JP2007191384A - Low emissivity glass - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a low emissivity glass especially having high heat shielding properties while having high visible light transparency. <P>SOLUTION: In a low emissivity glass, 2n layers (n≥1) of dielectric films and Ag films are alternately laminated in this order on a transparent substrate, and a dielectric film is laminated on the Ag film of the topmost layer. The low emissivity glass is characterized in that a ZnO film is laminated adjacent to the transparent substrate side of the Ag film, and a diffraction angle (2θ) of a diffraction peak of a 002 crystal plane of the ZnO film in X-ray diffraction method by wherein CuKα ray is used is 33.9° or less. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a low resistance film and a low radiation glass using the low resistance film.

  As disclosed in Patent Document 1, a low emission glass is known in which a dielectric film and an Ag film are repeatedly laminated on a glass plate by 2n + 1 (n ≧ 1) layers, and the uppermost layer is a dielectric film. ing. A metal transparent oxide film is used for the dielectric film.

  The low emission glass has a high heat-shielding property due to the excellent infrared reflection effect of the Ag film while preventing the reflection of visible light by the dielectric film laminated before and after the Ag film and ensuring high visible light transmittance. It is well known as an opening member that expresses.

  Such low-emission glass is often used in a double-glazed construction in which a window glass of a building is provided with an air insulation layer in order to make full use of heat insulation.

  Since this low emission glass dielectric film or Ag film is used for a window, it can be formed on a large-area glass plate, and mass production is required, so that it is formed by sputtering. In particular, the magnetron sputtering method is used in which a magnet is disposed behind a sputtering target, a plasma is confined in the vicinity of the target surface by a generated magnetic field, and film formation is performed with particles sputtered from the target.

  A low radiation glass using an Ag film is required to have a high heat-shielding property and a high visible light transmittance in order to be used for an opening.

The high infrared reflectance of the Ag film is necessary for the expression of heat shielding properties, and the smaller the resistance of the Ag film, the higher the infrared reflectance. The resistance of the Ag film can be lowered by increasing the thickness of the Ag film. However, since the visible light transmittance of the Ag film decreases as the thickness increases, the thickness of the Ag film depends on the transmittance and emissivity of the Ag film. Determined by the balance of
JP 2002-173343 A

  An object of the present invention is to provide a low emission glass having a particularly high heat shielding property while having a high visible light transmittance.

  In the low emission glass of the present invention, a dielectric film and an Ag film are alternately laminated in this order on a transparent substrate, and a dielectric film is laminated on the uppermost Ag film. In the low emission glass, the ZnO film is laminated adjacent to the transparent substrate side of the Ag film, and the diffraction angle 2θ of the diffraction peak by the 002 crystal plane of the ZnO film by the X-ray diffraction method using CuKα rays. Is a low-emission glass characterized by being 33.9 ° or less.

  The low emission glass of the present invention is the low emission glass, wherein n = 1, the uppermost dielectric film includes a ZnO film, and the thickness of the ZnO film used for the first dielectric film is 20 The thickness of the second layer Ag film is in the range of 5 to 30 nm, and the thickness of the ZnO film used for the dielectric film of the third layer is in the range of 20 to 60 nm. Or n = 2, the uppermost dielectric film includes a ZnO film, the thickness of the ZnO film used for the first dielectric film is in the range of 20 to 60 nm, and the second layer The thickness of the Ag film is in the range of 7.5 to 17.5 nm, the thickness of the ZnO film used for the dielectric film of the third layer is in the range of 40 to 120 nm, and the Ag film of the fourth layer The thickness of the ZnO film used for the fifth dielectric film is in the range of 7.5 to 17.5 nm A low-E glass, characterized in that in the range of 20 to 60 nm.

  The low emission glass of the present invention is the low emission glass according to the low emission glass, wherein at least one of the dielectric films is only a ZnO film.

  The low emission glass of the present invention is characterized in that in the low emission glass, a zinc oxide layer containing 2 to 12% by weight of Al for preventing oxidation of the Ag film is formed immediately above the Ag film. Low reflection glass.

  The low emission glass of the present invention is a low reflection glass characterized in that in the low emission glass, a protective metal layer for preventing oxidation of the Ag film is formed immediately above the Ag film.

  In the low emission glass of the present invention, the protective metal layer in the low emission glass contains a metal selected from the group consisting of Zn, Sn, Ti, Al, NiCr, Cr, Zn alloy, and Sn alloy only. The low-reflection glass is characterized in that the metal contains 0.0 to 10.0% by weight of Al or Sb.

  The low emission glass of the present invention provides a low emission glass having high visible light transmittance and excellent daylighting.

  The low resistance film of the present invention is highly transparent and is preferably used for low radiation glass for the purpose of heat insulation of building windows.

  As shown in FIG. 1, the low emission glass is formed by laminating 2n (n ≧ 1) layers of a transparent substrate 3 by alternately repeating a dielectric film 11 and an Ag film 12 from the transparent substrate, and the uppermost film is a dielectric. A low resistance film made of the body film 11 is formed.

  As the transparent substrate 3, a plate glass such as soda lime glass or quartz glass, a transparent resin plate or film such as polycarbonate or polyester terephthalate, and the like can be suitably used. Inexpensive float plate glass is particularly suitable.

  The dielectric film 11 laminated in contact with the transparent substrate 3 increases the adhesion between the transparent substrate and the Ag film 12 and the adhesion between the low resistance film and the strength of the laminated film of low radiation glass. In order to increase the durability, it is further used to increase the visible light transmittance of the low emission glass.

  The dielectric film 11 preferably uses a ZnO film adjacent to the transparent substrate side of the Ag film in order to obtain suitable film strength and durability of the low emission glass and high transmittance.

  In addition to the ZnO film, the dielectric film 11 is made of a transparent oxide film such as Si, Sn, Al, or Ti, or a nitride film or nitride oxide film such as Si, Sn, Zn, Al, or Ti. A dielectric film formed by selecting at least one kind may be used.

  The above-described dielectric film is preferably selected in consideration of the optical film thickness, the light absorption characteristics in the visible range, the mechanical strength of the dielectric film itself, and the adhesion with the adjacent dielectric film and Ag film. .

  The thickness of the ZnO film used for the dielectric film 11 formed directly on the transparent substrate 3 and the thickness of the ZnO film used for the uppermost dielectric film 11 are preferably 20 nm to 60 nm, and other dielectrics. The thickness of the ZnO film used for the film 11 is preferably 40 to 120 nm.

  Further, the thickness of the lowermost dielectric film 11 formed directly on the transparent substrate 3 and the thickness of the dielectric film 11 formed as the uppermost layer of the low resistance film is such that the low resistance film can be transmitted in the visible region. In order to improve the properties, it is preferable to make the film thickness the same.

  The reason why the lower limit of the thickness of the ZnO film is 20 nm is to maintain the adhesion with the adjacent layer. The upper limit of the thickness of the ZnO film is 60 nm for the lowermost dielectric film 11 and the uppermost dielectric film 11 formed directly on the transparent substrate, and 120 nm for the other dielectric films. ) Exceeding the above range, a preferable transmittance in the visible range cannot be obtained.

  When n = 1, that is, when the Ag film is one layer, the thickness of the Ag film 12 is preferably in the range of 5 to 30 nm. When the thickness is less than 5 nm, the resistance value is large and an effective heat shielding performance cannot be obtained. When the thickness exceeds 30 nm, the transparency is impaired and it is not preferable for use in a building window.

  Furthermore, when n = 2, that is, when the Ag film is two layers, the total thickness of the two layers of the Ag film 12 is preferably in the range of 15 to 35 nm. When the total thickness of the two layers of Ag film is less than 15 nm, the resistance value is large and effective heat shielding performance cannot be obtained. When the total thickness exceeds 35 nm, the transparency is impaired, and the window of the building is damaged. It is not preferable to use it.

  Further, it is desirable to form a protective metal layer between the Ag film 12 and the dielectric film 11 in order to prevent oxidation of the Ag film 12.

  For the protective metal layer, it is possible to use 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.

  Further, it is preferable to use zinc oxide (ZnAlOx) containing 2 to 12% by weight of Al (hereinafter referred to as an AZO film) instead of the protective metal layer.

  The Ag film 12 and the dielectric film 11 are preferably formed by a sputtering method, and particularly preferably formed using a magnetron sputtering apparatus as shown in FIG.

  In the film forming apparatus shown in FIG. 2, a metal or oxide target is used as the target 1, the transparent substrate 3 is held by the substrate holder 2, and then the vacuum chamber 8 is evacuated using the vacuum pump 5, A mass flow controller (not shown) is used to form a metal oxide film from the gas introduction pipe 7 in the vacuum chamber 8 using O 2 gas or a mixed gas of Ar and O 2, and Ar gas for forming an Ag film. The low resistance film is produced on the transparent substrate.

  The transparent oxide film is formed by using a metal target as the target 1 and introducing oxygen gas from a gas introduction pipe, or by forming the target 1 using the same oxide target as the oxide to be formed. Can be membrane.

  For example, when forming a ZnO film, a Zn target can be used as the target 1 and an Ar gas and an oxygen gas having an appropriate mixing ratio can be introduced from the gas introduction pipe 7. Alternatively, a ZnO film may be formed by introducing only Ar gas from the gas introduction pipe 7 using a ZnO target as the target 1.

  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 O 2 gas introduced by being controlled by a vacuum pump and a mass flow controller. It is preferable. The pressure in the vacuum chamber 8 is measured by a vacuum gauge 8 '.

  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 ray 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.

  It is desirable to change the diffraction angle 2θ of the diffraction peak maximum intensity by the ZnO (002) plane, which is measured by the X-ray diffraction method using CuKα rays, by adjusting the pressure in the vacuum chamber during film formation.

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

Example 1
As shown in FIG. 3, a low emission glass in which a dielectric film 11, an Ag film 12, and a dielectric film 11 were laminated in this order on a transparent substrate 3 was produced. As the transparent substrate, glass having a thickness of 6 mm was used.

  The Ag film and the dielectric film were formed using a DC magnetron sputtering apparatus shown in FIG.

  As the dielectric film 11, a ZnO film was formed on the transparent substrate 3. A Zn target was used as the target 1 and the transparent substrate 3 was held by the substrate holder, and then the inside of the vacuum chamber 8 was evacuated by the vacuum pump 5. During film formation, the vacuum pump was continuously operated.

  The atmospheric gas in the vacuum chamber 8 was adjusted by introducing oxygen gas from the gas introduction pipe 7 and controlling the flow rate of the oxygen gas with a mass flow controller (not shown).

  A cryopump was used as the vacuum pump 5. The pressure in the vacuum chamber-8 during film formation was adjusted to 0.1 Pa by controlling the O2 gas flow rate to 20 sccm with a mass flow controller (not shown).

  The ZnO film increases the adhesion between the Ag film and the transparent substrate, and was formed to a thickness of 37 nm. The film thickness of the ZnO film and the transparent oxide film formed on the upper layer is designed to increase the transmittance in the visible region of the low emission glass.

  Next, after evacuating the inside of the vacuum chamber 8, Ar gas is introduced into the vacuum chamber 8 by controlling with a mass flow controller (not shown) from the gas introduction pipe 7, the inside of the vacuum chamber 8 is made into Ar gas atmosphere, and the Ag target is An Ag film 12 was formed on the ZnO film 11 using the target 1. The thickness of the Ag film 12 was 10 nm.

  During the formation of the Ag film 12, the pressure in the vacuum chamber was kept at 0.5 Pa or less by the vacuum pump 5 and the opening / closing valve 6.

  Next, an AZO (Al 2 wt% -containing ZnO) target was used on the Ag film 12 to form an AZO film having a thickness of 5 nm (not shown in FIG. 3).

  During the formation of the AZO film, the gas atmosphere and pressure in the pressure chamber 8 were the same as those for forming the Ag film 12.

  Further, a ZnO film having a thickness of 37 nm was formed on the AZO film. The pressure in the vacuum chamber-8 during film formation was adjusted to 0.5 Pa by controlling the O2 gas flow rate to 100 sccm with a mass flow controller (not shown). Other conditions were the same as those for the ZnO film formed on the transparent substrate 3.

Example 2
The film configuration and thickness were all the same as in Example 1. In addition, when forming a ZnO film on the transparent substrate 3, the pressure in the vacuum chamber 8 during film formation is adjusted to 0.3 Pa by controlling the O2 gas flow rate to 60 sccm by a mass flow controller (not shown). Except for this, all the film forming conditions were the same as in Example 1.

Example 3
The film configuration and thickness were all the same as in Example 1. Further, when a ZnO film is formed on the transparent substrate 3, the pressure in the vacuum chamber 8 during the film formation is adjusted to 0.5 Pa by controlling the O2 gas flow rate to 100 sccm by a mass flow controller (not shown). Except for this, all the film forming conditions were the same as in Example 1.

Example 4
The film configuration and thickness were all the same as in Example 1. Further, when a ZnO film is formed on the transparent substrate 3, the pressure in the vacuum chamber 8 during the film formation is adjusted to 0.9 Pa by controlling the O2 gas flow rate to 200 sccm by a mass flow controller (not shown). Except for this, all the film forming conditions were the same as in Example 1.

Comparative Example 1
The film configuration and thickness were all the same as in Example 1. In addition, when the ZnO film is formed on the transparent substrate 3 and when the ZnO film is formed on the AZO film, the pressure in the vacuum chamber 8 during the film formation is changed to O 2 by a mass flow controller (not shown). The film forming conditions were all the same as in Example 1 except that the gas flow rate was controlled to 100 sccm and adjusted to 1.0 to 1.2 Pa.

Comparative Example 2
The film configuration and thickness were all the same as in Example 1. In addition, when the ZnO film is formed on the transparent substrate 3 and when the ZnO film is formed on the AZO film, the pressure in the vacuum chamber 8 during the film formation is changed to O 2 by a mass flow controller (not shown). The film forming conditions were all the same as in Example 1 except that the gas flow rate was controlled to 200 sccm and adjusted to 1.0 to 1.2 Pa.

  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 of the low emission glasses prepared in Examples 1 to 4 and Comparative Examples 1 to 2, and the specific resistance Table 1 shows the optical characteristics.

  As shown in Table 1, in Examples 1 to 4, the diffraction angle was in the range of 33.7 degrees to 33.8 degrees, and the specific resistance was 5.1 × 10 −6 Ωcm or less. Comparative Example 1 and Comparative Example 2 had a diffraction angle of 34 ° or more and a specific resistance of 6.3 × 10 −6 Ωcm or more, which was larger than that of the example.

  Further, as shown in Table 1, the visible light transmittance and the solar reflectance of Example 1 to Example 4 are both larger than those of Comparative Examples 1 and 2, and have good heat shielding performance and are open as bright low-radiation glass. It was used for the part. The visible light transmittance and the solar reflectance are values measured according to JIS R3106-1998.

Example 5
As shown in FIG. 4, two layers of dielectric films 11 and Ag films 12 are alternately formed on a transparent substrate 3, and the dielectric film 11 is formed on the uppermost film to produce a low emission glass. .

  The Ag film 12 and the dielectric film 11 were formed using a DC magnetron sputtering apparatus shown in FIG. A ZnO film was formed as the dielectric film 11.

  The pressure in the vacuum chamber-8 during the ZnO film formation formed on the transparent substrate 3 and the fourth layer from the transparent substrate is adjusted to 0.1 Pa by controlling the O2 gas flow rate to 20 sccm or less by a mass flow controller. The other film forming conditions were the same as in Example 1.

  The thickness of the transparent oxide film 11 formed on the transparent substrate 3 and the thickness of the uppermost transparent oxide film 11 were both 37 nm. The thickness of the transparent oxide film 11 between the two Ag films 12 was 74 nm.

  Further, before forming the dielectric film 11 on the Ag film 12, an AZO film (not shown) was formed on the Ag film 12 in the same manner as in Example 1.

  The two layers of Ag film 12 had the same film thickness of 10 nm, and a low emission glass having a total thickness of two layers of 20 nm was produced.

Example 6
The film configuration and thickness were all the same as in Example 5. The pressure in the vacuum chamber 8 during the formation of the ZnO film formed on the transparent substrate 3 and the fourth layer from the transparent substrate is controlled to 0.1 Pa by controlling the O2 gas flow rate to 60 sccm or less by the mass flow controller. The other film formation conditions were the same as in Example 1.

Example 7
The film configuration and thickness were all the same as in Example 5. The pressure in the vacuum chamber 8 during the formation of the ZnO film formed on the transparent substrate 3 and the fourth layer from the transparent substrate is controlled to 0.9 Pa by controlling the O2 gas flow rate to 200 sccm or less by the mass flow controller. The other film formation conditions were the same as in Example 1.

Comparative Example 3
The film configuration and thickness were all the same as in Example 5. The three-layer ZnO film was formed in the same manner as in Comparative Example 1. The other film formation was the same as in Example 1.

  Diffraction angle 2θ of diffraction peak maximum intensity measured by X-ray diffraction method using CuKα ray of the low emission glass prepared in Examples 5 to 7 and Comparative Example 3, 2θ, specific resistance, and optics The characteristics are shown in Table 2. The visible light transmittance and the solar reflectance are values measured according to JIS R3106-1998.

  As shown in Table 2, for Examples 5 to 7, the diffraction angle was in the range of 33.6 degrees to 33.9 degrees, and the specific resistance was 5.1 × 10 −6 Ωcm or less. In Comparative Example 3, the diffraction angle was 34 degrees or more and the specific resistance was 6.5 × 10 −6 Ωcm or more, which was larger than that of the example.

  Further, as shown in Table 2, the visible light transmittance and the solar reflectance of Example 5 to Example 7 are both larger than those of Comparative Example 3, have good heat shielding performance, and are bright as low emission glass in the opening. It was used.

  The film configurations and film formation conditions of Examples 1 to 4 and Comparative Examples 1 and 2 are shown in Table 3, and the film structures and film formation conditions of Examples 5 to 7 and Comparative Example 3 are shown in Table 4.

It is sectional drawing which shows the film | membrane structure of low radiation glass. It is the schematic of a film-forming apparatus. It is sectional drawing which shows a film | membrane structure of the low radiation glass produced in Examples 1-4 and Comparative Examples 1-2. It is sectional drawing which shows a film | membrane structure of the low radiation glass produced in Examples 5-7 and Comparative Example 3. FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Target 2 Substrate holder 3 Transparent substrate 4 Cathode magnet 5 Vacuum pump 6 On-off valve 7 Gas introduction tube 8 Vacuum chamber 8 'Vacuum gauge 9 Power cord 10 DC power source 11 Dielectric film 12 Ag film

Claims (7)

  In a low radiation glass in which 2n layers (n ≧ 1) are alternately laminated in this order on a transparent substrate, and a dielectric film is laminated on the uppermost Ag film, Ag A ZnO film is laminated adjacent to the transparent substrate side of the film, and the diffraction angle 2θ of the diffraction peak due to the 002 crystal plane of the ZnO film by X-ray diffraction using CuKα rays is 33.9 ° or less. Low emission glass characterized by that.   n = 1, the uppermost dielectric film includes a ZnO film, the thickness of the ZnO film used for the first dielectric film is in the range of 20 to 60 nm, and the thickness of the second Ag film The low emission glass according to claim 1, wherein the thickness of the ZnO film used for the dielectric film of the third layer is in the range of 20 to 60 nm.   n = 2, the uppermost dielectric film includes a ZnO film, the thickness of the ZnO film used for the first dielectric film is in the range of 20 to 60 nm, and the thickness of the second Ag film Is in the range of 7.5 to 17.5 nm, the thickness of the ZnO film used for the third-layer dielectric film is in the range of 40 to 120 nm, and the thickness of the fourth-layer Ag film is 7 The low emission glass according to claim 1, wherein the thickness of the ZnO film used for the fifth dielectric film is in the range of 20 to 60 nm.   The low emission glass according to any one of claims 1 to 3, wherein at least one of the dielectric films is made of only a ZnO film.   The low reflection glass according to any one of claims 1 to 4, wherein a zinc oxide layer containing 2 to 12% by weight of Al for preventing oxidation of the Ag film is formed directly on the Ag film.   The low reflection glass according to any one of claims 1 to 4, wherein a protective metal layer for preventing oxidation of the Ag film is formed directly on the Ag film.   The protective metal layer includes a metal selected from the group consisting of Zn, Sn, Ti, Al, NiCr, Cr, Zn alloy, and Sn alloy only, and the metal contains Al or Sb in an amount of 0.0 to 10. The low reflection glass according to claim 6, comprising 0% by weight.