JPH11157880A - Glass sheet having improved functionality - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a glass sheet which is excellent in a see-through property from a glass surface side and a mirror effect on a film surface side by forming an oxide film, metallic film and nitride film respectively of specific thicknesses and specific metals on the front surface of a transparent glass substrate and forming these films in such a manner that the films have specific color tones, the excitation purity of reflected light, etc. SOLUTION: The transparent color tone of the glass sheet obtd. by successively depositing and laminating the oxide film of Ti having the film thickness of 45 to 60 nm as the first layer, the metallic film consisting of >=1 of Cr, nichrome, a stainless steel and Ta and having the film thickness of 5 to 15 nm as the second layer and the nitride film of Ti having the film thickness of 5 to 20 nm as the third layer on the front surface of the transparent glass substrate is formed to a neutral color tone and the excitation purity of the reflected light from the glass surface side in a visible ray wavelength region is specified to <=12% and the excitation purity of the reflected light from the film surface side to <=10%. In addition, the reflectivity difference of the reflected light from the glass surface side and the film surface side is specified to >=30%. More preferably the visible light reflectivity from the glass surface side is confined to <=12%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of coating a simple three-layer laminated film, giving a neutral perspective color and exhibiting a silver-based film surface reflection color tone, and achieving a good balance between the transparency and the mirror effect of the glass plate. , At the same time,
A glass plate that is friendly to people and the environment, expresses privacy and visibility, and has a higher level of function than normal privacy glass.For example, it is easy to see the dark corridor from the bright indoor side, and conversely, the dark corridor The present invention relates to a glass with enhanced functionality that makes it difficult to see a bright indoor side from the side.

In particular, the present invention provides a glass excellent in functionality, livability and environment that can utilize its functions in applications inside buildings, such as partition materials for offices and hospitals, and door window materials.

[0003]

2. Description of the Related Art There have conventionally been demands for glass plates or window glasses for protecting and protecting privacy, and various proposals have been made. In particular, recently, there is an increasing demand for window glasses for hospitals and automobiles.

[0004] For example, JP-A-6-80441 describes a heat-treatable sputter-coated glass product and a method for forming the same, a) selected from the group consisting of tin, zinc, titanium and alloys thereof. A first layer comprising a metal oxide selected from the group consisting of nickel and a metal alloy selected from the group consisting of nickel alloys having at least about 50% nickel by weight; c) a third layer of a metal selected from the group consisting of nickel and a nickel alloy having at least about 50% nickel by weight; d)
A fourth layer consisting of an oxide or nitride of a metal selected from the group consisting of nickel and a nickel alloy having at least about 50% nickel by weight; e) selected from the group consisting of tin, zinc, titanium and their alloys. A glass substrate having thereon a coating comprising a coated fifth layer of a metal oxide.

Among them, a glass substrate / SnO ₂ (1 to
1000 nm) / highness 214 (5 to 100 nm, oxide of Ni) / Ni (20 to 250 nm) / highness 214
(5-100 nm, oxide of Ni) / SnO ₂ (20-10
For example, a green tinted float glass, which has an achromatic gray color from the glass side and a gold color from the coating side, and has a visible transmittance of about 22 to 23% and about 11 to 11%.
A vehicle privacy window or the like having a glass side visible reflectance of 12% and a film side visible reflectance of about 31-33% is disclosed.

For example, Japanese Unexamined Patent Publication (Kokai) No. 6-321580 describes a wear-resistant low-transmittance glass in which a heat ray shielding film, a first transparent protective film, and a second transparent protective film are provided on the glass surface. A wear-resistant low-transmittance glass laminated sequentially, wherein the thickness of the second transparent protective film is 2 to 20 nm,
The sum of the thickness of the first transparent protective film and the thickness of the second transparent protective film is 25 nm or less, the visible light transmittance of the abrasion-resistant low transmittance glass is 40% or less, and The visible light reflectance of the glass surface of the abrasion-resistant low transmittance glass is 3
Those with 0% or less are disclosed.

Among them, specifically, for example, a glass plate /
CrN _x (26 nm) / SnO ₂ (10 nm) / Ta ₂ O ₅ (5
nm) or glass plate / TiN ₂ (60 nm) / SnO
₂ (5 nm) / ZrO ₂ (5 nm) etc., it has better wear resistance and chemical durability than conventional privacy glass, and can be used even under harsh conditions such as automotive door glass. Have been.

Further, for example, Japanese Patent Application Laid-Open No. Hei 5-10079 describes a light shielding window material and a light shielding method, and a polarizing plate is provided on one side of a transparent window material support such as a glass plate, an acrylic plate or a polycarbonate plate. It discloses that a plate having an additional plate and the light-shielding window material are used in combination with adjacent or opposing windows so that their polarization axes are orthogonal to each other.

[0009] Specifically, for example, by the structure of a glass substrate / adhesive layer / polarizing element / adhesive layer / glass substrate, the outside can be seen from the inside of a vehicle or a building, and the other can be seen from both windows. It is disclosed that the inside of a vehicle or a building is not visible, so that privacy protection and infringement are prevented from each other.

[0010] For example, Japanese Patent Application Laid-Open No. 1-127786 discloses a door of a hospital room, in which a dimming glass which can be turned on / off at a nurse station and a vicinity of a patient's bed is attached. Is disclosed.

Specifically, for example, instead of blinds, instantaneous dimming glass composed of laminated glass with a liquid crystal sheet sandwiched between two transparent glasses is used. Utilizing the characteristics of liquid crystal that aligns,
It discloses that the transparency of the glass is controlled, the opacity is always opaque, and the glass is transparent when energized, so that the patient can protect the privacy by simple operation, can operate from the nurse station side, and can respond quickly.

Further, for example, Japanese Patent Application Laid-Open No. 7-232934 discloses a heat ray reflective glass capable of exhibiting various colors to suppress the visible light reflectance on the outdoor side (the glass substrate side) and maintain the design. A heat ray reflective glass comprising a transparent metal oxide layer as a first layer, a metal film as a second layer, and a titanium nitride film as a third layer on a glass substrate is disclosed as a film configuration. .

Among them, specifically, a glass substrate / a transparent metal oxide layer (film thickness: titanium, tin, tantalum, etc.)
5 to 45 nm) / metal layer made of chromium, nichrome, stainless steel, etc. (film thickness: 1 to 20 nm) / titanium nitride (film thickness: 1)
(25 nm) or the like.

[0014]

In the above-mentioned conventional, for example, a heat-treatable sputter-coated glass product and a method of forming the same described in Japanese Patent Application Laid-Open No. 6-80441, for example, the visible light transmittance is suppressed. Therefore, privacy is intended to be exhibited by reducing the transparency, and the film configuration is made up of five layers, which is not always simple and easy.

For example, in the abrasion-resistant low transmittance glass described in JP-A-6-321580, for example, privacy is intended to be exhibited by reducing the transparency by suppressing the visible light transmittance. However, it is difficult to reduce the visible light reflectance from the film surface side due to the film configuration and film thickness of the house or building at night when the room is brighter than the outside at night. It is difficult to satisfy conditions that make it easy to see a dark room from a bright place.

Further, for example, the light shielding window material and the light shielding method described in JP-A-5-10079 do not depart from the technical matters of the conventional privacy glass, as is clear from the above-mentioned specific examples. In addition, it is difficult to say that the light shielding window material is always a simple structure, for example, it is necessary to use a light shielding window material in combination with an adjacent or opposing window so that the polarization axes thereof cross each other.

Furthermore, for example, in the ward of a hospital room described in Japanese Patent Application Laid-Open No. 1-127786, instantaneous light control glass composed of laminated glass with a liquid crystal sheet sandwiched between two transparent glasses is used and electrically operated. It can be used as a substitute for opening and closing the blinds, and the interior can be seen through or not seen from both the indoor side and the outdoor side as desired. Among them, those having transparency and visibility are hardly achieved.

Further, for example, the heat ray reflective glass described in Japanese Patent Application Laid-Open No. 7-232934 has an outdoor side (glass substrate side).
This is a glass that has the same reflectance as ordinary transparent plate glass and does not adversely affect the surroundings due to glare, etc., and is suitable for windows to the outside where sunlight is radiated, but color tone and perspective for use inside buildings It is hardly possible to satisfy simultaneously the balance between the properties and privacy by the mirror effect and the durability of the film in a well-balanced manner.

[0019]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned conventional problems, and has a combination of the specified three-layer film structure and the film thickness, and has a neutral transmission color tone. The stimulus purity in the visible light wavelength range of the reflected light from the glass surface side and the film surface side is specified, and the glass surface side has excellent reflection with low reflection, and the mirror surface has high reflection on the film surface side. In order to make the effect excellent,
By specifying the difference in the reflectance of the reflected light from the glass surface side and the film surface side in the visible light wavelength range, the reflection of the background on the glass surface is suppressed and the visibility in the dark place side is improved. At the same time, it is possible to enhance the reflection of the background on the film surface and reduce the visibility on the light place side. As a result, while exhibiting the design, see-through, mirror, and heat insulating properties, it has well-balanced optical properties, and has durability such as chemical resistance, weather resistance, and abrasion resistance. Glass having enhanced functionality with unprecedented unique optical properties that can express the above can be provided at low cost.

That is, according to the present invention, as a first layer, a Ti oxide film having a thickness of 45 nm to 60 nm is formed on a transparent glass substrate surface, and a second layer having a thickness of 5 nm to 15 nm is formed.
Cr, nichrome (hereinafter abbreviated as NiCr),
Stainless steel (hereinafter abbreviated as SUS), a metal film made of at least one of Ta, and a film thickness of 5 nm as a third layer
A glass plate in which a Ti nitride film having a thickness of at least 20 nm or less is sequentially formed and laminated, and the transmission color tone of the laminated glass plate is a neutral color tone, and reflected light from the glass surface side in a visible light wavelength region. Has a stimulus purity of 12% or less, a stimulus purity of light reflected from the film surface side is 10% or less, and a difference in reflectance between the glass surface side and the film surface side of 3%.
The present invention relates to a glass having enhanced functionality characterized by being 0% or more.

The reflectance of visible light from the glass surface side is 1
It is preferable that the content be 2% or less. Further, it is desirable that the visible light transmittance of the glass be 20 to 30%. Furthermore, it is preferable that the reflection color tone from the film surface side of the glass is a silver color tone.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION The glass with enhanced functionality of the present invention is implemented as follows. First, as the transparent glass substrate, for example, an inorganic glass plate which is a commercially available soda lime glass used for various glass plates such as buildings, especially float glass, and polycarbonate and acrylic are most suitable. A so-called glass plate made of an organic material may be used. Clear glass is best, and colored glass such as green glass, UV or heat ray absorbing glass may be used, flat or bent glass, and further strengthened. Glass, laminated glass,
Various processed glass such as a multi-layered glass and a surface-treated glass or glass for various uses may be used. Further, the shape of the glass plate is not particularly limited,
The one having a substantially quadrilateral shape consisting of a long side and a short side is most preferably employed. The thickness of the transparent glass substrate is not particularly limited.

Also, a Ti oxide film having a thickness of 45 nm or more and 60 nm or less as a first layer, and a Cr or NiCr film having a thickness of 5 nm or more and 15 nm or less as a second layer on the surface of the transparent glass substrate. , SUS, or a metal film made of at least one of Ta and a third layer having a thickness of 5 nm or more and 20 nm or more.
The glass substrate formed by laminating and laminating the following Ti nitride films is that the first oxide film of at least one of Sn and Ta is a mixture of argon and oxygen. A film formed by sputtering in a sputtering gas atmosphere in which the proportion of oxygen in the gas is 20 to 100% by volume. Each of the films has a refractive index (1.5) higher than that of glass. Since it is lower than the film, it is effective as an interference film that reduces the reflectance from the glass surface side, and was selected because it is a transparent dielectric film with a wealth of track record.

Further, a second layer of Cr, NiCr, SU
A metal film made of at least one of S and Ta has a higher electron density than a nitride film and an oxide film.
It is a film material that is effective for increasing the reflectance from the film surface side.

Next, with respect to the third Ti nitride film, a mixed gas of argon and nitrogen having a nitrogen content of 20 to
A film formed by sputtering in a sputtering gas atmosphere of 100% by volume, without impairing the reflection characteristics of the second metal film, and maintaining the mechanical and chemical durability of the metal film. Used as a protective film to improve. Therefore, the geometric film thickness is not defined by the color tone to be developed.

As a film forming method, a sputtering method is optimal, but other film forming methods which are commonly used, for example, CVD
Method, a vapor deposition method, a printing method, a spray method, various roll coating methods, a flow coating method, a flexo method, and the like.

Further, the transmission color tone of the glass on which the film is laminated is a neutral color tone, the stimulating purity of the reflected light from the glass surface side in the visible light wavelength range is 12% or less, and the reflected light from the film surface side is The stimulus purity is 10% or less, and the difference between the reflectance of the reflected light from the glass surface and the reflectance of the film surface is set to 30% or more. It detracts from aesthetics. Therefore, in order to suppress glare while having a low reflectance equal to or lower than that of the float glass, the first oxide thin film has a refractive index larger than that of glass and smaller than that of the metal film of the second layer. Thereby, the stimulus purity of the reflection color tone from the glass surface side is set to 12% or less, and a light pinkish tint is exhibited, thereby realizing a glass surface reflection color tone exhibiting an unprecedented aesthetic appearance.

On the other hand, when the reflectance of the reflected light from the film surface side is increased, the reflection color tone gradually shows metallic luster. Therefore, by setting the stimulating purity of the reflected light from the film surface side to 10% or less, the glare is weakened, and the mirror is enhanced by giving a silver-based color.

Further, since the transmission color tone of the glass is a neutral color tone and the difference between the reflectances of the reflected light from the glass surface and the film surface is 30% or more, the transparency and the mirror effect are appropriately provided. It is difficult to generate glare, discomfort is unlikely to occur, it is friendly to people and the environment, more effective dark place fluoroscopy function from the light place side and more effective light place non-transparency from the dark place side Functions can be optimally expressed.

Further, if the thickness of the first layer is less than 45 nm, the thickness of the second layer is less than 5 nm, and the thickness of the third layer is less than 5 nm, for example, the visible light transmittance is reduced to 30%. The function is not sufficient, for example, the translucency becomes stronger, and sufficient durability cannot be obtained, and the thickness of the first layer exceeds 60 nm and the thickness of the second layer is 15 nm. If the thickness exceeds 3 nm and the thickness of the third layer exceeds 20 nm, for example, the visible light transmittance is too low, the transparency is weak, the glass surface reflection is too high, and the productivity is poor. This is because the glass plate cannot be said to be a glass plate with enhanced initial functionality.

Further, the reason why the reflectance on the glass surface side in the visible light wavelength range is set to 12% or less is to suppress the reflection of the background on the glass surface side, and to more effectively see through a dark place. Visible light reflectance is 8 to exhibit function
% (Equivalent to float glass). The reason why the difference between the reflectances of the reflected light from the glass surface side and the film surface side is set to 30% or more is to exhibit optical properties such as initial transparency and mirror properties. Furthermore, the reason why the visible light transmittance is set in the range of 20 to 30% is to achieve both appropriate transparency and mirror properties.
However, the visible light transmittance is not limited to this range as long as the dark place seeing function from the light place side and the light place shielding function from the dark place side can be optimally exhibited.

In general, the optical characteristics are the balance of the transmittance, the reflectance, and the absorptance. If the optical characteristics are within the above-mentioned range, the transparency and the reflection, that is, the mirror properties, are well-balanced at the same time, and it is friendly to people and the environment. It can satisfy the comfort of living. In addition, durability (abrasion resistance, chemical resistance, etc.) is an important characteristic when wiping the film surface side with a detergent or the like when the glass becomes dirty.

Further, regarding the glass with enhanced functionality, when the film surface side having high reflection is defined as a dark place side and the glass surface side having low reflection is defined as a bright place side, more effective light from the bright place side is obtained. The present invention can be appropriately and optimally developed with a dark place perspective function and a more effective light place shielding function from the dark place side, and particularly when used in a state where the brightness difference between indoors and outdoors is not relatively large. The most effective and sufficient use of privacy glass is particularly effective in building interior, for example, as a glass plate for a partition or door between a nurse station and a corridor.

[0034]

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

Example 1 A float clear glass having a size of 300 mm × 300 mm and a thickness of 6 mm was sequentially washed with a neutral detergent, water rinse, and isopropyl alcohol, dried, and then set in a vacuum chamber of a DC magnetron sputtering apparatus. Some Ti, Cr, T
The target was set so that it could reciprocate upward, facing the target. Then, the inside of the tank was evacuated to about 5 × 10 ⁻⁶ Torr with a vacuum pump, and then O ₂ gas and Ar gas [however, ,
The gas flow ratio between Ar gas and O ₂ gas is O ₂ / (Ar + O ₂ )
Should be in the range of 0.2 to 1.0 (the Ar gas flow rate is zero at the value of 1.0).] And the degree of vacuum is reduced to about 2 × 10 ^−3. Torr, a power of about 3.0 kw was applied to the Ti target, and D
By transporting the glass sheet at a speed of about 45 mm / min through the C magnetron reactive sputter above the Ti target, a TiO _x (1
<X ≦ 2) A film was formed as a first layer. After the film formation was completed, the application to the Ti target was stopped. In Table 1, TiO _x is shown as TiO. (All TiO _x films formed in Examples and Comparative Examples described below are T
iO).

Next, while the plate glass is placed in the vacuum tank, the inside of the tank is evacuated to about 5 × 10 ⁻⁶ Torr by a vacuum pump, and Ar gas is introduced into the vacuum tank to reduce the degree of vacuum. Is maintained at about 2 × 10 ⁻³ Torr, a power of about 0.12 kw is applied to the Cr target, and a DC magnetron sputter by the Ar gas is performed at a speed of about 271 mm / min above the Cr target. By transporting the glass sheet, a Cr film having a thickness of about 6 nm was formed as a second layer on the TiO _x film surface of the glass sheet. After the film formation was completed, the application to the Cr target was stopped.

Subsequently, while the plate glass was kept in the vacuum chamber, the inside of the chamber was evacuated to about 5 × 10 ⁻⁶ Torr by a vacuum pump, and then N ₂ gas and Ar gas [ However,
The gas flow ratio of N ₂ gas to Ar gas is such that the value of N ₂ / (Ar + N ₂ ) is 0.2 to 1.0 (when the value is 1.0, the Ar gas flow is zero). , The degree of vacuum is maintained at about 2 × 10 ⁻³ Torr, a power of about 1.0 kw is applied to the Ti target, and D
By transporting the plate glass at a speed of about 104 mm / min above the Ti target in the C magnetron reaction sputtering, a TiN film having a thickness of about 14 nm was formed as a third layer. After the film formation was completed, the application to the Ti target was stopped.

With respect to the obtained glass sheet with a laminated thin film having three layers, the visible light transmittance (Tv) and the visible light reflectance (R
v), visible light reflectance difference, stimulus purity (Pv) (the wavelength range of measurement is 380 nm to 780 nm), and solar transmittance (Ts) and solar reflectance (Rs) (all of the wavelength range of measurement) Is in the range of 340 to 1800 nm).
Type spectrophotometer (manufactured by Hitachi, Ltd.) to measure the transmittance and reflectance data for each predetermined wavelength and JIS Z8
722, the optical characteristics (light source: D65 2 ° visual field) are respectively obtained according to JIS R 3106, and visible light transmittance, visible light reflectance, visible light reflectance difference, solar transmittance and main wavelength, stimulus purity, glass surface Table 1
It was shown to.

For the durability test, see JIS R
The chemical resistance test was performed based on 3221. For the glass sheet with a laminated thin film, the change in visible light transmittance (ΔTv) after immersion in a solution of 1N each of acid and alkali at 23 ± 2 ° C. for 6 hours. ,%).

In the Taber test, a change in the visible light transmittance (ΔTv,%) and a haze value of a sheet glass with a laminated thin film using a wear wheel (CS-10F) after rotating the load 500 g-300 times were used. Change (H%)
Was evaluated. In addition, each mark of (◎), (○), (△), and (×) in the column of the durability test in Table 1 is indicated by ◎.
△ Tv <1%, ○: 1% ≦ △ Tv <3%, △;
3% ≦ ΔTv <4%, mark x: 4% ≦ ΔTv.

As a result, G (glass) / TiO _x (45n
m) / Cr (6 nm) / TiN (14 nm) and the laminated glass sheet with a three-layered film structure, as shown in Table 1, has a visible light transmittance (Tv) of 23.2% and a glass surface side. Has a visible light reflectance (Rg) of 6.4%, a visible light reflectance (Rf) from the film surface side of 51.7%, and a visible light reflectance difference (△ Rv) between the film surface and the glass surface of 45%. 0.3%, the stimulating purity of visible light transmission is 2.1%, the stimulating purity of visible light reflection from a glass surface is 10.9%, and the stimulating purity of visible light reflection from a film surface is 4. 9%. 9%, which has a good balance between transparency and mirror effect, is gentle to people and the environment, and has heat insulation such as a solar radiation transmittance (Ts) of 20.6%. It is very effective.

Furthermore, the durability and the change in visible light transmittance (ΔTv) in the Taber test are about 2.2%, and the change in haze value (ΔH) is about 2.7%. Glass with excellent chemical resistance such as acid and alkali, and a pink color with a light reflection color from the glass surface and a silver color with a light reflection from the film surface. Met.

Examples 2 and 3 The above-mentioned Example 1 was performed using a 6 mm-thick float clear glass.
Since the film configuration is the same as that of Example 1,
And a sheet glass with a laminated thin film was obtained.

As a result of evaluating the obtained plate glass with a laminated thin film, as shown in Table 1, in the same manner as in Example 1, the visible light transmittance, the visible light reflectance, the visible light reflectance difference and the main wavelength, the stimulus purity, etc. In addition to the optical characteristics, the thermal performance and the color tone based on the solar transmittance were all within the desired range, and the glass plate had the desired functionality enhanced.

Example 4 The above-mentioned Example 1 was performed using 6 mm thick float clear glass.
A film was formed in the same manner as in Example 1 so as to have a film thickness shown in Table 1, and a sheet glass with a laminated thin film was obtained. The second metal film was changed to SUS as compared with Example 1.

That is, the second layer was formed by using a SUS target instead of the Cr target used in Example 1, applying a power of about 0.12 kw to the SUS target, and applying a DC magnetron using the Ar gas. A speed of about 20 above the SUS target in the sputtering
By transferring the glass sheet at 7 mm / min, a 7 nm thick SUS film was formed as a second layer on the TiO _x thin film surface of the glass sheet. After film formation is completed, SUS
The application to the target was stopped. The first layer and the third layer
The layers were formed in the same manner as in Example 1 so as to have the thickness shown in Table 1.

As a result of evaluating the obtained plate with a laminated thin film,
As shown in Table 1, in the same manner as in Example 1, not only optical characteristics such as visible light transmittance, visible light reflectance, visible light reflectance difference, main wavelength, and stimulus purity, but also thermal performance and color tone due to solar transmittance. All were within the target range, and the glass plate had the desired functionality.

Comparative Example 1 A 6 mm thick float clear glass was used in the same manner as in Example 1, and the film configuration and thickness were changed as shown in Table 1 in the same manner as in Example 1 to obtain a sheet glass with a laminated thin film. Obtained. As for the film configuration, the first layer was formed of a SnO _x film as compared with Example 1.

That is, in the same manner as in Example 1, the O ₂ gas and Ar gas were introduced using a Sn target in a DC magnetron reactive sputtering apparatus, and about 1.0 kW.
Is applied and the sheet glass transport speed is about 142 mm /
A SnO _x thin film having a thickness of about 30 nm in min was formed as the first layer. After the film formation was completed, the application to the Sn target was stopped. In Table 1, SnO _x is shown as SnO. (Note that SnOx formed in a comparative example described later is similarly shown as SnO in Table 1).

Then, using a Cr target, an Ar gas was introduced, an electric power of about 0.12 kW was applied, and a Cr film having a thickness of about 5 nm was formed as a second layer at a sheet glass conveyance speed of about 326 mm / min. Filmed. After the film formation is completed,
The application to the Cr target was stopped.

[0051] Then, N ₂ gas and Ar gas [except the vacuum chamber, the gas flow ratio of N ₂ gas and Ar gas is N ₂ / (Ar +
N ₂ ) is 0.2 to 1.0 (when the value of 1.0 is A
r gas flow rate should be in the range of zero), a power of about 1.0 kw is applied to the Ti target, and the Ti gas is mixed in the DC magnetron reaction sputtering by the mixed gas. By transporting the plate glass at a speed of about 145 mm / min above the target, a TiN film having a thickness of about 10 nm was formed as a third layer. After the film formation was completed, the application to the Ti target was stopped.

With respect to the obtained plate glass with a laminated thin film, each measurement was carried out using each device in the same manner as in Example 1 and evaluated.
As a result, as shown in Table 1, the difference between the film surface reflectance and the glass surface reflectance was 25.
It was as small as 5%, and it was hard to say that the glass plate had the desired functionality.

Comparative Example 2 A plate glass with a laminated thin film was obtained by using float clear glass having a thickness of 6 mm and having the same film configuration as in Comparative Example 1, and changing the film thickness as shown in Table 1.

As a result, in the obtained plate glass with a laminated thin film, as shown in Table 1, the difference between the film surface reflectance and the glass surface reflectance was as small as 23.7%, and the glass surface reflectance was 22.2%.
It was as large as 5%, poor in visibility from the glass surface side, and could hardly be said to be a glass plate with enhanced intended functionality.

Comparative Example 3 The above-mentioned Example 1 was performed using 6 mm thick float clear glass.
A film was formed in the same manner as in Example 1 so as to have a film thickness shown in Table 1, and a sheet glass with a laminated thin film was obtained. It should be noted that the second metal film was changed to Ti in comparison with Comparative Example 1. .

That is, the second layer was formed by using a Ti target instead of the Cr target used in Comparative Example 1.
An electric power of about 0.12 kw was applied to the Ti target, and a speed of about 181 mm / mi was applied above the Ti target in the DC magnetron sputtering using the Ar gas.
By transporting the plate glass with n, a Ti film having a thickness of 15 nm was formed as a second layer on the SnO _x thin film surface of the plate glass. After the film formation was completed, the application to the Ti target was stopped. The first and third layers were formed in the same manner as in Comparative Example 1 so as to have the thickness shown in Table 1.

As a result of evaluating the obtained plate with a laminated thin film,
As shown in Table 1, the change in visible light transmittance (△ Tv) after the Taber test is extremely bad at 33.6%, which is not suitable for practical use, and the change rate of haze (△ H) is as large as 4.2% ( The glass plate with the intended functionality enhanced, such as passing the JIS R 3221 of 4% or less for the above-mentioned durability test), extremely weak abrasion resistance, poor acid resistance and poor chemical resistance. It was hard to say.

COMPARATIVE EXAMPLE 4 Since a 6 mm thick float clear glass was used and had the same film configuration as in Example 1, the thickness was as shown in Table 1 in the same manner as in Example 1, and a sheet glass with a laminated thin film was prepared. Obtained.

As a result of evaluating the obtained glass sheet with a laminated thin film, the obtained glass sheet with a laminated thin film had a stimulus purity of 38.5 for reflected light from the glass surface as shown in Table 1.
%, The reflection color tone on the glass surface side was a yellow color tone, a strong glare was generated, and both aesthetics and design were lacking. Further, the change in haze after the Taber test was 3% or more, and it was hard to say that the glass plate had the intended functionality enhanced.

Comparative Example 5 Using a 6 mm-thick float clear glass, the film configuration and the film thickness were changed as shown in Table 1 in the same manner as in Example 1, and two layers were formed in the same manner as in Example 1. A sheet glass with a laminated thin film was obtained.

That is, first, using a Ti target,
O ₂ introduced gas and Ar gas, applying a power of about 3.0 kW, a film of TiO _x about 36nm thick with the conveying speed of about 34 mm / min of the glass sheet was formed as the first layer. After the film formation was completed, the application to the Ti target was stopped.

[0062] Then, N ₂ gas and Ar gas [except the vacuum chamber, the gas flow ratio of N ₂ gas and Ar gas is N ₂ / (Ar +
N ₂ ) is 0.2 to 1.0 (when the value of 1.0 is A
r gas flow rate is zero). ], And apply about 0.5kw of electric power to the SUS target,
In the DC magnetron sputtering by the mixed gas,
Speed about 105 above the SUS target
By transporting the glass sheet at a rate of about 20 mm / min.
A SUSN thin film having a thickness of nm was formed as a second layer. After the film formation was completed, the application to the SUS target was stopped.

As a result of evaluating the obtained glass sheet with a laminated thin film, the obtained glass sheet with a laminated thin film had an excitation purity of 19.0 as reflected light from the glass surface as shown in Table 1.
The result was a large, strong glare, and lacked both aesthetics and design. Furthermore, the amount of change in visible light transmittance after the Taber test is also slightly large, which is not preferable, and it is hardly possible to say that the glass plate has the desired functionality enhanced, such as poor acid resistance and poor chemical resistance. there were.

Comparative Example 6 Using a 6 mm-thick float clear glass, in the same manner as in Example 1, the film configuration and the film thickness were changed as shown in Table 1 to obtain a sheet glass with a laminated thin film.

As compared with the first embodiment, the second layer was formed of oxynitrided stainless steel (hereinafter abbreviated as SUSNO) and the third layer was formed of TiOx. That is, the second layer uses a SUS target, introduces O ₂ gas and N ₂ gas, applies electric power of about 0.5 kw, and transfers the sheet glass at a speed of about 204 mm / min.
An O film was formed as a second layer. After film formation is completed, SU
The application to the S target was stopped.

Subsequently, O ₂ gas and Ar gas were introduced into the vacuum chamber, an electric power of about 3.0 kw was applied, and a TiO having a thickness of about 10 nm was transported at a sheet glass conveyance speed of about 121 mm / min.
_{An x} film was formed as a third layer. After the film formation is completed, T
The application to the i target was stopped.

As a result of evaluating the obtained glass sheet with a laminated thin film, the obtained glass sheet with a laminated thin film had a high stimulating purity of 24.0 as reflected light from the film surface as shown in Table 1; Became yellow with a glaring feeling and was not suitable for practical use. In addition, it was hardly possible to say that a glass plate had the desired functionality, such as poor acid resistance and poor chemical resistance.

[0068]

[Table 1]

[0069]

As described above, according to the present invention,
The film configuration and thickness of the glass substrate having a simple three-layered thin film layer formed on the surface, the transmission color tone of the glass is neutral, and the stimulation purity of the reflection color tone from the glass surface side and from the film surface side is determined. By specifying, and making the difference in the reflectance of the reflected light between the glass surface side and the film surface side 30% or more, it is impossible to achieve both the dark place transparency and the bright place transparency shielding with the conventional privacy glass. However, the reflectance difference makes the film surface on the dark place side highly reflective to make an astigmatic effect, making it difficult to see the scenery on the light place side, and making the glass surface on the light place side low reflective and astigmatic. The privacy glass can be made more functional, such as making the view on the film surface easier to see without causing any effects.The privacy glass with enhanced functionality can be provided at a low cost with a simple film configuration etc. Especially for indoor use , There is provided an office can exert its function in a variety of applications in, hospitals or the like, a glass with improved comfort and environmental resistance even with functionality.

Claims (4)

[Claims] 1. A Ti oxide film having a thickness of 45 nm or more and 60 nm or less as a first layer on a surface of a transparent glass substrate;
Cr having a thickness of 5 nm or more and 15 nm or less as a second layer;
A glass plate in which a metal film made of at least one of nichrome, stainless steel, and Ta, and a nitride film of Ti having a thickness of 5 nm or more and 20 nm or less are sequentially formed and laminated as a third layer, The transmission color tone of the laminated glass plate is a neutral color tone, the excitation purity of reflected light from the glass surface side in the visible light wavelength range is 12% or less, and the excitation purity of reflected light from the film surface side is 10% or less. In addition, the difference in reflectance of the reflected light from the glass surface side and the film surface side is set to 30% or more, and the excellent transparency from the glass surface side and excellent functionality of the mirror effect on the film surface side. Enhanced glass. 2. The visible light reflectance from the glass surface side is 12%.
The glass with enhanced functionality according to claim 1, wherein: 3. The glass with enhanced functionality according to claim 1, wherein the glass has a visible light transmittance of 20 to 30%. 4. The glass with enhanced functionality according to claim 1, wherein the reflection color tone from the film surface side of the glass is a silver color tone.