JP2019182684A - Low radiation glass - Google Patents

Abstract

To provide a low radiation glass having appropriate thermal insulation properties and capable of collecting solar radiation.SOLUTION: In the low radiation glass including a low radiation film which has one Ag film and is formed on the surface of a glass plate, the low radiation film comprises a first dielectric film, a second dielectric film, an Ag film, a barrier film and a third dielectric film in this order from the glass plate side. The first dielectric film is a Ti oxide layer having an optical film thickness of 30-50 nm; the second dielectric film has a crystalline dielectric layer contacting the Ag film; the second dielectric film has an optical film thickness of 15-35 nm in total; the third dielectric film has an optical film thickness of 80-120 nm in total; and the Ag film has a geometrical film thickness of 11-14 nm.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a low emission glass having one Ag film in a low emission laminated film.

  In recent years, for the purpose of improving cooling and heating efficiency, window glass using low radiation glass in which a low radiation laminated film (hereinafter sometimes referred to as a low radiation film) is formed is becoming widespread. This low-emission glass incorporates visible light into the room and satisfies the daylighting requirements of window glass, while the low-emission film reflects light from the near-infrared to the infrared, so the indoor temperature rises due to sunlight. Can be suppressed. In addition, when a double-glazed glass incorporating low-emission glass is used as a window glass, the hollow layer of the double-glazed glass and the low-emission film block the transfer of heat from the room to the outside. It is possible to improve.

  The above-mentioned low-emission film is usually formed by laminating an Ag film and a dielectric film, but various optical characteristics can be obtained by setting the thickness and ratio of thickness of each film and each layer within a specific range. Can be as desired.

  For example, in Patent Document 1, a titanium oxide layer, a metal layer, and a titanium oxide layer are alternately stacked in this order by 2n + 1 (n is an integer) layers, and at least 1 between the metal layer and the titanium oxide layer. In particular, a laminate having an intermediate layer having a refractive index at 550 nm of less than 2.4 is disclosed. In this document, an Ag layer is used as a metal layer in order to achieve low radiation, and a titanium oxide layer is used in order to improve the reflection color tone. Moreover, in order to suppress that visible light transmittance | permeability falls significantly, said intermediate | middle layer is used. Moreover, silicon nitride, niobium oxide, zinc oxide, and tin oxide are disclosed as the intermediate layer.

  For example, in Patent Document 2, a thin film in which a first titanium oxide-containing layer, a low emissivity metal layer mainly composed of silver, and a second titanium oxide-containing layer containing a titanium oxide are laminated in this order. A low emissivity laminate having a laminate portion has been proposed.

  For example, in Patent Document 3, a first dielectric layer containing a first metal oxide; a low-emission layer; and a first layer containing a second metal oxide and a second layer containing silicon aluminum nitride are sequentially provided. A second dielectric layer laminated with a refractive index of the first metal oxide and the second metal oxide being 2.2 to 2.6 for a wavelength of 550 nm, respectively. A coating has been proposed. As the second metal oxide, titanium oxide, zirconium oxide, and niobium oxide are disclosed.

  For example, Patent Document 4 proposes a low emissivity plate glass including a thin layer combination on a glass plate. According to the above document, the combination comprises at least one metal layer that reflects infrared rays, which metal layer is provided between the metal layer and the glass plate on the one hand and on the metal layer on the other hand. Titanium oxide or titanium suboxide (TiOx; 1.7 <x <1...) Is disposed between the above dielectric layers, and this metal layer is deposited in a weak oxidizing atmosphere under reduced pressure using a conductive titanium oxide cathode. It is disclosed that it is covered with a protective barrier layer comprising the layer 9).

JP 2000-246831 A Japanese Patent No. 5846203 Special table 2017-530074 gazette Special table 2009-538815

  Conventionally, high heat insulation and heat insulation have been required for window glass for the purpose of saving air conditioning costs. In particular, higher performance is required for heat insulation, and the required heat insulation is achieved by using a low radiation film with an increased number of laminated Ag films or by improving the heat insulation of the hollow layer of the multilayer glass. Has achieved sex.

  In general, the low radiation film has a high heat insulating property as well as a heat insulating property as the number of laminated Ag films increases. If the heat shielding property is high, the intrusion of solar radiation into the room is hindered, and the feeling of cooling around the window may be strongly felt even in the daytime in winter. As described above, the heat insulating property can be improved to some extent by devising the hollow layer, but the heat shielding property depends on the low radiation film. Therefore, for the purpose of suppressing the feeling of cooling around the window, there is a demand for a low radiation glass having an appropriate heat insulating property and capable of taking in solar radiation.

  Therefore, an object of the present invention is to obtain a low radiation glass having an appropriate heat insulating property and capable of taking in solar radiation.

  According to a first aspect of the present invention, in the low emission glass in which the low emission film having one Ag film is formed on the surface of the glass plate, the low emission film is in order from the glass plate side, the first dielectric film, A dielectric film, an Ag film, a barrier film, and a third dielectric film, wherein the first dielectric film is a Ti oxide layer having an optical film thickness of 30 to 50 nm, and the second dielectric film The film has a crystalline dielectric layer in contact with the Ag film, the total optical film thickness of the second dielectric film is 15 to 35 nm, and the third dielectric film has a total optical film thickness The Ag film is a low emission glass characterized by a geometric film thickness of 11 to 14 nm.

The second invention is a multi-layer glass in which the low emission film having one Ag film has a low emission glass formed on the surface of the glass plate and a glass plate, and the low emission film is made of glass. In order from the plate side, the first dielectric film, the second dielectric film, the Ag film, the barrier film, and the third dielectric film are included, and the first dielectric film has an optical film thickness of 30 to A 50 nm Ti oxide layer, and the second dielectric film has a crystalline dielectric layer in contact with the Ag film, and the total optical film thickness of the second dielectric film is 15 to 35 nm, The third dielectric film has a total optical film thickness of 80 to 120 nm, the Ag film has a geometric film thickness of 11 to 14 nm, and the low emission glass has a thickness of 10 to 16 mm from the glass plate. are arranged with a spacing, the heat transmission coefficient calculated in conformity with JIS R3107 of the plurality glazing is 1.9 W / m K or less, solar heat gain coefficient calculated in conformity with JIS R3106 is double glazing, characterized in that at least 0.50.

  According to the present invention, it has become possible to obtain a low emission glass having appropriate heat insulating properties and capable of taking in solar radiation.

It is a cross-sectional schematic diagram of the low radiation glass showing one Embodiment of 1st invention. It is a cross-sectional schematic diagram of the multilayer glass showing one Embodiment of 2nd invention.

1: Explanation of terms Terms used in the present specification will be described below.

(Various optical properties)
In this specification, the following various optical characteristics are all measured using a self-recording spectrophotometer (manufactured by Hitachi, U-4100) and a Fourier transform infrared spectrophotometer (manufactured by JASCO, FT / IR-4200). The measurement results were used.

(Visible light transmittance, visible light reflectance)
“Visible light transmittance and visible light reflectance” in the present specification used values calculated by a method based on JIS R3106 (1998) from the transmittance and reflectance measured with a self-recording spectrophotometer. In addition, “visible light transmittance and visible light reflectance” in the present specification indicate values when a general transparent float glass plate having a thickness of 3 mm is used as a base material unless otherwise specified. is there.

(Transparent color tone, reflective color tone)
The transmitted color tone and reflected color tone in this specification refer to the color tone of transmitted light and reflected light. Further, the reflection on the glass surface side, which is the non-film-forming surface of the low emission glass, may be referred to as “glass surface reflection”, and the reflection on the film surface on the low emission film surface side may be referred to as “film reflection”. The various color tones are represented by the values expressed in the CIE L ^* a ^* b ^* chromaticity coordinate diagram for the color tones of transmitted light and reflected light calculated according to JIS Z8781-4. In addition, in this specification, unless there is special description, the value at the time of using a general transparent float glass plate with a thickness of 3 mm as a base material shall be shown.

(Vertical emissivity)
The “vertical emissivity” of the film surface of the low emission film in this specification is a value indicating the heat insulation performance of the low emission film, and conforms to JIS R3106 (1998) from the reflectance measured with a Fourier transform infrared spectrophotometer. The value calculated by the method is used. The vertical emissivity of the glass surface is defined as 0.89 in JIS R3107 (1998).

(Solar radiation transmittance)
The “sunlight transmittance” in the present specification is a value indicating the heat shielding property of the low radiation glass, and a value calculated by a method based on JIS R3106 (1998) from the transmittance measured with a self-recording spectrophotometer was used. Further, the “sunlight transmittance” in this specification indicates a value when a general transparent float glass plate having a thickness of 3 mm is used as a base material.

(Heat flow rate)
“Heat transmissivity” in this specification is a value indicating the heat insulation performance of the double-glazed glass, and a value calculated by a method based on JIS R3107 (1998) was used. Moreover, in this specification, what has a heat transmissivity of 1.9 W / m < ² > K or less was set as "it has moderate heat insulation."

(Solar heat acquisition rate)
The “solar heat acquisition rate” in the present specification is a value indicating the heat shielding performance of the multilayer glass, and a value calculated by a method based on JIS R3106 (1998) was used. Further, in the present specification, a solar radiation heat acquisition rate of 0.5 or more is defined as “capable of capturing solar radiation”.

(Geometric film thickness)
The geometrical film thickness means the same as a commonly used film thickness and refers to a physical film thickness. Since it is difficult to measure the film thickness of one film after stacking, in this specification, the film thickness of a single layer film produced under the same film formation conditions as in the film formation of the low radiation film and the transportation of the glass plate are first described. From the product with the speed, the film formation speed for producing the monolayer film is calculated in advance, and then the film thickness is calculated from the film formation speed when the low-emission film is actually formed. The value obtained was used as the geometric film thickness.

(Optical film thickness)
The optical film thickness is a value represented by the product of the geometric film thickness and the refractive index. Since it is difficult to measure the refractive index of one film after stacking, in this specification, a refractive index and a refractive index at a wavelength of 550 nm are preliminarily determined for a single layer film manufactured under the same film formation conditions as those for the low radiation film formation. Calculate the film speed, then calculate the film thickness from the film formation speed when the low-emission film was actually formed, and use the value obtained from the product of the film thickness and the refractive index as the optical film thickness. It was. The refractive index in the present invention was calculated by measuring the transmittance and reflectance of a single layer film, and using the obtained values by optical simulation (Reflectance-transmittance method).

2: Each configuration of the low emission glass The first invention is a low emission glass in which a low emission film having one Ag film is formed on the surface of the glass plate. The first dielectric film has a first dielectric film, a second dielectric film, an Ag film, a barrier film, and a third dielectric film, and the first dielectric film has a Ti oxide layer having an optical film thickness of 30 to 50 nm. The second dielectric film has a crystalline dielectric layer in contact with the Ag film, and the total optical film thickness of the second dielectric film is 15 to 35 nm, and the third dielectric film Has a total optical film thickness of 80 to 120 nm, and the Ag film is a low emission glass characterized by a geometric film thickness of 11 to 14 nm.

  One preferred embodiment of the first invention is shown in FIG. Each configuration will be described below.

(Glass plate G)
The glass plate G to be used is not particularly limited as long as a low radiation film can be formed. For example, commonly used soda lime glass, alkali-free glass, high transmission glass, air-cooled tempered glass, chemical Tempered glass, netted glass, lined glass, borosilicate glass, low expansion glass, zero expansion glass, low expansion crystallized glass, zero expansion crystallized glass, and the like can be used.

  Although the thickness of the glass plate G is not specifically limited, It is good also as 3-19 mm generally used as a window glass for construction.

(Low radiation film 60)
The low radiation film 60 includes, in order from the glass plate G side, the first dielectric film 1, the second dielectric film 2, the Ag film 3, the barrier film 4, and the third dielectric film 5, and the glass plate G It is formed on the surface. “Surface” refers to contact with the glass plate G. Further, between the glass plate G and the first dielectric film 1, between the first dielectric film 1 and the second dielectric film 2, and between the barrier film 4 and the third dielectric film 5, any film Or layers may be interposed. In addition, an arbitrary film may be formed on the third dielectric film 5 as long as desired heat insulating properties, heat shielding properties, and various optical characteristics are not impaired. The arbitrary film may be various dielectric films, metal films, resinous films or films.

(First dielectric film 1)
The first dielectric film 1 is a film formed on the surface of the glass plate G, and is a Ti oxide layer 10 having an optical film thickness of 30 to 50 nm. The Ti oxide layer 10 can suppress the tint of the transmission color tone and the reflection color tone from being yellowish or reddish due to the thick film thickness of the Ag film 3. It is possible to improve both the heat insulating properties of the radiation film 60 and realize a preferable appearance as a window glass. The Ti oxide to be used may be a transparent film, for example, a TiO _x film (1.8 ≦ x ≦ 2) obtained by a sputtering method using a Ti target and an atmosphere gas containing oxygen (hereinafter, referred to as “1.8 ≦ x ≦ 2”). Or simply “TiO ₂ ”). In addition, for the purpose of stabilizing the discharge, improving the deposition rate, or improving the durability of the obtained film, an alloy target in which Zr, Nb or the like is mixed with the target is used, or C, N, or the like is used as the atmospheric gas. TiO _x : Y film obtained by using a gas mixed with (Y is a trace component contained in the film) may be used. The TiO _x : Y film may be a transparent film, and as the “Y” component, for example, Zr, Nb, C, N, or the like may be contained at 10 at% or less with respect to Ti. When the optical film thickness of the Ti oxide layer 10 is less than 30 nm, the transmittance from the visible to the near-infrared region is low and the reflectance is high. End up. On the other hand, if it exceeds 50 nm, the reflection color tone is strong and reddish, which is not preferable as the appearance of the window glass. Moreover, it is good also as 33-46 nm preferably.

(Second dielectric film 2)
The second dielectric film 2 is formed on the first dielectric film 1, has a crystalline dielectric layer 20 in contact with the Ag film 3, and the optical film thickness of the second dielectric film 2. Is a total of 15 to 35 nm. If the total optical film thickness is less than 15 nm, the visible to near-infrared transmittance is low and the reflectance in the same wavelength region is high, so that the solar radiation entering the room is easily blocked. Further, the glare of the reflected light is easily visually recognized. On the other hand, if it exceeds 35 nm, the reflected color tone is strongly reddish, which is not preferable as the appearance of the window glass.

  The crystalline dielectric layer 20 is a layer that improves the crystallinity of the Ag film 3, and is formed on the uppermost layer of the second dielectric film 2. The crystalline dielectric layer 20 has a zinc oxide structure, and it is preferable to use a Zn oxide layer. Examples of the Zn oxide include ZnO and ZnAlO. Note that the above “ZnAlO” indicates that Zn is mixed with Al, and does not indicate that Zn: Al: O = 1: 1: 1. In addition, the optical film thickness of the crystalline dielectric layer 20 is preferably 10 nm or more in order to develop sufficient crystallinity.

In FIG. 1, the second dielectric film 2 has an arbitrary dielectric layer 21 between the first dielectric film 1 in addition to the crystalline dielectric layer 20. The dielectric layer 21 is used for the purpose of improving the adhesion between the Ti oxide layer 10 and the crystalline dielectric layer 20, improving the durability of the low radiation film 60, and adjusting the transmission color tone and reflection color tone. For example, Sn oxide or a mixed oxide of Zn and Sn can be used. The above Sn oxide include SnO ₂ and the like. The optical film thickness of the dielectric layer 21 is not particularly limited as long as the total optical film thickness of the second dielectric film 2 falls within the above-described range.

(Ag film 3)
The Ag film 3 is a film having a function of reflecting infrared rays, and one Ag film 3 is used in the low radiation film 60. In the present invention, by using one Ag film 3 having a geometric film thickness of 11 to 14 nm, it is possible to achieve both appropriate heat insulation and solar radiation. When two or more Ag films 3 are used, the heat shielding property is increased, and it may be difficult to suppress the cooling around the window described above. As the Ag film 3, Ag or an Ag alloy film containing Ag as a main component is used. The Ag alloy film may contain, for example, metals such as palladium, gold, platinum, nickel and copper within a range of 5 wt% or less.

  In the present invention, the geometric film thickness of the Ag film 3 is set to 11 to 14 nm. When the thickness is less than 11 nm, the heat insulating property tends to be poor, and when it exceeds 14 nm, the transmittance of solar radiation decreases and the reflectance increases, and the reflected color tends to be reddish.

(Barrier film 4)
The barrier film 4 is formed on the surface of the Ag film 3, and when the dielectric layer such as the third dielectric film 5 is formed on the barrier film 4, the Ag film 3 is reactive gas such as oxygen gas. It suppresses deterioration by. The barrier film 4 is obtained by forming a metal film or an alloy film in an inert gas atmosphere so that the Ag film 3 is not deteriorated when formed. Many metal films and alloy films absorb visible light. However, when a dielectric layer is formed on the barrier film 4, oxidation or acid is caused by plasma generated from a gas containing oxygen or nitrogen used at this time. By being nitrided, it becomes possible to reduce the amount of absorption of visible light.

  As the barrier film 4, it is preferable to use ZnAl (Zn and Al alloy), Ti, NiCr (Ni and Cr alloy), Nb, stainless steel, and the like. The preferred film thickness varies depending on the type of film used and the film formation conditions. For example, the geometric film thickness is 1 to 3.5 nm for ZnAl, 1 to 3 nm for Ti, 1 to 2 nm for NiCr, and 1 for Nb. ˜2 nm, and stainless steel may be 1.5 to 2.5 nm. Note that the description of alloys such as “ZnAl” and “NiCr” does not indicate that, for example, Zn: Al = 1: 1 or Ni: Cr = 1: 1.

(Third dielectric film 5)
The third dielectric film 5 is formed on the barrier film 4 and has a total optical film thickness of 80 to 120 nm. When the thickness is less than 80 nm, the reflected color tone is strongly reddish, which is not preferable as the appearance of the window glass. Moreover, if it exceeds 120 nm, the transmittance | permeability of visible light will become low, and a reflectance will become high, and it will become easy to block the sunlight which will impair daylighting property or enter a room | chamber interior. Further, the glare of the reflected light is easily visually recognized. In FIG. 1, the third dielectric film 5 is composed of two layers. However, if the optical film thickness is within the above range and the desired optical characteristics are not impaired, one layer may be used, and three or more layers may be used. But you can.

The third dielectric film 5 is preferably made of a material excellent in moisture resistance and physical / chemical durability. In particular, it is preferable to dispose a layer having high physical and chemical durability as the uppermost layer farthest from the glass plate G. For example, it is preferable to use ZnSnO excellent in moisture resistance, TiO ₂ or Si ₃ N ₄ excellent in physical and chemical durability, and the like. In addition, said ZnSnO is an alloy oxide which contains Zn and Sn, and does not show Zn: Sn: O = 1: 1: 1.

  Moreover, it is preferable to have a dielectric layer containing an oxide of a metal element contained in the barrier film 4 on a contact surface in contact with the barrier film 4. For example, when Zn is used for the barrier film 4, it is preferable to use an oxide containing Zn for the dielectric layer. The above configuration is preferable because the adhesion between the barrier film 4 and the third dielectric film 5 is improved, and the moisture resistance and physical durability may be improved.

(Passivation film)
A passivation film (not shown) is usually formed on the surface of the glass plate G, and suppresses the diffusion and intrusion of various components of the glass plate G from the glass plate G to each layer of the low radiation film. Has the function of In FIG. 1, the first dielectric film 1 is formed on the surface of the glass plate G, but the passivation film may be provided between the glass plate G and the first dielectric film 1. As the passivation film, a dielectric film having a passivation function may be used, and examples thereof include Si oxides such as SiO ₂ and SiAlO. The refractive index of the Si oxide as described above is suitable because there is no significant difference from the refractive index of the glass plate G and the optical characteristics of the low emission glass are not greatly impaired.

(Low emission glass 6)
The low emission glass of the first invention has a visible light transmittance of 75 to 85%, clear transmission color tone (-3 ≦ a ^* ≦ 0, −3 ≦ b ^* ≦ 5), and a reflectance of film surface reflection of 6 -16%, reflection color tone can be blue (-3≤a ^* ≤3, -20≤b ^* ≤-10). When the reflection color tone a ^* is a positive value, the reflection color tone of the low-emission glass single plate exhibits a reddish color. Redness tends to ease. However, if a ^* is excessively high, it will exhibit a reddish color even after being incorporated into the double-glazed glass. Therefore, the a ^{* of the} low emission glass is preferably 3 or less. Moreover, the solar radiation transmittance of the said low radiation glass can be 50 to 60%, and the perpendicular | vertical emissivity of a film surface can be 0.04 to 0.06.

3: Multi-layer glass The second invention is a multi-layer glass in which a low emission film having one Ag film has a low emission glass formed on the surface of the glass plate and a glass plate, and the low emission film Has, in order from the glass plate side, a first dielectric film, a second dielectric film, an Ag film, a barrier film, and a third dielectric film, and the first dielectric film has an optical film thickness. Is a 30-50 nm Ti oxide layer, and the second dielectric film has a crystalline dielectric layer in contact with the Ag film, and the total optical film thickness of the second dielectric film is 15-35 nm. The third dielectric film has a total optical film thickness of 80 to 120 nm, the Ag film has a geometric film thickness of 11 to 14 nm, and the low emission glass has a thickness of 10 The thermal conductivity calculated in accordance with JIS R3107 of the multilayer glass is 1. W / ^m and is ² K or less, solar heat gain coefficient calculated in conformity with JIS R3106 is double glazing, characterized in that at least 0.50. In addition, it is preferable to arrange | position a low radiation film | membrane on the surface by the side of the hollow layer of the indoor side glass of a multilayer glass for the purpose of taking in more solar radiation indoors.

  One preferred embodiment of the second invention is shown in FIG. Each configuration will be described below. In addition, about the film | membrane (1-5) of the low radiation film | membrane 60, the low radiation film | membrane 60, and the low radiation glass 6, since it is the same as that of description mentioned above, it abbreviate | omits.

(Glass plate G)
The glass plate G described here is the glass plate G on which the low radiation film 60 is not formed as shown in FIG. The glass plate G is not particularly limited, but as described above, for example, commonly used soda lime glass, alkali-free glass, high transmission glass, air-cooled tempered glass, chemically tempered glass, netted glass, Lined glass, borosilicate glass, low expansion glass, zero expansion glass, low expansion crystallized glass, zero expansion crystallized glass, and the like can be used. Moreover, you may use a laminated glass. The thickness of the glass plate G is not particularly limited, but may be 3 to 19 mm.

(Spacer 8)
The spacer 8 is a long member provided between the low emission glass 6 and the glass plate G, and is installed along the periphery of the low emission glass 6 and the glass plate G. By providing the spacer 8, the low emission glass 6 and the glass plate G can be arranged at a predetermined interval, and the range surrounded by the low emission glass 6, the spacer 8, and the glass plate G is hollow. Layer 7 is formed.

  The spacer 8 may be an existing one, and usually a lightweight aluminum material or resin material is used. Further, the inside of the spacer 8 may be filled with a desiccant (not shown) or the like. The spacer 8 is bonded to the low radiation glass 6 and the glass plate G by a sealing material such as butyl rubber or silicone, and seals the hollow layer 7.

(Hollow layer 7)
As described above, the hollow layer 7 is a range surrounded by the low radiation glass 6, the spacer 8, and the glass plate G, and by sealing the gas to the hollow layer 7, heat insulation and sound insulation are improved. Is possible. Examples of the gas to be sealed include inert gases such as Ar, He, Ne, Kr, and Xe, dry air, and N _2. Dry air is particularly preferable because it can be easily used. Further, by setting the thickness to 10 to 16 mm, it is possible to obtain a desired heat transmissibility.

(Multilayer glass 9)
As described above, the multi-layer glass 9 is formed by integrating the low emission glass 6 and the glass plate G through the spacer 8 with the primary sealant 81 and the secondary sealant 82, and the window of the building. It can be used as glass. The multilayer glass 9 of the second invention has a heat transmissivity calculated in accordance with JIS R3107 of 1.9 W / m ² K or less, and a solar heat gain rate calculated in accordance with JIS R3106 is 0.50. That's it. Preferably, the heat transmissivity may be 1.2 to 1.9 W / m ² K and the solar heat gain may be 0.55 to 0.65.

4: Manufacturing method of low radiation glass An example of the manufacturing method of the low radiation glass of this invention is demonstrated below. The present invention is not limited to the following.

  The low emission film of the low emission glass of the present invention is preferably formed by a sputtering method, an electron beam evaporation method, an ion plating method or the like, but the sputtering method is suitable in that it is easy to ensure productivity and uniformity. Yes. The formation of the low radiation film by the sputtering method is performed while the glass plate is transported through the apparatus in which the sputtering target as the material of each film is installed. At this time, an atmospheric gas used for sputtering is introduced into a vacuum chamber in which film formation is performed in the apparatus, and plasma is generated in the apparatus by applying a negative potential to the target to perform sputtering.

  The method of obtaining a desired film thickness is not particularly limited because it differs depending on the type of the sputtering apparatus, but the method of adjusting the film thickness by changing the film formation rate by adjusting the power input to the target and the conditions of the atmospheric gas. In addition, a known method such as a method of adjusting the film thickness by adjusting the substrate conveyance speed can be used.

When forming each dielectric film or dielectric layer, the target to be used may be either a ceramic target or a metal target. In any case, the gas conditions of the atmospheric gas to be used are not particularly limited. For example, the gas type and the mixing ratio may be appropriately determined according to the target film from Ar gas, O ₂ gas, N ₂ gas, or the like. The gas introduced into the vacuum chamber may include an optional third component in addition to Ar gas, O ₂ gas, and N ₂ gas.

Further, when the third dielectric film is formed, a reaction of O ₂ gas, N ₂ gas, CO ₂ gas, etc. is performed so that the barrier film formed under the third dielectric film can be oxidized or oxynitrided. It is preferable to form a film in a reactive gas atmosphere.

  When forming an Ag film, an Ag target or an Ag alloy target is used as a target to be used. Ar gas is preferably used as the atmospheric gas introduced at this time, but different types of gases may be mixed as long as the optical properties of the Ag film are not impaired.

  When the barrier film is formed, a target to be used may be selected as appropriate, and an inert gas such as Ar may be used as the introduced atmospheric gas. Further, in order to suppress a significant decrease in visible light transmittance, the thickness of the barrier film is desirably set to such a thickness that can be oxidized or oxynitrided in a later step.

  The plasma source can be a DC power supply, an AC power supply, a power supply in which AC and DC are superimposed, etc., but if abnormal discharge is likely to occur when forming a dielectric film or dielectric layer, the DC power supply It is preferable to use a power source to which a pulse is applied or an AC power source.

  Examples of the present invention and comparative examples are described below. In addition, this invention is not limited to the following aspects.

1: Production of low emission glass Low emission glass was produced by the following method. In all Examples and Comparative Examples, a film was formed on soda lime glass having a thickness of 3 mm using an inter-back magnetron sputtering apparatus. Further, in any of the examples and comparative examples, the glass plate and the film were not heated, and heating was not particularly performed except when the glass plate temperature increased due to sputtering during film formation.

Each layer obtained the film thickness described in Table 1 by adjusting the input power to the target or the conveyance speed of the glass plate. In addition, in the case where the film formation rate was slow or a film having a large thickness was formed, the number of times the glass plate was passed through the target facing surface was increased. In addition, the input power and the conveyance speed described above were calculated using the film formation speed obtained in advance by determining the film formation speed of the single-layer film for each type of film. In Table 1, the dielectric layer is described as an optical film thickness, and the Ag layer and the barrier layer are described as a geometric film thickness. In Table 1, the first dielectric film is denoted as D ₁ , the second dielectric film as D ₂ , the third dielectric film as D ₃ , the Ag film as Ag, and the barrier film as B.

(Examples 1-2, Comparative Examples 1-3)
First, a desired target was set in each vacuum chamber, and the inside of the vacuum chamber was evacuated by a vacuum pump. The target has a magnet disposed on the back side. Next, a glass plate was introduced into the vacuum chamber, and each layer was sequentially formed so as to have the film configuration shown in Table 1. Each layer was formed by the following method.

In forming the TiO ₂ layer, a Ti target was used as a target, and power of 8.1 W / cm ^{2 was} supplied to the target from a DC power source through a power cable. At this time, while continuously operating the vacuum pump, 0.1 L / min of argon gas and 1.4 L / min of oxygen gas were introduced into the vacuum chamber, and the pressure was adjusted to 0.5 Pa. Thereafter, the glass plate was passed through the front surface of the target at an appropriate speed and number of passes to obtain a TiO ₂ layer.

The ZnSnO layer is formed by using a Zn target (hereinafter also referred to as ZnSn) in which 50 wt% of Sn is added to the target, and the atmosphere gas in the vacuum chamber is argon gas of 0.1 L / min and oxygen gas. It was introduced at 1.6 L / min and the pressure was adjusted to 0.4 Pa. The power supplied from the DC power source was 2.3 W / cm ² . Film formation was performed under the above conditions to obtain a ZnSnO layer.

The ZnAlO layer is formed by using a Zn target (hereinafter also referred to as ZnAl) in which 2 wt% of Al is added to the target, and the atmosphere gas in the vacuum chamber is argon gas of 0.1 L / min and oxygen gas. It was introduced at 1.6 L / min and the pressure was adjusted to 0.4 Pa. The power input from the DC power source was 3.5 W / cm ² . Film formation was performed under the above conditions to obtain a ZnAlO layer.

An Sn target is used for forming the SnO ₂ layer, and the atmospheric gas in the vacuum chamber is introduced with argon gas at 0.1 L / min and oxygen gas at 1.6 L / min, and the pressure is adjusted to 0.4 Pa. did. The power supplied from the DC power source was 2.3 W / cm ² . Film formation was performed under the above conditions to obtain a SnO ₂ layer.

The Ag film and the barrier film (Ti film, ZnAl film) were simultaneously discharged and formed by the same transport path. The Ag film is formed by using an Ag target as the target, and adjusting the electric power input from the DC power source to a desired film thickness within a range of 6.8 to 9.6 W / cm ² to obtain an Ag film. It was.

The Ti film is formed using a Ti target as the target, and the electric power supplied from the DC power source is adjusted to a desired film thickness within the range of 6.7 to 7.0 W / cm ² to obtain the Ti film. It was.

For the formation of the ZnAl film, a ZnAl target with 4 wt% of Al added to the target is used, and the power supplied from the DC power source is set to a desired film thickness within a range of 0.7 to 1.4 W / cm ^2. The ZnAl film was obtained by adjusting.

  When forming the above Ag film and each barrier film, 0.7 L / min of argon gas was introduced into the vacuum chamber and the pressure was adjusted to 0.5 Pa.

2: Various optical characteristics of the low radiation glass Next, the solar radiation transmittance (T _sol ), visible light transmittance (T _v ), transmission color tone, and visible light reflectance (R _f ) of the film surface of the obtained low radiation glass The visible light reflectance (R _g ) of the glass surface, the reflection color tone, and the vertical emissivity (ε _n ) of the film surface were measured. Moreover, all measured using the self-recording spectrophotometer (the Hitachi Ltd. make, U-4100) and the Fourier-transform infrared spectrophotometer (the JASCO make, FT / IR-4200).

(Solar radiation transmittance)
As the solar transmittance (T _sol ), a value calculated by a method based on JIS R3106 (1998) from the transmittance measured with the above-mentioned self-recording spectrophotometer was used.

(Visible light transmittance, visible light reflectance)
For the visible light transmittance (T _v ) and visible light reflectance (R _f and R _g ), values calculated by a method based on JIS R3106 (1998) from the transmittance and reflectance measured with a self-recording spectrophotometer are used. It was.

(Transparent color tone, reflective color tone)
The transmitted color tone and the reflected color tone are shown by the CIE L ^* a ^* b ^* chromaticity coordinate diagram for each color tone of transmitted light and reflected light calculated in accordance with JIS Z8781-4.

(Vertical emissivity)
As the vertical emissivity (ε _n ) of the film surface of the low radiation film, a value calculated by a method based on JIS R3106 (1998) from the reflectance measured by the Fourier transform infrared spectrophotometer was used.

  From the results in Table 2, it was found that in all examples, the solar radiation transmittance was in the range of 50 to 60%, and the vertical radiation rate of the low radiation film was in the range of 0.04 to 0.06. The transmitted color tone was clear with no redness, and the reflection color tone was blue.

On the other hand, Comparative Example 1 had a large vertical emissivity (ε _n ) and a lower thermal insulation performance than the Examples. In Comparative Example 2, the heat shielding property and the heat insulating performance were equivalent to those in Examples, but the transmission color tone was strong yellow and the reflection color tone of the film surface and glass surface was reddish, so that the appearance was inferior. In Comparative Example 3, the heat shielding property and the heat insulating performance were equivalent to those in Examples, but the yellow color of the transmitted color tone was strong.

3: Production of multi-layer glass Multi-layer glass was produced using the obtained low emission glass, general float plate glass (thickness 3 mm), and an aluminum spacer filled with a desiccant inside. First, the low radiation glass and the float plate glass were opposed to each other so that the thickness of the hollow layer was 10 mm, and the spacer was disposed between the glass plates along the periphery of the glass plate. At this time, the low radiation membrane was in contact with the hollow layer.

  Next, all members were integrated using a primary sealing material made of butyl rubber between the spacer and the glass surface, and a secondary sealing material made of polysulfide sealant on the outer periphery of the spacer. The multilayer glass whose hollow layer is dry air was obtained by the above method.

4: Various evaluations of the double-glazed glass The self-recording spectrophotometer of the low-radiation glass shows the visible light transmittance, the outdoor and indoor visible light reflectance, the heat transmissivity, and the solar heat gain of the obtained double-glazed glass. And it calculated from the measurement result of a Fourier transform infrared spectrophotometer by the method based on JIS R3106 (1998) and JIS R3107 (1998), and the obtained result was shown in Table 3. In addition, the multi-layer glass was arrange | positioned so that the glass of the outdoor side might be general float plate glass, and the glass of the indoor side might be low radiation glass. In Table 3, “%” of “transmitted light” indicates visible light transmittance, and “%” of “reflected light” indicates respective visible light reflectance.

(Heat flow rate)
The value calculated by the method based on JIS R3107 (1998) was used for the heat transmissivity. Moreover, what has a heat transmissivity of 1.9 W / m ² K or less was defined as “having moderate heat insulation”.

(Solar heat acquisition rate)
The solar heat acquisition rate used the value computed by the method based on JISR3106 (1998). In addition, the solar heat acquisition rate of 0.5 or more was defined as “capable of capturing solar radiation”.

  From the heat transmissivity and solar heat gain of the double-glazed glass, it was found that both Examples 1 and 2 have moderate heat insulation properties and can incorporate solar radiation. Further, it was found that the visible light transmittance was 72% or more, and the daylighting property was sufficient.

On the other hand, Comparative Example 1 with a thin Ag layer could not achieve sufficient heat insulation. Further, Comparative Example 2 in which the second dielectric layer is thick has heat insulating properties and heat shielding properties equivalent to those of the example, but the reflection color tone is still reddish and the transmission color tone is also yellowish in the multilayer glass configuration. This was not preferable as the appearance of the window glass. The comparative example 3 in which the first dielectric layer is not Ti oxide but SnO ₂ is also not preferable as the appearance of the window glass because the transmission color tone is yellowish.

G: glass plate, 1: first dielectric film, 10: Ti oxide layer, 2: second dielectric film, 20: crystalline dielectric layer, 21: dielectric layer, 3: Ag film, 4: barrier Membrane, 5: Third dielectric film, 6: Low radiation glass, 60: Low radiation film, 7: Hollow layer, 8: Spacer, 81: Primary sealing material, 82: Secondary sealing material, 9: Multi-layer glass

Claims (4)

In the low emission glass in which the low emission film having one Ag film is formed on the surface of the glass plate,
The low radiation film has, in order from the glass plate side, a first dielectric film, a second dielectric film, an Ag film, a barrier film, and a third dielectric film,
The first dielectric film is a Ti oxide layer having an optical film thickness of 30 to 50 nm,
The second dielectric film has a crystalline dielectric layer in contact with the Ag film, and the total optical film thickness of the second dielectric film is 15 to 35 nm,
The third dielectric film has a total optical film thickness of 80 to 120 nm,
The low emission glass characterized in that the Ag film has a geometric film thickness of 11 to 14 nm. 2. The low emission glass according to claim 1, wherein the crystalline dielectric layer is a Zn oxide layer. 3. The third dielectric film according to claim 1, wherein the third dielectric film has a dielectric layer including an oxide of a metal element contained in the barrier film on a contact surface in contact with the barrier film. Low emission glass. The low emission film having one Ag film is a multi-layer glass having a low emission glass formed on the glass plate surface and a glass plate,
The low radiation film has, in order from the glass plate side, a first dielectric film, a second dielectric film, an Ag film, a barrier film, and a third dielectric film,
The first dielectric film is a Ti oxide layer having an optical film thickness of 30 to 50 nm,
The second dielectric film has a crystalline dielectric layer in contact with the Ag film, and the total optical film thickness of the second dielectric film is 15 to 35 nm,
The third dielectric film has a total optical film thickness of 80 to 120 nm,
The Ag film has a geometric film thickness of 11 to 14 nm,
The low emission glass is disposed with a distance of 10 to 16 mm from the glass plate,
The multilayer glass has a heat transmissivity calculated in accordance with JIS R3107 of 1.9 W / m ² K or less, and a solar heat gain rate calculated in accordance with JIS R3106 is 0.50 or more. Multi-layer glass.

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