JP6287502B2 - Low radiation window material - Google Patents

Description

  The present invention relates to a low radiation transparent substrate on which a low radiation film having heat shielding performance is formed.

  In window materials such as double-glazed glass laminated so as to form a hollow layer between two glass substrates, a low-radiation laminated film has recently been placed on the hollow layer side of the glass substrate for the purpose of improving cooling and heating efficiency. In addition, window materials using low emission glass are becoming widespread. This low-emission glass incorporates visible light into the room and satisfies the daylighting (transparency) required for window glass, while the low-emission film has a heat-shielding property that reflects light in the near infrared to infrared range. Therefore, the indoor temperature rise by sunlight can be suppressed. Moreover, in order to interrupt | block the transmission of the heat | fever from the room | chamber interior, the capability to heat-insulate and insulate a room | chamber interior is also high.

  As a window material for construction, one using a low radiation glass having an appropriate lighting property and heat shielding property has been proposed. Daylighting and heat-shielding properties of low-radiation glass tend to contradict each other, and increasing the heat-shielding property decreases the daylighting properties. Therefore, emphasis was placed on the type that emphasized daylighting and the heat-shielding property depending on the desired performance. Two types are being considered. Low-emission glass is usually used as a multi-layer glass, but when the daylighting and heat-shielding properties of the low-emission glass are simply evaluated, the visible light transmittance when measured with a single sheet of low-emission glass is daylighting and solar transmission The rate can be used as an evaluation criterion for thermal insulation.

  Many of the types that place importance on the daylighting property have a visible light transmittance of 70% or more. For example, in the patent document 1, the applicant of the present invention has a second layer and a second layer that are metal layers mainly composed of Ag. The total geometric thickness of the four layers is 22 to 29 nm, the geometric thickness of the second layer is 0.3 to 0.8 times the geometric thickness of the fourth layer, and is the first dielectric layer. The optical thickness of the third layer is 220 to 380 nm, the optical thickness of the third layer is 140 to 200 nm, the optical thickness of the first layer is 0.4 to 1.4 of the optical thickness of the fifth layer. A glass laminate for windows in which the reflectance in the near infrared region is improved by 5 times is disclosed. In the embodiment, the window glass laminate has a visible light transmittance of 70% or more and a solar radiation transmittance of about 33 to 40%.

  In addition, for example, office buildings are dazzled by sunlight and the reflected light from adjacent buildings, so the demand for window materials with a visible light transmittance lower than 70% for the purpose of reducing glare. As such a window material, the above-mentioned low radiation glass with an emphasis on the heat shielding property is used. As a type that attaches importance to heat shielding properties, low radiation glass having a visible light transmittance of less than 70% and a solar radiation transmittance of 40% or less is incorporated in a double-glazed glass, and the solar heat acquisition rate of the double-glazed glass Has been studied.

  For example, in Patent Document 2, an absorption layer that absorbs solar radiation to some extent is provided on a transparent plate, and solar radiation in which a laminated film including a layer mainly composed of Ag as described above and a transparent dielectric layer is formed thereon. A shielding light-transmitting plate is disclosed. In an Example, the solar radiation transmittance | permeability in the single plate | board of the said solar shading translucent board is 21-35% or less, and the solar heat acquisition rate when it is set as a multilayer glass is 0.29-0.40.

  In Patent Document 3, a first dielectric film, a film mainly composed of first Ag, and a second dielectric film are sequentially formed on one plate surface on a transparent glass plate from the glass plate side. In the solar shading glass in which the film mainly composed of the second Ag and the third dielectric film are laminated, the sum of the film thicknesses of the films mainly composed of the first and second Ag is 25 to 25. A solar radiation shielding glass is disclosed in which the film thickness of the film mainly composed of the first Ag at 35 nm is 30% or more and less than 50% of the film thickness of the film mainly composed of the second Ag. In an Example, the solar radiation transmittance | permeability in the single plate of the said solar shading glass is 27 to 36%, and the solar heat acquisition rate when it is set as a multilayer glass is 0.31-0.38.

  As a window glass for a high-rise building such as an office building, an appearance in which the appearance when viewed from obliquely below is not red or purple but neutral or blue is preferred. For example, Patent Document 4 discloses a laminate in which three transparent dielectric layers and two Ag layers are alternately laminated on a transparent substrate so that the Ag layers are interposed between the transparent dielectric layers. When the first Ag layer and the second Ag layer are sequentially formed from the transparent substrate side, the ratio of the physical film thickness of the second Ag layer to the first Ag layer is 1.05 or more, And the laminated body whose visible light transmittance | permeability of the said laminated body is 50% or less is disclosed.

JP 2010-195638 A JP-A-11-228185 JP 11-277668 A International Publication WO2012 / 115111

  In recent years, the demand for energy saving is increasing for the window material for construction, and the low radiation glass which has the outstanding heat-shielding property is being calculated | required. On the other hand, architectural window materials are important for the design and aesthetics of buildings. Especially when window windows of high-rise buildings are viewed from an obliquely outdoor position, the reflected light glare. There is a high demand for low-emission glass having good optical characteristics (hereinafter referred to as “appearance quality”) on the appearance such that the reflection color tone is achromatic to blue.

  In order to improve the heat shielding property of low emission glass, the thickness of the metal layer of the low emission film is generally increased. On the other hand, when the thickness of the metal layer is increased, the visible light reflectivity increases and the visible to the indoor side increases. The light transmittance is lowered. For this reason, when the low emission glass is viewed from the outside, the appearance of the reflected color tone of the reflected light is more strongly visually recognized, so that the appearance quality is easily deteriorated and the transparency is also deteriorated.

  Accordingly, an object of the present invention is to obtain a window material that exhibits an external appearance quality not found in conventional products and has excellent heat shielding properties without impairing transparency. Another object of the present invention is to obtain a low-emission window material having an achromatic to blue reflective color tone that is preferred for use in buildings such as office buildings where the appearance quality affected by solar radiation is particularly problematic.

  The present inventors diligently researched and developed a low-emission film. As a result, an Ag2 layer-type low-emission film is used to provide an appearance quality not found in conventional products, and without impairing transparency. It has been found that a window material having thermal properties can be realized, and the window material has an achromatic color to blue color, and can provide an environmentally preferable window material.

In other words, a first aspect of the present invention is a window material that separates the outdoors from the indoors, and the window material includes a dielectric layer and a metal layer mainly composed of Ag on a transparent substrate. A low radiation film having a low radiation film having a laminate in which a layer, a first metal layer, a second dielectric layer, a second metal layer, and a third dielectric layer are laminated in this order, and in contact with the outdoors on a transparent substrate surface Having a substrate, the laminate is
The optical thickness of the first dielectric layer is 60 to 110 nm,
The physical thickness of the first metal layer is 7.0 to 9.5 nm,
The optical thickness of the second dielectric layer is 190 to 250 nm,
The physical film thickness of the second metal layer is 16.5 to 19.5 nm,
The optical thickness of the third dielectric layer is 50 to 100 nm,
The total physical film thickness of the first and second metal layers is 23.5 to 29 nm,
A total value of optical film thicknesses of the first, third and fifth dielectric layers is within a range of 330 to 430 nm;
The optical characteristics of the low emission transparent substrate are:
The solar transmittance calculated according to JIS R3106 (1998) does not exceed 33%,
The visible light reflectance of the transparent substrate surface calculated according to JIS R3106 (1998) does not exceed 28%,
The reflected color tone of the outdoor surface in contact with the outdoors exhibits an achromatic color, or the color represented by ((a *) ² + (b *) ² ) ^1/2 in the CIE L * a * b * chromaticity coordinate diagram It is a low emission window material characterized by exhibiting a blue reflection color tone with a degree of 20 or less.

According to a second aspect of the present invention, there is provided a window material that separates the outdoors from the indoors, and the window material includes a dielectric layer and a metal layer containing Ag as a main component on a transparent substrate. A low radiation film having a laminated structure in which a layer, a first metal layer, a second dielectric layer, a second metal layer, and a third dielectric layer are laminated in this order is formed, and the low radiation transparent contact with the interior and the transparent substrate surface A substrate, and a transparent substrate between the low-emission transparent substrate and the outdoors, the laminate is
The optical thickness of the first dielectric layer is 60 to 110 nm,
The physical thickness of the first metal layer is 7.0 to 9.5 nm,
The optical thickness of the second dielectric layer is 190 to 250 nm,
The physical film thickness of the second metal layer is 16.5 to 19.5 nm,
The optical thickness of the third dielectric layer is 50 to 100 nm,
The total physical film thickness of the first and second metal layers is 23.5 to 29 nm,
A total value of optical film thicknesses of the first, third and fifth dielectric layers is within a range of 330 to 430 nm;
The optical characteristics of the low emission transparent substrate are:
The solar transmittance calculated according to JIS R3106 (1998) does not exceed 33%,
The visible light reflectance of the film surface calculated according to JIS R3106 (1998) does not exceed 28%,
The reflected color tone of the outdoor surface in contact with the outdoors exhibits an achromatic color, or the color represented by ((a *) ² + (b *) ² ) ^1/2 in the CIE L * a * b * chromaticity coordinate diagram It is a low emission window material characterized by exhibiting a blue reflection color tone with a degree of 20 or less.

  The object of the present invention is to prevent the solar radiation transmittance calculated in accordance with JIS R3106 (1998) for a low radiation transparent substrate from exceeding 33%. As described above, when a glass plate is used as the transparent substrate, the glass plate may be used as a multi-layer glass, but usually the heat shielding property of the multi-layer glass is evaluated by a solar heat gain rate. However, since the solar heat gain of a multi-layer glass varies depending on the thickness of the glass plate and the hollow layer and the type of gas in the hollow layer, the solar transmittance is used as a numerical value representing the heat shielding property that can be evaluated even with a single glass plate. It was. Moreover, when using solar radiation transmittance, even if it is transparent substrates other than a glass plate, it can evaluate. A solar radiation transmittance of 33% or less for a single glass plate generally corresponds to a solar heat acquisition rate of 0.35 or less for a multilayer glass.

  In the present invention, the optical and thermal characteristics of the low radiation transparent substrate were measured using a self-recording spectrophotometer (Hitachi, U-4000) and a Fourier transform infrared reflection spectrophotometer (Perkin Elmer, Paragon 1000). . Moreover, the reflection color tone described later was similarly measured using a self-recording spectrophotometer (manufactured by Hitachi, Ltd., U-4000).

  With regard to the present invention, “appearance quality”, which refers to optical characteristics that affect the appearance, refers to the color tone of reflected light that is visible and the presence or absence of glare, and “good appearance quality” refers to the above reflection when viewed from the outside. The color tone of light is within the target achromatic to blue range, and the reflected light is not glaring.

In addition, the “achromatic color” refers to a color tone that does not exhibit a tint such as red, green, yellow, and blue, in which the reflected color tone when viewed from the outside is visible. Further, in the CIE L * a * b * chromaticity coordinate diagram, the saturation represented by ((a *) ² + (b *) ² ) ^1/2 is closer to 0 and closer to the above achromatic color, and the value is The higher the color, the more intense the color. When used as a window glass for architecture, if the color is excessively strong, the design and aesthetics of the building may be impaired, and visual stimulation may become strong. is there. Accordingly, in the present invention, the saturation is set to 20 or less.

  Another object of the present invention is to ensure that the visible light reflectance of the transparent substrate surface or film surface calculated in accordance with JIS R3106 (1998) does not exceed 28%. As described above, if the reflectance of visible light is high, the appearance quality is liable to be lost due to glare, so that the reflectance of visible light is preferably as low as possible. In the case of this invention, when this visible light reflectance exceeded 28%, it turned out that there exists a tendency for glare to be visually recognized strongly.

  Further, in the first embodiment of the present invention, the reflection color tone of the transparent substrate surface calculated in accordance with JIS Z8729 (2004) is used for the reflection color tone when viewed from the outdoor side to be achromatic to blue. In the L * a * b * chromaticity coordinate diagram, it is preferable that a * ≧ b *, a * is within a range of −10 to 0, and b * is within a range of −20 to 0. The reflection color tone is closer to an achromatic color as it is closer to 0, and the green reflection color tone is more visually recognized as the value of a * is negative, and the blue reflection color tone is stronger as the value of b * is larger in the negative direction. become.

  Further, in the second embodiment of the present invention, the reflection color tone of the film surface calculated in accordance with JIS Z8729 (2004) is CIE L so that the reflection color tone when viewed from the outdoor side is achromatic to blue. In the * a * b * chromaticity coordinate diagram, it is preferable that a * is in the range of -5 to 5 and b * is in the range of -10 to 5. In the second embodiment, since the transparent substrate is interposed between the low radiation transparent substrate and the outdoors, there is a difference between the value obtained by directly measuring the reflection color tone of the film surface and the value when the window material is used. When the reflection color tone of the film surface of the single plate is within the above range, the reflection color tone when viewed from the outside can be set to an achromatic color to a blue color.

  The metal layer is a layer containing Ag as a main component, and is an Ag film or an Ag alloy film containing Ag as a main component. As the Ag alloy, metals such as palladium, gold, platinum, nickel, and copper are each 5 It may be contained within the range of mass% or less. Here, the “main component” indicates that containing 90% by mass or more of Ag.

  The dielectric layer adjusts the reflection color tone of the low-emission film. In particular, the upper dielectric layer of the metal layer serves as a protective layer for the metal layer, and includes Zn, Sn, Al, Ti, Si, And a transparent thin film of oxide, nitride, or oxynitride containing at least one metal selected from the group consisting of In and In.

  The physical film thickness of the metal layer can be obtained by dividing the film formation speed of each layer estimated by the following procedure by the base material conveyance speed set at the time of forming the low radiation film. The film formation speed (nm · mm / min) of each layer is the product of the thickness (nm) of the single-layer film and the substrate transport speed (mm / min) when the single-layer film of each layer is formed. It is obtained by calculating. The thickness of the single layer film is determined by marking the glass substrate with a marker such as an oil pen before film formation and removing the film after film formation. The level difference from the portion where it was not formed was measured using a stylus type level meter (Veeco, Dektak 150).

  The optical film thickness of the dielectric layer is a value calculated from the product of the refractive index and the film thickness at a wavelength of 550 nm of a single layer film produced under the same film formation conditions as those for producing the low radiation film. In the present invention, the refractive index is obtained by measuring the transmittance and reflectance of a single layer film with the spectrophotometer (U-4000, manufactured by Hitachi, Ltd.), and from the obtained value, an optical simulation (Reflectance-transmittance method). Calculated by

  According to the present invention, it is possible to obtain an architectural low radiation window material having an achromatic color to a blue reflection color tone, exhibiting a preferable appearance quality not found in conventional products, and having excellent heat shielding properties without impairing transparency. It has become possible.

  Therefore, the choice as a low radiation window material important for the design and aesthetics of a building can be expanded.

It is a cross-sectional schematic diagram of the form (a) which used the low radiation | emission transparent substrate by the single plate, and the form (b) incorporated in the multilayer glass about the 1st Embodiment of this invention. It is a cross-sectional schematic diagram of the form integrated in the multilayer glass about the 2nd Embodiment of this invention. It is the figure which showed the value of a * and b * of the reflective color tone of the glass surface in the single plate of a low radiation | emission transparent board | substrate about the Example and comparative example of this invention. It is the figure which showed the value of a * and b * of the reflective color tone of the film surface in the single board of a low radiation | emission transparent board | substrate about the Example and comparative example of this invention.

1. First Embodiment A first embodiment of the present invention is a window material that separates the outdoors and indoors, and the window material includes a dielectric layer and a metal layer mainly composed of Ag on a transparent substrate. A low-emission film having a laminate in which a dielectric layer, a first metal layer, a second dielectric layer, a second metal layer, and a third dielectric layer are laminated in this order is formed and is in contact with the outdoors on the transparent substrate surface Having a low radiation transparent substrate, the laminate is
The optical thickness of the first dielectric layer is 60 to 110 nm,
The physical thickness of the first metal layer is 7.0 to 9.5 nm,
The optical thickness of the second dielectric layer is 190 to 250 nm,
The physical film thickness of the second metal layer is 16.5 to 19.5 nm,
The optical thickness of the third dielectric layer is 50 to 100 nm,
The total physical film thickness of the first and second metal layers is 23.5 to 29 nm,
A total value of optical film thicknesses of the first, third and fifth dielectric layers is within a range of 330 to 430 nm;
The optical characteristics of the low emission transparent substrate are:
The solar transmittance calculated according to JIS R3106 (1998) does not exceed 33%,
The visible light reflectance of the transparent substrate surface calculated according to JIS R3106 (1998) does not exceed 28%,
The reflected color tone of the outdoor surface in contact with the outdoors exhibits an achromatic color, or the color represented by ((a *) ² + (b *) ² ) ^1/2 in the CIE L * a * b * chromaticity coordinate diagram It is a low emission window material characterized by exhibiting a blue reflection color tone with a degree of 20 or less.

  As described above, the present invention has a low radiation transparent substrate whose solar radiation transmittance calculated according to JIS R3106 (1998) does not exceed 33%. In the present invention, when the thickness of the transparent substrate is 3 mm, the visible light transmittance calculated in accordance with JIS R3106 (1998) is less than 70%. Usually, the lower the solar transmittance, the higher the heat shielding property, but the visible light transmittance also decreases accordingly. When used for a window material such as a window glass, the solar transmittance may be preferably 25 to 29% in order to achieve both heat shielding properties and appropriate daylighting. Further, the visible light transmittance is preferably 50 to 65%, and more preferably 55 to 65%.

  Moreover, this invention is a low radiation | emission transparent substrate whose visible light reflectance of the transparent substrate surface computed based on JISR3106 (1998) does not exceed 28%. When the visible light reflectance is increased, the appearance quality is liable to be deteriorated due to glare. Therefore, the visible light reflectance is preferably as low as possible.

In the present invention, the outdoor surface in contact with the outdoors exhibits an achromatic to blue reflected color tone, and the reflected color tone is represented by ((a *) ² + (b *) ² ) ^1/2. Is 20 or less. When the saturation exceeds 20, the color tone of the reflected color becomes strong, and the design and aesthetics of the building may be impaired. The embodiment is particularly suitable for obtaining a blue reflected color tone, and the saturation may be 10 or more and 20 or less.

  In the present invention, the reflection color tone of the transparent substrate surface calculated in accordance with JIS Z8729 (2004) is a * ≧ b *, a * is −10 to 0 and b in the CIE L * a * b * chromaticity coordinate diagram. * Is preferably in the range of -20 to 0. At this time, red and yellow are mentioned as the reflection color tone which is supposed to impair the appearance quality. When the reflection color tone becomes reddish, a * is 5 or more, and when the reflection color tone becomes yellowish, b * is 5 or more. When both a * and b * are near 0, the color is close to achromatic, but in particular, a * is light reddish when a * is near 2, and the appearance quality is likely to be impaired. Further, when a * is less than −10, the green color of the reflected color tone is strongly exhibited. On the other hand, when b * is less than −20, blue color is strongly exhibited. In order to obtain better appearance quality, a *> b * and b * may preferably be within a range of −18 to −2.

  Usually, in order to prevent physical damage such as scratches, the low emission film is arranged so as not to directly expose the low emission film to the outdoors. When using a low emission film having a layer mainly composed of Ag as in the present invention, Ag is liable to cause defects due to moisture, chlorine, etc. in the atmosphere, so the low emission film does not contact the atmosphere. It is desirable to apply the coating or coat with a protective layer. For example, the low radiation transparent substrate as shown in FIG. 1 (a) can be used as a single plate, the multilayer glass as shown in FIG. 1 (b), or laminated glass.

  The low radiation transparent substrate 1 is disposed on the outdoor side, and the transparent substrate surface of the low radiation transparent substrate 1 is in contact with the outdoors. In this embodiment, it is easy to adjust the reflection color tone. Moreover, when incorporating in a multilayer glass like FIG.1 (b), since incident light does not inject to the hollow layer 4, it is possible to improve a thermal-insulation effect more.

  In the present invention, it is preferable that the low radiation transparent substrate, the hollow layer, and the transparent substrate are arranged in this order from the outdoor side, and the transparent substrate surface of the low radiation transparent substrate is in contact with the outdoors.

  The transparent substrate is not particularly limited as long as it is a material having good durability against heat, light, scratches and the like. In particular, a glass substrate is preferably used, but other transparent resin plates and the like may be used.

  The glass substrate is not particularly limited, and for example, a commonly used float plate glass or an inorganic transparent glass plate such as soda lime glass produced by a roll-out method can be used. Examples of the glass substrate include alkali-free glass and highly transmissive glass. The shape of the glass substrate is not particularly limited, and various tempered glasses such as flat glass, bent plate glass, air-cooled tempered glass, and chemically tempered glass, and netted glass can also be used. Various glass substrates such as borosilicate glass, low expansion glass, zero expansion glass, low expansion crystallized glass, and zero expansion crystallized glass can be used.

  Examples of the transparent substrate other than the glass substrate include polyethylene terephthalate resin, polyethylene naphthalate resin, polyethersulfone resin, polycarbonate resin, and polyvinyl chloride resin.

  Although the thickness of a transparent substrate is not specifically limited, It is good also as 3-19 mm generally used as architectural glass. Visible light transmittance and solar radiation transmittance may be affected by the thickness of the substrate, and the transmittance tends to decrease as the substrate becomes thicker. For example, when a 3 mm glass substrate and a 6 mm glass substrate used as the building glass are compared, the 3 mm glass substrate has a higher visible light transmittance of about 0.5 to 1.5%.

  The low emission film of the present invention may include a film, a layer, or the like for the purpose of improving adhesion to the substrate between the transparent substrate and the laminate. In addition, for the purpose of protecting the laminated body, a film or a layer for improving moisture resistance, abrasion resistance, weather resistance, or the like may be included on the laminated body.

The dielectric layer is a layer for adjusting the reflection color tone of the low radiation film, and is an oxide, nitride, or at least one metal selected from the group consisting of Zn, Sn, Al, Ti, Si, and In, or A transparent thin film of oxynitride is preferably used. For the purpose of improving the adhesion between the transparent substrate and the metal layer, improving the chemical durability of the low-emission film, etc. in addition to adjusting the reflection color tone, the dielectric layer is made of ZnO, SnO ₂ , ZnSnO ₃ , Si ₃ N ₄ and TiO ₂ are preferably used. Each of ZnO, SnO ₂ , ZnSnO ₃ and TiO ₂ may be an oxide film or an alloy oxide film containing an arbitrary third component. Si ₃ N ₄ may be a nitride film or an alloy nitride film containing an optional third component.

  The first dielectric layer improves the adhesion between the transparent substrate and the first metal layer and interacts with the second dielectric layer and the third dielectric layer to adjust the reflection color tone and the solar transmittance. The optical film thickness is 60 to 110 nm. If it is less than 60 nm, the visible light reflectivity of the transparent substrate surface tends to be high, and if it exceeds 110 nm, the reflected color tone of the transparent substrate surface tends to be reddish or out of the target color tone range. There is. The lower limit is preferably 70 nm or more, more preferably 75 nm or more. Further, the upper limit is preferably 100 nm or less, more preferably 90 nm or less.

  The second dielectric layer is a layer that greatly affects the reflection color tone and solar transmittance, and has an optical film thickness of 190 to 250 nm. If it is less than 190 nm, the reflection color tone of the transparent substrate surface is not colorless to blue, or tends to be reddish, and if it exceeds 250 nm, the visible light reflectance of the transparent substrate surface increases. The lower limit is preferably 200 nm or more, and more preferably 205 nm or more. Further, the upper limit is preferably 240 nm or less, more preferably 230 nm or less.

  The third dielectric layer is a layer that interacts with the first dielectric layer and the second dielectric layer to adjust reflection color tone and solar transmittance, and has an optical film thickness of 50 to 100 nm. If the thickness is less than 50 nm, the visible light reflectance of the transparent substrate surface becomes high, and if it exceeds 100 nm, the reflection color tone of the transparent substrate surface is out of the target range or tends to be reddish. Moreover, it is good also as 60 nm or more and 75 nm or less preferably.

  Each of the dielectric layers may be a laminated film in which a plurality of dielectric films are laminated as long as the total thickness is within the above-described range. In particular, since the third dielectric layer is the layer closest to the outside air, a plurality of films may be used within a range not impairing the optical characteristics, thereby improving the moisture resistance and durability.

That is, the third dielectric layer is a laminate of two or more dielectric films, and the total optical film thickness of the dielectric films is preferably 50 to 100 nm. At this time, SnO ₂ , TiO ₂ , Si ₃ N ₄ or the like is suitable as the dielectric film used for the uppermost layer because it has excellent moisture resistance.

  In the low radiation film of the present invention, the total thickness of the first, second, and third dielectric layers is in the range of 330 to 430 nm. Since the first, second, and third dielectric layers interact with each other to adjust the reflection color tone and the solar radiation transmittance, the behavior with respect to the change in the total thickness of the dielectric layers becomes complicated. If it is less than 330 nm or exceeds 430 nm, the visible light reflectance of the transparent substrate surface becomes high, or the reflection color tone deviates from the range of colorless to blue. Moreover, it is good also as 340 nm or more and 420 nm or less preferably.

  The metal layer is a layer containing Ag as a main component, and is an Ag film or an Ag alloy film containing Ag as a main component. As the Ag alloy, metals such as palladium, gold, platinum, nickel and copper are used. It may be contained within a range of 5% by mass or less. Here, the “main component” indicates that containing 90% by mass or more of Ag.

  In the present invention, a low emission film having a total physical film thickness of 23.5 to 29 nm of the first metal layer and the second metal layer is used. If it is less than 23.5 nm, the heat shielding property may be insufficient. In general, when the thickness of the metal layer is increased, the heat shielding property is improved. However, the visible light reflectance is increased and the visible light transmittance is decreased accordingly. For this reason, since the color tone of the transmitted color tone and the reflected color tone is more visually recognized, the adjustment of the color tone on the appearance tends to be strict. In the present invention, the solar radiation transmittance does not exceed 33% even if the lower limit of the total thickness of the metal layer is about 22 nm or more and the upper limit is 29 nm or less as shown in Patent Document 1, and a preferable reflection color tone is obtained. Obtained. The total value of the physical film thicknesses of the first metal layer and the second metal layer may preferably have a lower limit of 24 nm or more and an upper limit of less than 29 nm.

  In the present invention, the physical thickness of the first metal layer is 7.0 to 9.5 nm, and the physical thickness of the second metal layer is 16.5 to 19.5 nm. When the physical film thickness of the first metal layer is less than 7 nm, the reflected color tone tends to be red. When it exceeds 9.5 nm, the reflected color tone is tinged with green or the saturation of the reflected color tone is excessively high. It becomes easy to become strong. Moreover, when the physical film thickness of the second metal layer is less than 16.5 nm, the heat shielding property tends to be insufficient. When it exceeds 19.5 nm, the heat shielding property is excellent, but the visible light transmittance is low. In addition, the visible light reflectance tends to be high.

  Moreover, it is preferable that a sacrificial layer is formed on each of the first metal layer and the second metal layer in order to prevent the Ag of the metal layer from deteriorating during the manufacturing process. The sacrificial layer can protect Ag from the reactive gas when the second dielectric layer and the third dielectric layer are formed in an atmosphere in which a reactive gas such as an oxidizing gas or a nitriding gas is present. is there. As the sacrificial layer, Zn, Sn, Ti, Al, NiCr, Cr, Zn alloy, Sn alloy and the like are preferable. In addition, when the second dielectric layer and the third dielectric layer are formed as the sacrificial layer, if the sacrificial layer is made transparent by being oxidized or nitrided by a reactive gas, the visible light transmittance is not impaired more than necessary. Therefore, it is preferable. Since the sacrificial layer only needs to prevent the lower metal layer from being deteriorated or denatured during film formation, the physical film thickness should be 1 nm or more, preferably 2 nm or more. On the other hand, when the thickness exceeds 4 nm, oxidation or nitridation with a reactive gas tends to be insufficient.

2. Second Embodiment A second embodiment of the present invention is a window material that separates the outdoors and indoors, and the window material includes a dielectric layer and a metal layer mainly composed of Ag on a transparent substrate. A low-emission film having a laminate in which a dielectric layer, a first metal layer, a second dielectric layer, a second metal layer, and a third dielectric layer are laminated in this order is formed, and is in contact with the indoor surface on the transparent substrate surface It has a low emission transparent substrate, and has a transparent substrate between the low emission transparent substrate and the outdoors, the laminate is
The optical thickness of the first dielectric layer is 60 to 110 nm,
The physical thickness of the first metal layer is 7.0 to 9.5 nm,
The optical thickness of the second dielectric layer is 190 to 250 nm,
The physical film thickness of the second metal layer is 16.5 to 19.5 nm,
The optical thickness of the third dielectric layer is 50 to 100 nm,
The total physical film thickness of the first and second metal layers is 23.5 to 29 nm,
A total value of optical film thicknesses of the first, third and fifth dielectric layers is within a range of 330 to 430 nm;
The optical characteristics of the low emission transparent substrate are:
The solar transmittance calculated according to JIS R3106 (1998) does not exceed 33%,
The visible light reflectance of the film surface calculated according to JIS R3106 (1998) does not exceed 28%,
The reflected color tone of the outdoor surface in contact with the outdoors exhibits an achromatic color, or the color represented by ((a *) ² + (b *) ² ) ^1/2 in the CIE L * a * b * chromaticity coordinate diagram It is a low emission window material characterized by exhibiting a blue reflection color tone with a degree of 20 or less.

  Regarding the second embodiment, differences from the first embodiment described above will be described below.

  In the second embodiment, the film surface of the low radiation film faces the outdoors. On the other hand, as described above, there is a high possibility of damaging the low-emission film when the low-emission film is brought into contact with the outdoor atmosphere. In this embodiment, a transparent substrate is interposed between the outdoor and the low-emission film. .

  Moreover, this invention is a low radiation | emission transparent substrate whose visible light reflectance of the film surface computed based on JISR3106 (1998) does not exceed 28%. When the visible light reflectance is increased, the appearance quality is liable to be deteriorated due to glare. Therefore, the visible light reflectance is preferably as low as possible.

  In the present invention, the outdoor surface in contact with the outdoors exhibits an achromatic to blue reflection color tone. The embodiment is particularly suitable for obtaining a reflection color tone of an achromatic color or a color in which the achromatic color is slightly bluish. Preferably, the saturation of the reflection color tone of the film surface may be 10 or less.

  For example, when implemented as a double-glazed glass as shown in FIG. 2, the low radiation transparent substrate 1 is disposed on the indoor side, and the low radiation film 2 of the low radiation transparent substrate 1 is in contact with the hollow layer 4. Since the reflected light of the film surface passes through the hollow layer 4 and the transparent substrate 3, the reflected color tone when the film surface is directly measured differs from the reflected color tone actually measured outdoors. When the reflection color tone from the film surface side is in the range of -5 to 5 and b * to -10 to 5 in the CIE L * a * b * chromaticity coordinate diagram, the appearance quality is good. . Preferably, a * may be −5 to 2 and b * may be −7 to 5.

  That is, in the present invention, it is preferable that the transparent substrate, the hollow layer, and the low emission transparent substrate are arranged in this order from the outdoor side, and the film surface of the low emission transparent substrate is in contact with the hollow layer.

  The low emission transparent substrate has a reflection color tone calculated on the basis of JIS Z8729 (2004), and a * ≧ b * and a * are − in the CIE L * a * b * chromaticity coordinate diagram. In the first embodiment, 10 to 0 and b * are in the range of −20 to 0, and the reflection color tone of the film surface is in the range of a * of −5 to 5 and b * of −10 to 5 This is preferable because it can be used in both the form and the second embodiment.

3. Low-emission transparent substrate production method The low-emission transparent substrate of the present invention is preferably formed by sputtering, electron beam vapor deposition, ion plating, etc., but sputtering is advantageous in that it is easy to ensure productivity and uniformity. The law is suitable.

  The formation of the low radiation film by the sputtering method is performed while the transparent substrate is transported in the apparatus in which the sputtering target as the material of each layer is installed. At this time, a gas used for sputtering is introduced into a vacuum chamber for film formation provided in the apparatus, and a negative potential is applied to the target to generate plasma in the apparatus to perform sputtering. .

  In addition, a method for obtaining a desired film thickness is not particularly limited because it varies depending on the type of the sputtering apparatus, but a method for controlling the film thickness by changing the film formation rate by adjusting the power input to the target or the introduction gas condition, A method of controlling the film thickness by adjusting the substrate conveyance speed is widely used.

When forming the dielectric layer, the target used may be either a ceramic target or a metal target. In any case, the gas conditions to be used are not particularly limited, and the gas type and mixing ratio may be appropriately determined from Ar gas, O ₂ gas, and N ₂ gas according to the target film. Further, as the gas to be introduced into the vacuum chamber, Ar gas, O ₂ gas, may include any third component other than N ₂ gas.

  In the case of forming a metal layer mainly composed of Ag, an Ag target or an Ag alloy target is used as a target to be used. Ar gas is preferably used as the 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.

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

In the present invention, a low emission transparent substrate may be used as a single plate as shown in FIG. 1 (a), but as a multilayer glass as shown in FIG. 1 (b) and FIG. It is preferable to use it because it is possible to protect the low emission film. When used as a multi-layer glass, the surface of the low emission transparent substrate 1 on which the low emission film 2 is formed is opposed to another transparent substrate 3 with a predetermined interval so as to form a hollow layer 4, and the peripheral portion is a spacer 5 or Seal with sealing material 6. The hollow layer 4 is filled with an inert gas such as Ar, He, Ne, Kr, or Xe, dry air, N ₂ or the like, and normally uses dry air, but further improves heat insulation performance and sound insulation performance. Ar gas, Ne gas, or the like may be used for the purpose.

  The spacer 4 has a desiccant inside, and is fixed between at least two glass substrates via a sealing material 6 such as butyl rubber or silicone, and a lightweight aluminum material or resin material is used. A portion surrounded by the spacer 4, the low radiation transparent substrate 1, and the transparent substrate 3 is a hollow layer 4, and the heat insulating property of the multilayer glass is changed depending on the thickness of the hollow layer 4 and the kind of gas to be enclosed. Is possible.

1. Production of Low Emission Film Examples and comparative examples of the present invention are shown below. Table 1 shows the film thicknesses of the dielectric layers and the metal layers of Examples 1 to 7 and Comparative Examples 1 to 12. In both Examples and Comparative Examples, a film was formed on soda lime glass having a thickness of 3 mm using a magnetron sputtering apparatus. Each layer obtained a desired film thickness by adjusting the conveyance speed of the glass substrate. Moreover, the said conveyance speed used the speed | rate calculated for every kind of film | membrane previously forming the single layer film | membrane. In any of the examples and comparative examples, a sacrificial layer is formed on the first metal layer and the second metal layer (not shown in Table 1), the substrate and the film are not heated, and sputtering is performed during film formation. Except for the case where the substrate temperature rises due to the origin, the substrate and the film were not heated.

Examples 1-7 and Comparative Examples 1-12
First, a glass substrate was held on a base material holder, and a desired target was placed in each vacuum chamber. The target has a magnet disposed on the back side. Next, the inside of the vacuum chamber was evacuated by a vacuum pump.

  Next, a first dielectric layer was formed on the glass substrate. A Zn target to which 2 wt% Al was added (hereinafter also referred to as “ZnAl”) was used as the target, and power of 1000 W was supplied from the DC power source to the ZnAl target through a power cable. At this time, while continuously operating the vacuum pump, oxygen gas was introduced into the vacuum chamber at 60 sccm and the pressure was adjusted to 0.3 Pa. Thus, a ZnAlO film was obtained.

  Next, an Ag film was formed as a first metal layer on the ZnAlO film. The target was an Ag target, and the atmosphere gas in the vacuum chamber was introduced with argon gas at 45 sccm, and the pressure was adjusted to 0.5 Pa. The power supplied from the DC power source was 360 W. As described above, an Ag film was obtained.

  Next, a first sacrificial layer was formed on the Ag film. A ZnAl target in which 4 wt% of Al was added to the target, and the atmosphere gas in the vacuum chamber was introduced with argon gas at 100 sccm, and the pressure was adjusted to 0.7 Pa. The power input from the DC power source was 120W. As described above, a ZnAl film having a physical film thickness of 2 nm was obtained.

  Next, a ZnAlO film was formed as a second dielectric layer on the sacrificial layer. The film forming conditions were the same as those of the first dielectric layer except that the conveyance speed was adjusted to obtain a desired film thickness.

  Next, an Ag film was formed as a second metal layer on the ZnAlO film. The film forming conditions were the same as those of the first metal layer except that the conveyance speed was adjusted to obtain a desired film thickness.

  Next, a ZnAl film was formed as a second sacrificial layer on the Ag film. The ZnAl film was deposited so that the physical film thickness was 2.5 nm, and other deposition conditions were the same as those for the first sacrificial layer.

  Next, a ZnAlO film was formed as a third dielectric layer on the sacrificial layer. The film forming conditions were the same as those of the first dielectric layer except that the conveyance speed was adjusted to obtain a desired film thickness. As described above, a low radiation film was formed on the glass substrate to obtain a low radiation transparent substrate.

Next, a SnO ₂ film was formed as a third dielectric layer on the ZnAlO film. An Sn target was used as the target, and power of 1000 W was supplied from the DC power source to the Sn target through a power cable. At this time, while continuously operating the vacuum pump, oxygen gas was introduced into the vacuum chamber at 60 sccm and the pressure was adjusted to 0.3 Pa. Thus, a SnO ₂ film was obtained.

2. Evaluation of optical characteristics of low emission transparent substrate The optical characteristics of the low emission transparent substrates obtained in the above-mentioned Examples and Comparative Examples were measured using a self-recording spectrophotometer (Hitachi, U-4000). Visible light transmittance, visible light reflectance, and solar radiation transmittance were calculated according to JIS R3106 (1998). Moreover, the reflection color tone of the film | membrane surface of a low radiation | emission transparent substrate and a glass plate surface was computed based on JISZ8729 (2004). The obtained results are shown in Table 2, FIG. 3 and FIG.

  From Table 2, FIG. 3 and FIG. 4, Examples 1 to 7 have a solar transmittance of 26.2 to 28.7%, and a visible light reflectance of 22.0 to 27.4% on the glass surface. When viewed from the glass surface, it was found to be a low radiation transparent substrate with no glare. Further, the visible light reflectance of the film surface was in the range of 21.3% to 26.5%, and it was found that the film was a low radiation transparent substrate that did not cause glare when viewed from the film surface. Moreover, Examples 1-7 had the visible light transmittance | permeability in the range of 55.8-60.6%, and had shown the visible light transmittance | permeability comparable as the conventional high heat-shielding type low radiation glass.

  In Examples 1 to 7, the reflection color tone of the glass surface is blue, a * is in the range of −7.7 to −3.1, and b * is in the range of −19.2 to −8.9. The saturation was in the range of 11.8 to 19.6. Moreover, the reflection color tone of the film surface was in the range of -3.7 to 1.2 and b * was within the range of -8.1 to 3.3, and the reflection color tone of the film surface was close to an achromatic color. .

  In each of Comparative Examples 1 to 10, the reflection color tone of the glass surface was red, yellow, green, or blue with a strong tint, which was not suitable for the present invention. Moreover, the comparative example 11 had high solar radiation transmittance | permeability, and heat insulation did not satisfy | fill a required characteristic. Further, in Comparative Examples 1, 4, 5, 8, and 12, the visible light reflectance of the glass surface exceeded 28%, resulting in glare. Further, in Comparative Examples 4, 5, 8, and 12, the visible light reflectance of the film surface exceeded 28%, and the reflection on the film surface was glaring.

3. Evaluation of optical properties of multilayer glass A multilayer glass is prepared using the low radiation transparent substrate of Example 1 and a 3 mm thick soda lime glass plate, and the reflection color tone of visible light from the outdoor surface side of the multilayer glass. Was measured. The produced multilayer glass was provided with a low radiation transparent substrate on the outdoor side, the hollow layer was 6 mm, and the low radiation film was in contact with the hollow layer. The measurement was performed in the same manner as when the low-emission transparent substrate was measured with a single plate.

  When the low radiation transparent substrate of Example 1 was a double-layer glass, the solar radiation transmittance was 24.5% and the visible light transmittance was 53.8%. The visible light reflection color tone on the outdoor surface side was a-6.1, b * was -12.9, the saturation was 14.3, and the target blue color was exhibited.

  Next, a multi-layer glass was prepared using the low radiation transparent substrate of Example 1 and a 3 mm thick soda lime glass plate, and the reflection color tone of visible light was measured from the outdoor surface side of the multi-layer glass. The produced multilayer glass was provided with a low radiation transparent substrate on the indoor side, the hollow layer was 6 mm, and the low radiation film was in contact with the hollow layer. The measurement was performed in the same manner as when the low-emission transparent substrate was measured with a single plate.

  The solar radiation transmittance of Example 1 was 24.5%, and the visible light transmittance was 53.8%. Further, the visible light reflection color tone on the outdoor surface side was a-1.5, b--3.3, saturation 3.6, and a near-achromatic blue color.

DESCRIPTION OF SYMBOLS 1 Low radiation transparent substrate 2 Low radiation film 3 Transparent substrate 4 Hollow layer 5 Spacer 6 Sealing material

Claims (6)

A window material for separating an outdoor and an indoor, wherein the window material includes a dielectric layer and a metal layer mainly composed of Ag on a transparent substrate, a first dielectric layer, a first metal layer, and a second dielectric. A low radiation film having a laminate in which a layer, a second metal layer, and a third dielectric layer are laminated in this order, and has a low radiation transparent substrate in contact with the outdoors on the transparent substrate surface,
The optical thickness of the first dielectric layer is 60 to 110 nm,
The physical thickness of the first metal layer is 7.0 to 9.5 nm,
The optical thickness of the second dielectric layer is 190 to 250 nm,
The physical film thickness of the second metal layer is 16.5 to 19.5 nm,
The optical thickness of the third dielectric layer is 50 to 100 nm,
The total physical film thickness of the first and second metal layers is 23.5 to 29 nm,
A total value of optical film thicknesses of the first, third and fifth dielectric layers is within a range of 330 to 430 nm;
The optical characteristics of the low emission transparent substrate are:
The solar transmittance calculated according to JIS R3106 (1998) does not exceed 33%,
The visible light reflectance of the transparent substrate surface calculated according to JIS R3106 (1998) does not exceed 28%,
The reflected color tone of the outdoor surface in contact with the outdoors exhibits an achromatic color, or the color represented by ((a *) ² + (b *) ² ) ^1/2 in the CIE L * a * b * chromaticity coordinate diagram A low emission window material characterized by exhibiting a blue reflected color tone having a degree of 20 or less. In the low radiation transparent substrate, the reflection color tone of the transparent substrate surface calculated according to JIS Z8729 (2004) has a * ≧ b * and a * of −10 in the CIE L * a * b * chromaticity coordinate diagram. The low emission window material according to claim 1, wherein ˜0 and b * are within a range of −20 to 0. 3. The low emission transparent substrate, the hollow layer, and the transparent substrate are arranged in this order from the outdoor side, and the transparent substrate surface of the low emission transparent substrate is in contact with the outdoors. Low emission window material. A window material for separating an outdoor and an indoor, wherein the window material includes a dielectric layer and a metal layer mainly composed of Ag on a transparent substrate, a first dielectric layer, a first metal layer, and a second dielectric. A low-emission film having a low-emission film having a laminate formed by sequentially laminating a layer, a second metal layer, and a third dielectric layer, and having a low-emission transparent substrate that is in contact with the interior and the transparent substrate surface; It has a transparent substrate between outdoors and the laminate is
The optical thickness of the first dielectric layer is 60 to 110 nm,
The physical thickness of the first metal layer is 7.0 to 9.5 nm,
The optical thickness of the second dielectric layer is 190 to 250 nm,
The physical film thickness of the second metal layer is 16.5 to 19.5 nm,
The optical thickness of the third dielectric layer is 50 to 100 nm,
The total physical film thickness of the first and second metal layers is 23.5 to 29 nm,
A total value of optical film thicknesses of the first, third and fifth dielectric layers is within a range of 330 to 430 nm;
The optical characteristics of the low emission transparent substrate are:
The solar transmittance calculated according to JIS R3106 (1998) does not exceed 33%,
The visible light reflectance of the film surface calculated according to JIS R3106 (1998) does not exceed 28%,
The reflected color tone of the outdoor surface in contact with the outdoors exhibits an achromatic color, or the color represented by ((a *) ² + (b *) ² ) ^1/2 in the CIE L * a * b * chromaticity coordinate diagram A low emission window material characterized by exhibiting a blue reflected color tone having a degree of 20 or less. The low emissivity transparent base plate is reflective color tone of the film surface was calculated in compliance with JIS Z8729 (2004) are in CIE L * a * b * chromaticity coordinates diagram, a * is -5 to 5 and b * The low emission window material according to claim 4, which is in a range of −10 to 5. The transparent substrate, the hollow layer, and the low emission transparent substrate are arranged in this order from the outdoor side, and the film surface of the low emission transparent substrate is in contact with the hollow layer. The low emission window material described.

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