf, Fe, Co and Ni and the thickness is desirably about 20-50 nm. The transparent colorless film is preferably a film of oxide of at least one selected from the group consisting of Ti, Zr, Ta, Al and Si, nitride of Al or nitride of Si and the thickness is desirably about 10-60 nm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a glass with a laminated film used as a window material for a building, a building, or a transfer machine of a vehicle, a ship, an aircraft, or the like. Of course, it is a film of low transmittance over the visible region, or even the ultraviolet region, especially in the summer, suppresses solar radiation energy that enters the interior of building vehicles and the like through window materials, increases the internal temperature, By reducing the cooling load and maintaining a moderately low visible light transmittance, it maintains the privacy of the see-through from the outside to the inside of the window material, and further suppresses the visible light reflectance to reflect the reflected image. The present invention relates to a glass having a low light reflectance and a low transmittance, which ensures transparency and visibility from the inside to the outside of the window material.

[0002]

2. Description of the Related Art In recent years, heat-shielding glass has been widely adopted which suppresses solar radiation energy entering into the interior through a vehicle window glass, a building window glass, or the like, and reduces an internal temperature rise and a cooling load. I have. In particular, the general direction toward recent RV vehicles (leisure vehicles) has been increased, and as a vehicle window material, a black-to-dark glass having a low transmittance in visible light including an infrared region (heat ray) and a glass having high privacy. Demand is growing.

[0003] In the case of producing a black-dark glass having a low light transmittance as an uncoated glass sheet, there is a remarkable difference in heat capacity, thermal conductivity and the like from ordinary glass base materials such as so-called clear glass and light-colored glass. Therefore, unlike the case of manufacturing those ordinary glasses, the transfer of heat of the glass base at the time of melting the glass, a unique soaking means taking into account the conduction, or adopting a special shape melting tank, etc. Requires design.

[0004] Further, when such a raw glass product requires a locally high light transmissive portion, for example, a high mount stop lamp portion is provided in a rear window of a vehicle, and the light transmissive portion of the portion is provided. It cannot be adopted when it is desired to increase the rate, or it is different from the purpose for privacy, but it cannot be adopted when it is necessary to arrange a clear vision part and a night vision part such as a shade band. Not a few.

On the other hand, there are quite a few known examples of a glass having a heat ray shielding film formed thereon, and in particular, a glass for a vehicle having a heat ray shielding property and a light shielding property is disclosed in, for example, Japanese Patent Application Laid-Open No.
Japanese Patent No. 170485 relates to a heat ray shielding film and a window glass for automobiles. The heat ray shielding film has a visible light transmittance of 35% or less and a sheet resistance of a specific value or more, and includes nitride, boride, oxynitride,
It is disclosed that glass formed with a film made of one kind of oxide (especially a film mainly composed of NbOx), and that the above-mentioned film is arranged in contact or non-contact with an antenna conductor patterned on glass. I have.

The known example suppresses the visible light transmittance,
Increase visible light reflectance. It is customary to arrange the film surface on the inside of the car (room) in the glass with the film. However, the film surface generally has high visible light reflectance, and for example, when seeing from inside the vehicle to the outside, the reflection image of the inside is displayed. Cause discomfort,
In addition, transparency and visibility are likely to be impaired.

Further, as for a glass in which a dielectric film and a heat ray shielding film are laminated, for example, Japanese Patent Publication No. 6-84256 relates to a single-plate heat ray reflective glass, and a transparent dielectric film having a specific thickness in order from the glass substrate side. Or a transparent conductive oxide film), then a nitride film, and further a transparent dielectric film (or a transparent conductive oxide film), and as an uppermost layer, a SiO ₂ -based oxide having a specific refractive index and a specific thickness or more. And the nitride film is effective as a heat ray reflective film. In particular, any one of TiN, ZrN, and HfN or a composite nitride thereof is used, and the transparent dielectric film (or transparent conductive film) is used. It is disclosed that the oxide film) has a specific refractive index or higher.

The known example has a visible light transmittance of about
It is high at around 70%, which is not appropriate for the purpose of protecting privacy.

Further, Japanese Patent Application Laid-Open No. 7-25647 discloses a heat ray shielding glass having reduced reflection on the film surface side, wherein one surface of a transparent glass substrate is made of at least one of a specific alloy or a metal having a specific film thickness. A film in which a specific metal oxide film having a specific thickness and a transparent film (SiO ₂ , Al ₂ O _3, etc.) having a specific thickness and a refractive index of a specific value or less are further laminated, and a glass is further disclosed. The visible light reflectance of light incident from the surface side is 25% or more, and the visible light reflectance of light incident from the film surface side is smaller than the visible light reflectance of the transparent glass substrate itself. It is disclosed that the color is 30 to 50%, and that the color is a neutral gray transmission color and a reflection color.

[0010] The known example discloses a film surface side reflectance (normal vehicle (room)).
(Disposed on the inside) is low, and therefore the reflection image is not conspicuous, but the reflectance on the glass side outside the car (room) is too high and the reflection image is conspicuous, which makes the surrounding environment uncomfortable, and from the viewpoint of privacy, There is a problem that the visible light excess ratio is too high.

[0011] Alternatively, JP-A-6-321580 relates to an abrasion-resistant low-transmittance glass in which a heat ray shielding film, a first transparent protective film, and a second transparent protective film are sequentially laminated on a glass plate surface. Glass, wherein the sum of the thicknesses of the first transparent protective film and the second transparent protective film is set to a specific value or less, the visible light transmittance of the glass with the film is 40% or less, and the glass surface side of the glass Of which the visible light reflectance is 30% or less is disclosed. Further, as the first transparent protective film, Si ₃ N ₄ , SiO ₂ ,
ZrO ₂ , Ta ₂ O, etc. for the second transparent protective film such as SnO ₂ , ZrBxOy, etc.
_5, Nb ₂ O ₅ , and the heat ray shielding film include at least one metal nitride selected from Ti, Zr, and Cr.

In the known example, as disclosed, the reflectance on the film surface side is relatively high, and the reflected image on the vehicle cabin side is remarkably reflected.

The present invention differs from the above-mentioned known examples in that, in addition to heat ray shielding properties or ultraviolet ray shielding properties, it has low visible light transmittance, moderate light shielding properties and privacy properties, and has a film surface and a glass surface side. Has low visible light reflectance and glare
It has no discomfort due to reflection and reflection image reflection, and has a transmission color tone close to black, and the glass surface side reflection color has a relatively pale green color, and is often used as a front door glass of automobiles, for example. It fuses with ultraviolet blocking green glass and the like, and is preferable from the viewpoint of sight. In addition, since a film unnecessary portion can be easily patterned by masking or the like and the film can be easily removed, a low reflectance that can be locally applied, for example, a transmittance can be increased in a high mount stop lamp portion of an automobile, and a wide range can be adopted. It proposes low transmittance glass.

[0014]

That is, the present invention relates to a laminated glass having a heat ray shielding film and a transparent non-colored film sequentially formed on a surface of a glass substrate. Low reflectance and low transmittance glass having a reflectance of 10 to 30%, a visible light reflectance of 12% or less, and a solar transmittance of 15% or less on the film surface and the glass surface side of the glass with a laminated film.

Further, the laminated film is an alternate layer film of a heat ray shielding film and a transparent and non-colored film, each having two or more layers.

The heat ray shielding film is made of Ti, stainless steel (hereinafter referred to as St-St.), Cr, Ni-Cr, Mo, W, Ti, Zr, Hf,
Desirably, the nitride is at least one of Fe, Co, and Ni.

Further, the transparent non-coloring film is made of Ti, Zr, Ta,
Desirably, it is at least one oxide of Al or Si, or at least one of Al nitride or Si nitride.

[0018]

DESCRIPTION OF THE PREFERRED EMBODIMENTS As a heat ray shielding film, a nitride film of Ti, Zr, Cr, Hf, Ta, and many other metals can be adopted as seen in known examples. These nitride films generally have high light reflectivity from the visible region to the infrared region, and also have a remarkable absorption of light in the region, block heat rays, and are colored to suppress transmission of visible light. Note that among metal nitrides, a Si nitride film and an Al nitride film, which have low heat ray shielding properties and relatively high visible light transmittance, are not suitable.

Among the heat ray shielding films, in particular, Ti, St-St.
If at least one nitride of Ni-Cr, Cr, Mo, W, Zr, Hf, Fe, Co or Ni is used, a relatively black color tone can be exhibited. Among them, nitrides of Ti and St-St. Are particularly excellent. The preferred thickness is about 20 to 50 nm.

A transparent non-colored film is a film having a high light transmittance from the visible region to the infrared region and, therefore, hardly colored at a film thickness of the order of μm or less. Transparent oxide film, or transparent protective film also called Ti, Zr, Hf, Ta, Nb, Si, Al, etc., which are difficult to color or poorly colored, oxide film of Si, nitride film of Si, Nitride films fall into that category. Especially Ti, Zr, Ta,
An oxide of at least one of Al and Si, or a nitride of Al or a nitride of Si can be recommended. The preferred thickness of the transparent non-coloring film is about 10 to 60 nm.

When the heat ray shielding film alone is used, the visible light reflectance on the film surface side exceeds 30%, and there is a problem that the reflected image inside the vehicle is reflected, making it difficult to see the outside. In addition to the heat-shielding properties of the heat-shielding film and the appropriate suppression of see-through, the film is formed into a laminated film in order to reduce the reflectance while exhibiting a black color tone due to the light interference effect between the films. Can be. Further, by forming two or more layers each of the heat ray shielding film and the transparent non-coloring film alternately and sequentially, the effect of further reducing the reflectance can be obtained.
Preferably 4 to 6 by a sputtering method that facilitates film formation.
It is preferable to form a laminated film of the layers.

In the case of using an inter-back type (a type in which the substrate is capable of reciprocating the substrate many times in the film forming chamber when the film is formed on the substrate, the outlet and the inlet are common) as the sputtering device, the heat ray shielding film is made of Ti. The target can be shared by using Ti and oxide for the nitride and transparent non-coloring film,
Productivity can be improved.

The transparent non-colorable film has abrasion resistance,
It is preferable to dispose it on the outermost surface layer from the viewpoints of chemical resistance, moisture resistance, etc., and it is particularly desirable to dispose Ta oxide. In addition, it is also useful to overcoat a hard coat film such as polysilazane.

The optical characteristics of the low-reflection glass and low-transmission glass of the present invention are contrasted with those of the uncoated film type, which is currently the mainstream of RV vehicles and is recommended. Colored glass (for example, dark gray color: visible light transmittance of about 20 to 30%, transmitted light dominant wavelength of 470 to 570 nm, visible light reflectance of 4 to 6%, reflected light dominant wavelength of 470 to 570 nm, solar light transmittance of about
15-20%, solar reflectance about 4-5%).

In the present invention, the visible light transmittance of the glass with a laminated film, in which a heat ray shielding film and a transparent non-coloring film are sequentially formed on the surface of the glass substrate, is set to 10 to 30%. You can match the rate. If the visible light transmittance is less than 10%, it is difficult to see the outside from the inside of the vehicle at night or the like, and if it exceeds 30%, the privacy protection effect is diminished. Although not particularly limited, by setting the stimulating purity of transmitted visible light to 5% or less, a blackish color tone is exhibited regardless of the main wavelength in any wavelength region, and how the color tone of the surrounding articles such as the body is changed. Regardless, it is easy to match the color tone.

By setting the visible light reflectance on the film surface and the glass surface side of the glass with the laminated film to 12% or less, reflection images inside and outside the car (room) as in the case where the visible light reflectance exceeds 12%. Is not noticeable and does not cause a sense of incongruity. Particularly, in the case of a vehicle, there is no possibility that the outside is difficult to see from the inside of the vehicle, which leads to erroneous recognition or oversight, which is not unsafe. The preferred visible light reflectance is about 10% or less.

Although not particularly limited, by setting the stimulating purity of the reflected visible light to 15% or less, the reflected color tone becomes colored as in the case where the stimulating purity of the reflected visible light exceeds 15%, causing a sense of visual discomfort. The tendency to do so is also reduced.
The more preferable stimulating purity of the reflected visible light is about 10% or less. In other words, low reflectance or even lower stimulus purity is preferable in terms of habitability, safety, and environment.

Although the solar transmittance is related to the function of the heat ray shielding film, it suppresses solar radiation energy that enters the inside through a vehicle window glass, a building window glass, or the like, suppresses an internal temperature rise, and reduces a cooling load. In addition, it is important for preventing ultraviolet rays or the like from affecting the human body.

The glass having a low light reflectance and transmittance of the present invention can be used as a single glass as it is, or as a tempered, bent or bent tempered glass, as well as a multi-layer glass or a laminated glass. It can be used for buildings, structures, vehicles such as automobiles, transfer machines for ships, aircrafts, etc., and particularly as window materials for automobiles, for example, rear window glass (shade band), side window glass (Privacy) or sunroof glass (light shielding).

The glass substrate is preferably an inorganic, transparent, colorless or colored glass such as a soda-lime-based, aluminosilicate-based, or borosilicate-based glass manufactured by various plate-making methods such as a float method. Is, for example, clear glass, green glass, bronze glass, gray
It can also be used for blue glass, blue glass, and the like.

[0031]

The present invention will be described below in detail with reference to examples. However, the present invention is not limited to such an embodiment.

[Preparation of glass with laminated film]
4. With respect to the glasses with laminated films of Comparative Examples 1 to 4, glasses with laminated films having the film configurations shown in Table 1 were produced.

Glass: Float glass cleaned by detergent washing, water rinsing, and alcohol washing, approximately 300 mm in size
300mm (common for each example and comparative example) used. Table 1 shows the color tone and plate thickness. Sputtering device: DC magnetron sputtering device used. Film forming conditions: Tables 3 to 10 show the respective examples and comparative examples. Place the indicated target in the vacuum chamber and place it so that the glass can reciprocate upwards.
After degassing to 6.7 × 10 ⁻⁴ Pa or less, a predetermined gas at a specified flow rate (SCCM: flow rate in standard condition cc / min) is introduced into the vacuum chamber to reduce the degree of vacuum to 2.7 × 10 ⁻¹ Pa And a predetermined power (KW) is applied to the target, and the first layer is formed by performing sputtering while conveying the glass at a predetermined speed (mm / min) above the target, Thereafter, the application of the target was stopped. The same operation as above was repeated to form the second and subsequent layers under the display conditions.

Regarding the thickness of each thin film, a portion (masking portion) where no film is formed at the time of film formation is provided for each thin film, and the step is measured with a surface roughness meter (DEKT, manufactured by SLOAN).
AK IIA).

[Measurement and Evaluation Methods] Optical characteristics: According to JISZ8722 and JISR3106, visible light (380 nm to 780 nm) was measured using a 340 type self-recording spectrophotometer (manufactured by Hitachi, Ltd.).
m) Transmittance, visible light reflectivity, solar radiation (340 nm to 1800 nm) Transmittance and solar reflectivity were measured, and optical characteristics such as dominant wavelength and stimulus purity were determined. Table 2 shows the results.

A sample having a visible light transmittance of 10 to 30%
Mark, those with a visible light reflectance of 12% or less were marked with a circle, those outside the above range were marked with a cross, and the solar radiation transmittance was
Those of 15% or less were evaluated by ○, and those out of the above range were evaluated by x.

Abrasion resistance (traverse test): Using a broad cloth # 40, under a load of 100 g / cm ² and a stroke distance of 1
The change (ΔH%) of the haze (degree of haze) after 5,000 strokes at 00 mm and the number of strokes was measured, and the degree of scratching was visually evaluated. Table 2 shows the results.

In addition, those with ΔH% of 4% or less and no scratches were judged as acceptable, and marked with ○, and those with ΔH% slightly exceeding 4% or with some scratches were marked with Δ, ΔH% Of 10% or more, those with marked scratches, and those with peeling of the film were evaluated with x marks.

Acid resistance and alkali resistance: (acid resistance)-After immersing the test piece in a 0.1 N H ₂ SO ₄ solution at room temperature for 24 hours, the appearance was evaluated by visual observation. (Alkali resistance) --- The test piece was immersed in a 0.1N NaOH solution at room temperature for 24 hours, and the appearance was visually evaluated. Table 2 shows the results.

In each case, the appearance was visually inspected. If no change was observed before the measurement, it was judged as acceptable. The evaluation was made with marks.

Moisture resistance: After being kept for 2 weeks in an environment of a temperature of about 50 ° C. and a humidity of 95% RH, the appearance of the film surface was visually evaluated.
Table 2 shows the results.

When the external appearance was visually observed and no change was observed, it was evaluated as "OK", when a slight change was observed, and when a slight change was observed, and when a clear change was observed, the cross was evaluated.

As a result, as shown in the display, it can be seen that good glass having low visible light transmittance and visible light reflectance, low solar light transmittance, and excellent heat ray shielding properties in the range of the embodiment can be obtained.

Comparative Example 1 has a high solar radiation transmittance and is inferior in heat ray shielding properties. In addition, the stimulus purity is too high, and it is difficult to obtain a neutral color tone. Comparative Example 2 has high visible light transmittance, visible light reflectance, and solar transmittance, and Comparative Example 3 has high visible light transmittance, solar transmittance, and durability. Comparative Example 4 which is inferior in properties and has a high reflectance is out of the scope of the present invention. (In each table, the stoichiometrically example TiOx is TiO _2, TiNx is Ti ₃ N ₄
, TaOx indicates Ta ₂ O ₅ , and ZrOx indicates ZrO ₂ , respectively. However, since the sputtering does not always take the strict bonding mode as described above, the symbols are shown as shown. )

[0045]

[Table 1]

[0046]

[Table 2]

[0047]

[Table 3]

[0048]

[Table 4]

[0049]

[Table 5]

[0050]

[Table 6]

[0051]

[Table 7]

[0052]

[Table 8]

[0053]

[Table 9]

[0054]

[Table 10]

[0055]

As described above, according to the present invention, it has an excellent heat ray shielding property, exhibits a black to dark color tone, exhibits suitable light shielding properties and privacy properties, and suppresses the reflectance. There is no sense of incongruity visually. Furthermore, it has the effect of excelling in abrasion resistance, chemical resistance and moisture resistance, as it is as a single glass, or as a tempered, bent, bent tempered glass, of course, as a multi-layer glass or laminated glass, for buildings, buildings, It can be used for transfer machines such as vehicles, ships, aircrafts, etc., and particularly as window materials for automobiles, for example, rear window glass (shade band), side window glass (privacy) or sunroof glass (light shielding). Applicable.

Claims (4)

[Claims] 1. A laminated glass having a heat ray shielding film and a transparent non-coloring film sequentially formed on a glass substrate surface, wherein the laminated glass has a visible light transmittance of 10 to 30%, The visible light reflectance on the film side and the glass side of
Low reflectance and low transmittance glass characterized by having a transmittance of 12% or less and a solar transmittance of 15% or less. 2. The low reflectivity and low transmittance glass according to claim 1, wherein the laminated film is an alternate layer film of a heat ray shielding film and a transparent non-coloring film, each having two or more layers. 3. The heat ray shielding film is made of Ti, stainless steel, Cr,
The low reflectance and low transmittance glass according to claim 1 or 2, wherein the glass is at least one kind of nitride of Ni-Cr, Mo, W, Zr, Hf, Fe, Co, or Ni. 4. The transparent non-coloring film is at least one oxide of Ti, Zr, Ta, Al, or Si, or at least one of nitride of Al or nitride of Si. The low-reflectance and low-transmittance glass according to claim 1 or 2, wherein: