JP2008222507A - Multiple glass - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a multiple glass, excellent in a heat insulative property suppressing the heat flow from the inside of a room to outdoor during winter, a heat-shielding property suppressing the flow of solar energy coming into a room during summer, high in visible light transmittance and excellent in giving lighting and visibility effects. <P>SOLUTION: The multiple glass is obtained by arranging two glass sheets apart from each other at a specific distance, where a low resistive film comprising successively laminated layers of the first Ag film, the second metal oxide film, the second Ag film and the third metal oxide film is placed at the side of a hollow layer, and the first metal oxide film, the second metal oxide film and the third metal oxide film comprise each a metal oxide film consisting mainly of ZnO film. The diffraction angle of the diffraction peak at the crystal face (002) of the ZnO film is at most 33.9°; the glass sheet has the thickness of at least 3 mm; and for the total thickness t1 of the two glass sheets, the visible light transmittance of the multiple glass is at least (70.0-0.3×t1)% and the solar heat gain coefficient is at most 0.38. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a multi-layer glass used for windows of buildings and vehicles.

  2. Description of the Related Art Recently, window glass of a building such as a house or a building is used as an energy-saving window material that suppresses inflow of solar radiation energy from outdoor to indoor in summer and suppresses heat flow from indoor to outdoor in winter. Multi-layer glass in which a sheet of transparent glass is combined through a spacer and an insulating air layer is formed between the two transparent glasses has come to be used.

  In addition, the window glass of buildings such as houses and buildings has become larger for the purpose of improving habitability and outdoor visibility, and as a result, inflow of solar energy into the room has increased in summer. The cooling load has increased.

  Therefore, in order to suppress the inflow of solar radiation energy into the room in summer and reduce the cooling load, low-emission glass in which an infrared reflecting film is formed on the indoor side glass of the multi-layer glass has come to be often used.

  As an infrared reflecting film, a laminated film in which ZnO films and Ag films are alternately laminated is known.

  Patent Document 1 discloses an infrared reflective film in which a ZnO film and an Ag film having a thickness of 110 mm or less are alternately laminated. In the examples in which the Ag film has one layer and two layers, visible light transmittance is disclosed. Is a low emission glass having a solar energy transmittance of 44% or more.

Patent Document 2 discloses a film in which a ZnO film, an Ag film, and a ZnO film are sequentially laminated on glass, and an amorphous layer (SiN _x ) is laminated thereon to improve durability. Moreover, the Example whose visible light transmittance is 78 to 83% is described. Patent Document 3 discloses a laminated film in which five layers of ZnO films and Ag films having a visible light transmittance of 71.2 to 80.0% and a solar radiation transmittance of 30.4 to 45.6% are alternately laminated. Is described.

  Furthermore, Patent Document 4 describes a multilayer glass having a visible light transmittance of 49 to 51% and a solar radiation transmittance of 30 to 32% using a heat shielding film and an antireflection film using one Ag film. ing.

  In the infrared reflection film in which the ZnO film and the Ag film are alternately laminated, the infrared reflectance increases as the resistance value of the Ag film decreases. Therefore, in order to increase the infrared reflectance and improve the shielding performance, Ag The film may be thickened to lower its resistance, but if the Ag film is thickened, the visible light transmittance is reduced and the lighting performance of the window is deteriorated.

Regarding the resistance of the Ag film, Patent Document 5 discloses that a laminated film in which ZnO films and Ag films are alternately laminated and four Ag films having a thickness of 12 nm are laminated to obtain a low resistance film of 4.2Ω / □. Is described. Furthermore, Patent Document 6 discloses that when the Ag film is formed by magnetron sputtering, the discharge voltage and the strength of the magnetic field on the surface of the Ag target are adjusted, and when the Ag film is a single layer, the thickness t1 of the Ag film. In the range of 5 to 30 nm, the specific thickness of the laminated film is (35.8 / t1 + 2.3) × 10 ⁻⁶ Ωcm or less, and the total thickness of the Ag film when the Ag reflective film has two layers. An infrared reflective laminated film is described in which the specific resistance of the laminated film is (168.6 / t2 + 1.3) × 10 ⁻⁶ Ωcm or less when t2 is in the range of 15 to 35 nm.

  In order to obtain high visible light transmittance, it is effective to reduce the thickness of the Ag film, which is a metal film. However, if the thickness of the Ag film is reduced, the infrared reflectance decreases, and the infrared reflectance is reduced. With the decrease, the solar reflectance decreases and the inflow of solar energy into the room increases, resulting in a decrease in heat shielding properties.

  Therefore, the film thickness of the Ag film is determined in consideration of the visible light transmittance and the solar reflectance.

Further, regarding the infrared reflective film in which the ZnO film and the Ag film are alternately laminated, the durability of the infrared reflective film is improved. Patent Document 7 describes the X-ray diffraction relating to the crystallinity of the ZnO film. Describes X-ray diffraction relating to the crystallinity of Ag.
JP 63-134232 A JP 2002-173343 A JP 2004-58592 A JP 2006-143525 A Japanese Patent Laid-Open No. 63-239044 JP 2006-206424 A JP-A-4-357525 Japanese Patent Laid-Open No. 5-24149

  An object of the present invention is to provide a multi-layer glass having a high visible light transmittance and a high heat shielding property with a small amount of solar energy flowing into a room.

  In the multilayer glass of the present invention, two sheet glasses are opposed to each other at a predetermined interval, and a spacer is disposed at the peripheral edge of the two sheet glasses so as to maintain the predetermined interval. In a multi-layer glass in which a hollow layer sealed between plate glasses is formed and a low resistance film is formed on one sheet glass, the low resistance film is disposed on the hollow layer side, and the low resistance film is a first layer. A metal oxide film, a first Ag film, a second metal oxide film, a second Ag film, and a third metal oxide film are sequentially laminated, and are a first metal oxide film and a second metal oxide film. The third metal oxide film is a metal oxide film mainly composed of a ZnO film, and the ZnO film is diffracted by a diffraction peak by the (002) crystal plane of the ZnO film by an X-ray diffraction method using CuKα rays. The angle 2θ is 33.9 ° or less, and the two glass sheets of the multilayer glass are both 3 mm or more in thickness. The visible light transmittance according to JIS R3106: 1998 of the multilayer glass is not less than (70.0−0.3 × t1)% with respect to the total thickness t1 (mm) of the two plate glasses. Yes, the double-glazed glass is characterized in that the solar heat acquisition rate based on JIS R3106: 1998 is 0.38 or less.

  Further, in the multilayer glass of the present invention, in the multilayer glass, the laminated film has a total thickness of the first Ag film and the second Ag film of t2 (nm), and the surface resistance of the low resistance film is (3 4-0.04 × t2) A double glazing characterized by being Ω / □ or less.

  Further, in the multilayer glass of the present invention, in the multilayer glass, the optical thickness of the first metal oxide film is in the range of 57 nm to 77 nm, the thickness of the first Ag film is in the range of 12 nm to 16 nm, The optical thickness of the metal oxide film is in the range of 160 nm to 200 nm, the thickness of the second Ag film is in the range of 12 nm to 16 nm, and the optical thickness of the third metal oxide film is in the range of 62 nm to 82 nm. It is a multilayer glass.

  Further, in the multilayer glass of the present invention, in the multilayer glass, the reflection color of the glass surface of the plate glass on which the low resistance film is formed is −20 ≦ a in the CIE L * a * b * chromaticity coordinate diagram. * ≦ −5, −10 ≦ b * ≦ 5.

  The double-glazed glass of the present invention realizes a bright and excellent heat-shielding window by providing a double-glazed glass having a low solar heat acquisition rate and a high visible light transmittance.

  The double-glazed glass of the present invention is highly transparent and is used for a window glass intended to block solar radiation in buildings such as houses and buildings.

  As shown in FIG. 1, the multi-layer glass of the present invention has a transparent plate glass 1 on which a low-resistance film 2 is formed and another transparent plate glass 1 facing each other, and the periphery of the plate glasses 1 and 1 ′. The portion is bonded to the spacer 4 with the adhesive 3, and the peripheral portion is sealed with a sealing material 5 to form a sealed hollow layer between the two transparent plate glasses 1, 1 ′.

  When the multilayer glass of the present invention is installed in a building window, it is preferable that the transparent plate glass 1 on which the low-resistance film 2 is formed be the outdoor side.

  In order to prevent condensation of the hollow layer, the spacer 4 is preferably a pacer filled with a drying material (not shown).

  A low resistance film 2 formed by alternately laminating metal oxide films and Ag films as shown in FIG. 2 is formed on two transparent plate glasses 1.

  A protective metal film (not shown) is preferably formed on the surface of each Ag film opposite to the plate glass in order to prevent the Ag film from being oxidized when the metal oxide film is formed.

  For transparent plate glass, inexpensive float plate glass such as soda lime glass and high transmission glass with less iron oxide content than soda lime glass is suitable, but besides transparent glass, polycarbonate, polyethylene terephthalate, etc. A transparent resin substrate, a film substrate, or the like can be suitably used.

  The metal oxide film is used to increase the adhesion between the plate glass and the Ag film and the adhesion between the low resistance films, and to increase the strength and durability of the laminated film of the low emission glass. Used to increase the visible light transmittance of glass.

  As the metal oxide film, it is preferable to use a ZnO film adjacent to the transparent glass side of the Ag film in order to obtain a suitable film strength and durability of the low emission glass and high transmittance.

  In addition to the ZnO film, the metal oxide film includes at least one of an oxide film such as Si, Sn, Al, Ti, a nitride film such as Si, Sn, Zn, Al, Ti, or a nitride oxide film. A metal oxide film selected from one or more types may be used.

  The metal oxide film is formed by using a metal target as the target 20 and introducing an oxygen gas from the gas introduction pipe 26 using a magnetron sputtering apparatus as shown in FIG. A dielectric film can be formed using an oxide target.

  The transparent glass plate 21 is held by the substrate holder 22, the inside of the vacuum chamber 23 is evacuated by using the vacuum pump 25 by opening the main valve 24, and the metal oxide is further introduced into the vacuum chamber from the gas introduction pipe 25. In the case of forming a film, it is preferable to adjust the pressure in the vacuum chamber 23 by introducing oxygen gas or a mixed gas of Ar and oxygen while controlling the gas flow rate by the mass flow controller 26.

  The substrate holder 22 holding the transparent plate glass 21 has a movable structure (not shown), and the time for the plate glass 21 to pass the target 20 is changed by changing the moving speed of the substrate holder 22. It is desirable to control the thickness of the film to be formed.

  For example, when forming a ZnO film, it is possible to form a film by using a Zn target as the target 20 and introducing Ar gas and oxygen gas in an appropriate mixing ratio from the gas introduction pipe 25. Alternatively, a ZnO film may be formed by introducing only Ar gas from the gas introduction pipe 25 using a ZnO target as the target 20.

  Furthermore, the ZnO film preferably has a diffraction peak maximum intensity position of 33.9 ° or less by the ZnO (002) plane as measured by X-ray diffraction.

  The pressure in the vacuum chamber 8 at the time of film formation is adjusted by the flow rate of oxygen gas introduced by being controlled by a vacuum pump and a mass flow controller, but the film is formed at a pressure as low as possible within a range where stable discharge can be maintained. It is preferable. The pressure in the vacuum chamber 23 is measured by a vacuum gauge 26.

  When the diffraction angle 2θ of the diffraction peak maximum intensity by the ZnO (002) plane measured by the X-ray diffraction method using CuKα rays is 34 ° or more, the resistance value per unit thickness of the Ag film is large. Therefore, when the diffraction angle 2θ of the diffraction peak maximum intensity by the ZnO (002) plane measured by the X-ray diffraction method using CuKα rays is 34 ° or more, in order to reduce the resistance value of the Ag film, Ag The film must be thick, and it becomes difficult to obtain a preferable visible light transmittance.

  In order for the diffraction angle 2θ of the ZnO film to be 33.9 ° or less, the flow rate of oxygen gas is preferably 200 sccm or less, and the pressure in the vacuum chamber 23 is preferably 0.9 Pa or less. Is as low as possible.

  Similarly to the metal oxide film, the Ag film can be formed by the magnetron sputtering apparatus shown in FIG. 3. The Ag film and the metal oxide film can be formed in contact with the ZnO film of the metal oxide film. This is preferable because the adhesiveness is maintained.

  An Ag metal target is used as the target 20, a transparent plate glass 21 is held by a substrate holder 22, the inside of the vacuum chamber 23 is evacuated by using a vacuum pump 25 by opening the main valve 24, and further inside the vacuum chamber. Ar gas is introduced from the gas introduction pipe 25 by controlling the gas flow rate by the mass flow controller 26, the target is passed through the substrate holder 22 holding the transparent plate glass 21 at a desired speed, and an Ag film is formed on the transparent plate glass. Form.

  For the Ag film, a metal film is formed using an Ag target containing about 0.0 to 10.0% by weight of a metal such as Pt, Bi, Cu, or Au, and Pt, Bi containing Ag as a main component. Alternatively, a metal film containing 0.0 to 10.0% by weight of a metal such as Cu or Au may be used.

  The selection of the metal oxide film described above is desirably performed in consideration of optical characteristics in the visible region, mechanical strength of the metal oxide film itself, and adhesion to the adjacent metal oxide film and Ag film.

When the refractive index at a wavelength of 550 nm of the metal oxide film is n, and the optical film thickness is n _d when the geometric film thickness of the metal oxide film is d (nm), the first metal oxide film n _d is in the range of 57Nm～77nm, _{n d} of the second metal oxide film is in the range of 160Nm～200nm, it is preferable _{that n d} of the third metal oxide film is in the range of 62Nm～82nm.

  Lower limit of optical thickness of metal oxide film (57 nm for first metal oxide film directly deposited on transparent glass, 160 nm for second metal oxide film, third metal oxide film Or less than 62 nm), or the upper limit of the optical film thickness of the metal oxide film (in the case of the first metal oxide film formed directly on the transparent glass, 77 nm, the second metal oxide In the case of a film, if it exceeds 200 nm, and in the case of a third metal oxide film, it exceeds 82 nm), the visible light transmittance is lowered, and further, it is impossible to obtain a reflection color tone preferable for building use.

  Furthermore, the sum of the geometric thickness of the first Ag film and the geometric thickness of the second Ag film, that is, the total geometric thickness of the Ag film is preferably in the range of 24 to 32 nm. When the total geometric film thickness is less than 24 nm, the solar reflectance is decreased, and effective heat shielding is not obtained. When the total geometric film thickness exceeds 32 nm, the visible light transmittance is decreased, Furthermore, it becomes a reddish reflection color tone, which is not preferable for building use.

  Further, in order to prevent the first Ag film from being damaged by the plasma during the formation of the second metal oxide film, a protective film having a geometric film thickness of about 2 nm between the first Ag film and the second metal oxide film. It is desirable to form a metal film. Similarly, it is desirable to form a protective metal film between the second Ag film and the third metal oxide film.

  As the protective metal film, use may be made of Zn, Sn, Ti, Al, NiCr, Cr, Zn alloy, Sn alloy, and each metal containing 0.0 to 10.0% by weight of Al, Sb metal. it can.

  In place of the protective metal film, zinc oxide (ZnAlOx) containing 2 to 12% by weight of Al (hereinafter referred to as an AZO film) can be used.

  The Ag film and the metal oxide film are preferably formed by a sputtering method, and particularly preferably formed using a magnetron sputtering apparatus as shown in FIG.

  The metal oxide film is formed by using a metal target as a target and introducing oxygen gas from a gas introduction pipe, or by forming the target using the same oxide target as the oxide to be formed. be able to.

  Hereinafter, the present invention will be described in detail with reference to the drawings.

Example 1
As shown in FIG. 2, the first metal oxide film 10, the first Ag film 13, the second metal oxide film 11, the second Ag film 14, and the third metal oxide film 12 are shown in FIG. The low resistance film 2 was formed by stacking using a magnetron sputtering apparatus. As the plate glass 1, soda lime glass having a thickness of 3 mm was used.

  As the first metal oxide film 10, a ZnO film was formed on soda lime glass having a thickness of 3 mm. A Zn target was used as the target 20, soda lime glass was held on the substrate holder 22, and then the vacuum chamber 23 was evacuated by the vacuum pump 25. During film formation, the vacuum pump 25 was continuously operated.

  The atmospheric gas in the vacuum chamber 23 was adjusted by introducing an oxygen gas from a gas introduction pipe 26 and controlling the flow rate of the oxygen gas by a mass flow controller 27.

  A cryopump was used as the vacuum pump 25. The pressure in the vacuum chamber during film formation is controlled by controlling the oxygen gas flow rate to 60 sccm or less by the mass flow controller 27 and introducing it into the pressure chamber 23 to adjust the pressure in the pressure chamber 23 to a desired 0.3 Pa. did.

  A ZnO film was used as the first metal oxide film and was formed with a geometric thickness of 32 nm. The geometric thickness of the ZnO film was adjusted by the conveyance speed of the plate glass.

Refractive index at a wavelength of 550nm of the formed ZnO film (the real part of the complex refractive index) is 2.1, the optical thickness _{n d} of the ZnO film of the first metal oxide 10 was 67 nm.

  Next, after evacuating the oxygen gas in the vacuum chamber 23, the Ar gas is controlled by the mass flow controller 27 from the gas introduction pipe 26 and introduced into the vacuum chamber 23, and the inside of the vacuum chamber 23 is made an Ar gas atmosphere. A 1 Ag film 13 was formed.

  The first Ag film was formed on the first metal oxide film (ZnO film) using an Ag target as the target 20. The geometric thickness of the first Ag film was 14 nm.

  During the formation of the first Ag film, the pressure in the vacuum chamber was set to 0.5 Pa by a vacuum pump and an opening / closing valve.

  Next, a ZnAl film having a geometric thickness of 2 nm (not shown in FIG. 2) was formed on the first Ag film using a ZnAl (Al4 wt% -containing ZnO) target.

  During the formation of the ZnAl film, the gas atmosphere and pressure in the pressure chamber were the same as in the formation of the Ag film.

  Further, a ZnO film was formed as a second metal oxide film 11 on the ZnAl film with an optical thickness of 182 nm. The film formation conditions were the same as those for the ZnO film of the first metal oxide film 10 formed on the surface of the plate glass 21.

  Further, a second Ag film 14 was formed on the second metal oxide film 11 with a geometric film thickness of 14 nm. The second Ag film 14 was formed in the same manner as the first Ag film.

  Next, a ZnAl film having a geometric thickness of 2 nm (not shown in FIG. 2) was formed on the second Ag film using a ZnAl (Al4 wt% -containing ZnO) target. The film formation was performed in the same manner as the ZnAl film formed on the first Ag film.

  Furthermore, a ZnO film having an optical thickness of 72 nm was formed as the third metal oxide film 12 on the ZnAl film. The film formation was performed in the same manner as the ZnO film formed as the first metal oxide film 10 on the surface of the plate glass.

  A multi-layer glass as shown in FIG. 1 was produced using the plate glass 1 on which the low resistance film 2 was formed in this way. As the plate glass 1 ′, soda lime glass having a thickness of 3 mm was used.

  The multi-layer glass was composed of soda lime glass having a thickness of 3 mm and a soda lime glass having an air layer of 6 mm and a thickness of 3 mm formed with a low resistance film 2 from the outdoor side.

  As a result of calculating the visible light transmittance and the solar heat acquisition rate based on JIS R3106: 1998, the visible light transmittance was 69.3% and the solar heat acquisition rate was 0.36. In addition, in the CIEL * a * b * chromaticity coordinate diagram, the reflection color of the non-film surface of normal incident light was −9.2 and b * was −5.3.

Example 2
A multilayer glass was produced in the same manner as in Example 1 except that soda lime glass having a thickness of 6 mm was used for the plate glasses 1 and 1 ′.

  When the plate glass 1 was set to the outdoor side, the visible light transmittance calculated in accordance with JIS R3106: 1998 was 67.0%, and the solar heat gain rate was 0.36. In addition, the reflection color of the non-film surface of normal incident light was −9.3 for a * and −6.1 for b *.

Example 3
The same procedure as in Example 1 was performed except that soda lime glass having a thickness of 12 mm was used for the plate glasses 1 and 1 '.

  When it calculated based on JISR3106: 1998 when the plate glass 1 was made into the outdoor side, the visible light transmittance | permeability was 63.7% and the solar radiation heat acquisition rate was 0.35. The reflection color of the non-film surface of normal incident light was a * of -10.5 and b * of -5.6.

Example 4
The same procedure as in Example 1 was performed, except that a high transmittance glass having a thickness of 6 mm and a visible light transmittance of 91% was used for the plate glasses 1 and 1 ′.

  When it calculated based on JISR3106: 1998 when the plate glass 1 was made into the outdoor side, the visible light transmittance | permeability was 69.9% and the solar radiation heat acquisition rate was 0.35. In addition, the reflection color of the non-film surface of the normal incident light was a * of −11.2 and b * of −6.6.

Example 5
Example 1 is the same as Example 1 except that a high transmittance glass having a visible light transmittance of 91% having a thickness of 6 mm is used for the plate glass 1 and a high transmittance glass having a thickness of 90% having a visible light transmittance of 12 mm is used for the plate glass 1 ′. I made it.

  When it calculated based on JISR3106: 1998 when the plate glass 1 was made into the outdoor side, the visible light transmittance | permeability was 69.2% and the solar radiation heat acquisition rate was 0.34. Further, the reflection color of the non-film surface of the normal incident light was a * of −11.2 and b * of −6.6.

Example 6
The same high-transmission glass with a thickness of 6 mm as in Example 5 is used for the plate glass 1, and a SnO ₂ film is formed on the plate glass 1 as the first metal oxide film 10, and then a ZnO film is formed on the SnO ₂ film. A film was formed.

The SnO ₂ film was formed by using a Sn target as the target 20, holding the highly transmissive glass on the substrate holder 22, and then evacuating the vacuum chamber 23 with the vacuum pump 25. During film formation, the vacuum pump 25 was continuously operated.

  The atmospheric gas in the vacuum chamber 23 was adjusted by introducing an oxygen gas from a gas introduction pipe 26 and controlling the flow rate of the oxygen gas by a mass flow controller 27.

  A cryopump was used as the vacuum pump 25. The pressure in the vacuum chamber during film formation is controlled by controlling the oxygen gas flow rate to 60 sccm or less by the mass flow controller 27 and introducing it into the pressure chamber 23 to adjust the pressure in the pressure chamber 23 to a desired 0.3 Pa. did.

The ZnO film is formed by using a Zn target as the target 20, holding the highly transmissive glass on which the SnO ₂ film is formed on the substrate holder 22, and, similarly to the formation of the SnO ₂ film, using the mass flow controller 27 with the oxygen gas flow rate. Was controlled to 60 sccm or less, and the pressure in the pressure chamber 23 was adjusted to a desired 0.3 Pa.

The optical film thickness of the SnO ₂ film formed as the first metal oxide film 10 was 46.2 nm, and the optical film thickness of the ZnO film was 21 nm.

  A first Ag film 13 having a geometric thickness of 14 nm was formed on the first metal oxide film 10 in the same manner as in Example 1.

As the second metal oxide film 11, an SnO ₂ film having an optical film thickness of 119.1 nm and a ZnO film having an optical film thickness of 63 nm were used. The second metal oxide film 11 was formed in the same manner as the first metal oxide film 10.

  A second Ag film 14 having a geometric thickness of 14 nm is formed on the second metal oxide film 11 in the same manner as the first Ag film 13, and the geometric thickness of the first Ag film 13 and the second Ag film 14 is increased. The total was 28 nm.

  A ZnO film having an optical film thickness of 71.8 nm was formed as the third metal oxide film 12 on the second Ag film 14. The film forming method was the same as that of the ZnO film of the first metal oxide film 10.

  A multi-layer glass as shown in FIG. 1 was produced by using a highly transparent glass having a thickness of 6 mm for the plate glass 1 ′.

  As a result of calculating the visible light transmittance and the solar heat gain of this multilayer glass based on JIS R3106: 1998, the visible light transmittance was 71.6% and the solar heat heat gain was 0.36. In addition, in the CIEL * a * b * chromaticity coordinate diagram, the reflection color of the non-film surface of the normal incident light was a * of −7.8 and b * of −3.4.

Comparative Example 1
The structure of the low resistance film formed on the plate glass 1 having a thickness of 3 mm uses a ZnO film having an optical film thickness of 50 nm for the first metal oxide film 10 and an optical film thickness for the second metal oxide film 11. A ZnO film with a thickness of 191 nm is used, a ZnO film with an optical thickness of 80 nm is used for the third metal oxide film 12, and the total geometric thickness of the first Ag film 13 and the second Ag film 14 is 31 nm. did.

  The ZnO films of the first metal oxide film 10, the second metal oxide film 11, and the third metal oxide film 12 are formed by using a Zn target as the target 20 and exhausting the vacuum chamber 23 by using a vacuum pump 25. Are continuously operated, and the atmospheric gas in the vacuum chamber 23 is adjusted by introducing oxygen gas from the gas introduction pipe 26 and controlling the flow rate of the oxygen gas to 100 sccm or less by the mass flow controller 27. The inside pressure was adjusted to 1.0 to 1.2 Pa. The first Ag film 13 and the second Ag film were formed by the same film forming method as in Example 1.

  The soda lime glass was used for the plate glass 1 ′ having a thickness of 3 mm, and the multilayer glass shown in FIG.

  As a result of calculating the visible light transmittance and the solar heat gain of this multilayer glass based on JIS R3106: 1998, the visible light transmittance was 60.4% and the solar heat heat gain was 0.35. In addition, in the CIEL * a * b * chromaticity coordinate diagram, the reflection color of the non-film surface of normal incident light was −3.0 and b * was −9.3.

Comparative Example 2
A multilayer glass was prepared in the same manner as in Comparative Example 1 except that a high transmittance glass having a visible light transmittance of 91% and a thickness of 6 mm was used for the plate glasses 1 and 1 ′.

  When the plate glass 1 was set to the outdoor side, the visible light transmittance calculated in accordance with JIS R3106: 1998 was 62.2%, and the solar heat acquisition rate was 0.35. The reflection color of the non-film surface of the normal incident light was a * of −2.4 and b * of −10.0.

Comparative Example 3
A multilayer glass was produced in the same manner as in Comparative Example 1 except that soda lime glass having a thickness of 12 mm was used for the plate glasses 1 and 1 ′.

  When the plate glass 1 was set to the outdoor side, the visible light transmittance calculated in accordance with JIS R3106: 1998 was 56.5%, and the solar heat gain rate was 0.35. In addition, the reflection color of the non-film surface of normal incident light was a * of -1.97 and b * of -9.40.

Comparative Example 4
A soda lime glass having a thickness of 10 mm is used for the plate glass 1, 1 ′, a ZnO film having an optical film thickness of 61 nm is used for the first metal oxide film 10, and an optical film thickness is used for the second metal oxide film 11. A ZnO film with a thickness of 221 nm is used, a ZnO film with an optical thickness of 69 nm is used for the third metal oxide film 12, and the total geometric thickness of the first Ag film 13 and the second Ag film 14 is 22 nm. A film was formed by the same film forming method as in Comparative Example 1, and the other processes were performed in the same manner as in Example 1 to produce a multilayer glass shown in FIG.

  When the plate glass 1 was set to the outdoor side, the visible light transmittance calculated in accordance with JIS R3106: 1998 was 51.5%, and the solar heat acquisition rate was 0.37. Moreover, the reflection color of the non-film surface of normal incident light was −6.50 for b * and 1.70 for b *.

Comparative Example 5
A multilayer glass shown in FIG. 1 was prepared in the same manner as in Comparative Example 4 except that soda lime glass having a thickness of 12 mm was used for the plate glasses 1 and 1 ′.

  When the plate glass 1 was placed on the outdoor side, the visible light transmittance calculated in accordance with JIS R3106: 1998 was 60.3%, and the solar heat gain rate was 0.37. Moreover, the reflection color of the non-film surface of normal incident light was −6.50 for b * and 1.70 for b *.

Comparative Example 6
A soda lime glass having a thickness of 12 mm is used for the plate glass 1, 1 ′, a ZnO film having an optical film thickness of 48 nm is used for the first metal oxide film 10, and an optical film thickness is used for the second metal oxide film 11. A multilayer glass shown in FIG. 1 was produced using a ZnO film of 139 nm, the geometric thickness of the first Ag film 13 being 12 nm, and without forming the third metal oxide film and the second Ag film. .

  The first and second metal oxide films and the first Ag film were formed in the same manner as in Comparative Example 1.

  When the plate glass 1 was set to the outdoor side, the visible light transmittance calculated in accordance with JIS R3106: 1998 was 65.5%, but the solar heat gain rate was 0.48, and the heat shielding property was poor. In addition, the reflection color of the non-film surface of normal incident light was a * of −2.38 and b * of −16.79.

  Table 1 shows the film configurations of the low resistance films of Examples 1 to 5 and Comparative Examples 1 to 5, and Table 2 shows visible light based on JIS R3106: 1998 of Examples 1 to 5 and Comparative Examples 1 to 5. It shows transmittance, solar heat gain rate and reflection color.

  Table 3 shows the diffraction angle of the diffraction peak by the (002) crystal plane of the ZnO film and the value of the surface resistance of the resistance film of the ZnO film formed in the example and the comparative example by the X-ray diffraction method using CuKα rays. Indicates.

  The diffraction angles of Examples 1 to 6 were all 33.9 ° or less, and in Comparative Examples, they were larger than 33.9 °.

  The surface resistance of the low resistance film of the example is a total t2 of the thickness of the first Ag film and the thickness of the second Ag film of 28 nm, which is lower than the value 2.28 of 3.4-0.04 × t2. Resistance value.

  The surface resistance of the low resistance films of Comparative Examples 1 to 3 is that the total t2 of the thickness of the first Ag film and the thickness of the second Ag film is 31 nm, whereas the value 2.16 of 3.4-0.04 × t2 is All were high resistance values.

  The surface resistance of the low resistance films of Comparative Examples 4 and 5 is that the total t2 of the thickness of the first Ag film and the thickness of the second Ag film is 22 nm, and the value 2.52 of 3.4-0.04 × t2 is 2.52. On the other hand, the resistance value was high.

It is sectional drawing which shows the structure of the multilayer glass of this invention. It is sectional drawing which shows the film | membrane structure of a low resistance film. It is the schematic of a magnetron sputtering apparatus. It is a graph which shows the relationship of the visible light transmittance | permeability with respect to the thickness of transparent glass.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Plate glass 2 Low resistance film 3 Adhesive 4 Spacer 5 Sealing material 10 1st metal oxide 11 2nd metal oxide 12 3rd metal oxide 13 1st Ag film 14 2nd Ag film 20 Target 21 Plate glass 22 Substrate holder 23 Vacuum chamber 24 Main valve 25 Vacuum pump 26 Gas introduction pipe 27 Mass flow controller

Claims (4)

  The two plate glasses are spaced apart from each other at a predetermined interval, a spacer is disposed at the peripheral portion of the two plate glasses so as to maintain the predetermined interval, and the hollow is sealed between the two plate glasses. In a multi-layer glass in which a low resistance film is formed on one sheet glass, the low resistance film is disposed on the hollow layer side, and the low resistance film includes a first metal oxide film and a first Ag film. , A second metal oxide film, a second Ag film, and a third metal oxide film are sequentially laminated. The first metal oxide film, the second metal oxide film, and the third metal oxide film are A ZnO film is mainly a metal oxide film, and the ZnO film has a diffraction angle 2θ of a diffraction peak due to the (002) crystal plane of the ZnO film by X-ray diffraction using CuKα rays of 33.9 ° or less. The two glass sheets of the multi-layer glass both have a thickness of 3 mm or more and have two sheet glass. The visible light transmittance according to JIS R3106: 1998 of the multilayer glass is (70.0-0.3 × t1)% or more with respect to the total thickness t1 (mm) of the glass, and the multilayer glass has JIS R3106 : A double-glazed glass characterized in that the solar heat acquisition rate according to 1998 is 0.38 or less.   The laminated film has a total thickness of the first Ag film and the second Ag film of t2 (nm), and the surface resistance of the low resistance film is (3.4-0.04 × t2) Ω / □ or less. The multilayer glass according to claim 1, wherein:   The optical thickness of the first metal oxide film is in the range of 57 nm to 77 nm, the thickness of the first Ag film is in the range of 12 nm to 16 nm, and the optical thickness of the second metal oxide film is in the range of 160 nm to 200 nm, 3. The multilayer glass according to claim 1, wherein the thickness of the second Ag film is in the range of 12 nm to 16 nm, and the optical thickness of the third metal oxide film is in the range of 62 nm to 82 nm. .   The reflection color of the glass surface of the plate glass on which the low resistance film is formed is −20 ≦ a * ≦ −5, −10 ≦ b * ≦ 5 in the CIE L * a * b * chromaticity coordinate diagram. The multilayer glass according to any one of claims 1 to 3.

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