JP2010195638A - Glass laminate for window - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a glass laminate for a window which achieves reduction in reddish reflection tone including an oblique direction and improvement in the reflectivity of a near-infrared region. <P>SOLUTION: The glass laminate includes: a glass substrate; and a thin film laminated body formed on the glass substrate. The thin film laminated body includes, in order from the glass substrate side, a first layer made of a dielectric substance, a second layer made of a metal containing Ag as an essential component, a third layer made of a dielectric substance, a fourth layer made of a metal containing Ag as an essential component, and a fifth layer made of a dielectric substance. The total of the geometric thickness of the second layer and the fourth layer is 22 to 29 nm, the geometric thickness of the second layer is 0.3 to 0.8 times that of the fourth layer, the total optical thickness of the first, third and fifth layers is 220 to 380 nm, the optical thickness of the third layer is 140 to 200 nm, and the optical thickness of the first layer is 0.4 to 1.5 times that of the fifth layer. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a glass laminate for a window having a glass substrate and a laminated film formed on the glass substrate, and particularly to Low-E (low emission) glass.

  For the purpose of improving heat insulation of window glass such as double-glazed glass, a glass laminate is used on at least one surface of double-glazed glass, and a low-radiation laminated film of the glass laminate is disposed. is there.

  Among the above-mentioned double-glazed glass, in window glass used in areas that do not require indoor heating as in cold districts such as Hokkaido, the temperature rise of the indoor atmosphere due to sunlight is suppressed, and heat inflow from the outdoor to the indoor is blocked It is required to improve the cooling efficiency by performing the above, that is, imparting heat shielding properties to the window glass.

  A glass laminated body for windows in which a low-emissivity laminated film is formed includes a first layer made of a metal oxide, a second layer containing Ag as a main component, and a third layer made of a metal oxide, sequentially on a glass substrate. , A fourth layer composed mainly of Ag and a fifth layer composed of a metal oxide are being used.

  Patent Document 1 discloses that the optical thickness of the first layer is 32 nm to 41 nm, the geometric thickness of the second layer is 6 nm to 9 nm, the optical thickness of the third layer is 113 nm to 145 nm, As a laminated film having a geometric thickness of 8 nm to 12 nm and an optical thickness of the fifth layer of 45 nm to 60 nm, the change in reflection color tone from the glass substrate side is small even when the incident angle is changed, It is a glass laminate for windows with excellent heat insulation performance.

Further, Patent Document 2 reduces the redness of the reflection color tone when the glass laminate is viewed obliquely by setting the thickness of the first layer to 0.45 to 0.9 times the thickness of the third layer. I am letting.
JP 11-34216 A JP 2004-58592 A

  In order to save energy such as improvement of cooling efficiency, the glass laminate for windows is required to have not only low radiation but also further improvement of heat shielding properties. If the thickness of the metal layer containing Ag as a main component is increased, the reflectance in the near-infrared region is increased, and the heat shielding property can be improved. However, simply increasing the thickness of the metal layer will reduce the visible light transmittance of the glass laminate. Accordingly, a first layer made of a dielectric, a second layer made of a metal containing Ag as a main component, a third layer made of a dielectric, and a fourth layer made of a metal containing Ag as a main component are sequentially formed on the glass substrate. And the visible light transmittance is adjusted by using two metal layers like a laminated film in which a fifth layer made of a dielectric is laminated and utilizing the light interference effect.

  The higher the heat shielding property of the laminated film, that is, the reflectance in the near infrared region, the more influence is exerted on the reflectance near 700 nm, which is the boundary region between the visible region and the near infrared region, and the reflection color tone of the glass laminate. Becomes reddish, and the reflection color tone in the oblique direction is particularly reddish. When the laminate is used for a window of a building or a house, it is preferable to avoid a reddish reflection color tone because a gentle appearance color tone is preferred in these applications. In order to respond to social demands, the reflection color tone of the glass laminate is not reddish, and the reflectance in the near infrared region is improved, that is, the total thickness of the metal layer mainly composed of Ag is increased. It can be said that there is a contradictory relationship.

  In consideration of the above, the present invention overcomes the above-mentioned two-way reciprocal relationship, reduces the reddish reflection color tone including the oblique direction, and improves the reflectance in the near-infrared region. The challenge is to provide a body.

  The glass laminate for windows of the present invention comprises a glass substrate and a thin film laminate formed on the glass substrate, and the thin film laminate is a first comprising a dielectric sequentially from the glass substrate side. A second layer made of metal containing Ag as a main component, a third layer made of dielectric, a fourth layer made of metal containing Ag as a main component, and a fifth layer made of dielectric. The sum of the geometric thicknesses of the two layers and the fourth layer is 22 to 29 nm, preferably 24 to 29 nm, and the geometric thickness of the second layer is 0.3 to 0 of the geometric thickness of the fourth layer. 0.8 times, preferably 0.5 to 0.7 times, and the total optical thickness of the first, third, and fifth layers is 220 to 380 nm, preferably 260 to 360 nm, and the optical thickness of the fifth layer. 140 to 200 nm, preferably 160 to 190 nm, and the optical thickness of the first layer is 0.4 to 1.5 of the optical thickness of the fifth layer. In the CIE L * a * b * chromaticity coordinate diagram, the reflection color tone from the glass substrate side is preferably 0.8 to 1.4 times, and the incident angle is in the range of 0 ° to 60 °. * Is less than 3.

  In order to solve the problems of the present invention, the configurations of the second layer and the fourth layer may be important. When the total geometric thickness of the second layer and the fourth layer is less than 22 nm, the solar radiation emits near the infrared region having a large thermal effect, for example, the light wavelength region of 750 to 2000 nm, particularly the visible region. The effect of improving the reflectance in the light wavelength region of 750 to 1000 nm, in which the energy intensity is particularly large, becomes small.

  Looking at the reflectance from the film surface direction, for example, at a light wavelength of 750 nm, when the total geometric thickness is about 20 nm, it is 20 to 25%, whereas when the total is about 25 nm, It can be seen that a large difference of ˜60%, 2-3 times, occurs.

  On the other hand, if it exceeds 29 nm, the visible light transmittance is likely to be lowered, and it becomes difficult to make the visible light transmittance at the glass laminate 70% or more.

  Further, by setting the geometric thickness of the second layer to 0.3 to 0.8 times the geometric thickness of the fourth layer, the reflection color tone from the glass substrate side has an incident angle of 0. In the range of 60 ° to 60 °, a * in the CIE L * a * b * chromaticity coordinate diagram is set to less than 3 to facilitate the reduction. By setting the a * to less than 3, not only the frontal color (incident angle is close to 0 °) but also the oblique direction (incident angle up to 60 ° is considered) in the reflected color tone. ) Can be reduced, and a window glass having a gentle appearance color tone can be provided.

  When the geometric thickness of the second layer is less than 0.3 times the geometric thickness of the fourth layer, the geometric thickness of the fourth layer must be increased, and the glass laminate is visible. In addition to the low light transmittance, the reflected color tone tends to exhibit a reddish color tone even when viewed from the front. If it is more than 0.8 times, the reflected color tone from the oblique direction tends to exhibit a reddish color tone.

  In the present invention, the total optical thickness of the first, third, and fifth layers is preferably 220 to 380 nm, and the optical thickness of the third layer is preferably 140 to 200 nm. When the optical thickness of the third layer is less than 140 nm, the reflected color tone in the front view tends to exhibit a reddish color tone. On the other hand, when it exceeds 200 nm, the visible light transmittance of the glass laminate tends to be low.

  Furthermore, it is preferable that the optical thickness of the first layer is 0.4 to 1.5 times the optical thickness of the fifth layer. When the ratio is less than 0.4 times, the second layer metal layer tends to have low crystallinity and low visible light transmittance. On the other hand, in the case of more than 1.5 times, the reflected color tone tends to exhibit a reddish color tone even in front view.

  The glass laminate of the present invention is not only excellent in low radiation, but also has improved near-infrared reflectivity, so that the use of the laminate for window glass can improve indoor heating and cooling efficiency, Succeeded in energy saving. Further, since the reflection color tone of the glass laminate is not reddish from the front to the diagonal direction, it is possible to meet the social demand that the window glass is preferred to have a gentle appearance color tone.

  The glass laminate for windows of the present invention comprises a glass substrate and a thin film laminate formed on the glass substrate, and the thin film laminate is a first comprising a dielectric sequentially from the glass substrate side. A second layer made of a metal containing Ag as a main component, a third layer made of a dielectric, a fourth layer made of a metal containing Ag as a main component, and a fifth layer made of a dielectric, The thin film stack is preferably formed using a vapor deposition process such as sputtering.

  The glass substrate is not particularly limited, and for example, inorganic transparency such as window glass for buildings, commonly used float glass, or soda lime glass produced by a roll-out method. You can use flat glass. The plate glass can be used for both colorless glass such as clear glass and high transmission glass and green colored glass such as heat ray absorbing glass, and is not particularly limited to the shape of the glass, but visible light. In consideration of the transmittance, it is preferable to use colorless glass such as clear glass and high transmittance glass. In addition to flat glass, bent glass, various glass such as air-cooled tempered glass and chemically tempered glass, netted glass can be used. Furthermore, 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.

  In the laminated body of the present invention, the first, third, and fifth layers made of a dielectric may be layers having the same composition or may be layers having different compositions. In addition, each of the first, third, and fifth layers may be configured by a layer having a single composition as a whole, or may be formed by stacking layers having a plurality of different compositions.

  The first, third, and fifth layers made of a dielectric are zinc oxide, aluminum oxide, silicon oxide, titanium oxide, tantalum oxide, tin oxide, zirconium oxide, zinc-tin alloy oxide, silicon nitride, aluminum nitride, It is preferable to include a layer made of at least one dielectric selected from the group consisting of silicon oxynitride, aluminum oxynitride, titanium oxynitride, zirconium oxynitride, and tin oxynitride.

  The second layer and the fourth layer containing Ag as a main component may be made of Ag or may contain up to 5% by mass of a metal such as Pd, Au, Pt, or Ni. The layer containing Ag as the main component is preferably in contact with the oxide layer containing Zn as the main component of the cationic metal on the glass substrate side.

  An oxide layer containing Zn as the main component of the cation metal tends to improve the crystallinity of the metal layer containing Ag as the main component. The oxide containing Zn as the main component of the cation metal may be zinc oxide, or may contain at least one metal selected from Sn, Al, Ti, Si, Cr, Mg, and Ga. These metals may be contained up to 0.4 times the number of Zn atoms.

  From the viewpoint of improving the crystallinity of the metal layer containing Ag as a main component, an oxide containing Zn as the main component of the cation metal is obtained by an X-ray diffraction method using CuKα rays. It shows a diffraction peak due to the (002) crystal plane of zinc oxide, and the diffraction angle 2θ of the peak is preferably 33.9 ° or less.

  The thin film laminate of the present invention is composed of a first layer made of a dielectric, a second layer made of a metal containing Ag as a main component, a third layer made of a dielectric, and Ag as a main component, sequentially from the glass substrate side. A fourth layer made of metal and a fifth layer made of dielectric are formed. When the third and fifth dielectric layers are formed, the metal layer containing Ag as a main component may be oxidized or nitrided due to the influence of atmospheric conditions during the formation of the dielectric layer. . In order to prevent this, a sacrificial layer made of a thin metal layer, metal oxide layer, or metal nitride layer may be laminated between the second layer and the third layer and between the fourth layer and the fifth layer. .

  As the sacrificial layer, a metal, a metal oxide, or a metal nitride can be used. For example, at least one metal selected from the group consisting of Zn, Ti, Sn, Ta, Nb, Si, Al, and Cr, or the metal Oxides, nitrides, and oxynitrides of the above can be used, and those that are transparent with the sacrificial layer stacked, or those that are oxidized or nitrided when the third and fifth layers are formed and become transparent In particular, an alloy of zinc and aluminum, aluminum, or zinc oxide doped with aluminum oxide is preferable. The geometric thickness as the sacrificial layer is preferably about 1 to 7 nm, more preferably about 2 to 6 nm.

  In the glass laminate of the present invention, there is a case where a metal remains in the sacrificial layer. However, unlike a metal mainly composed of Ag, the metal contributes little to improving near infrared reflectance. Although not included in the geometric thicknesses of the second layer and the fourth layer, when it is changed to a dielectric or originally a dielectric, it acts as an optical interference film. It is included in the optical thickness of the five layers.

  Moreover, it is preferable that the glass laminated body of this invention is made to oppose another glass base material, and a peripheral part is sealed with a spacer, an adhesive, etc. to make a multilayer glass. At this time, it is preferable that the laminated film is directed to the internal space formed by the facing. This internal space is occupied by an inert gas such as Ar, He, Kr, and Xe, dry air, nitrogen, and the like. When forming a window using this multilayer glass, it is preferable to arrange | position a glass laminated body on the outdoor side from a viewpoint of making heat-shielding property favorable.

1. Preparation of Sample A laminated film was formed by a DC magnetron sputtering method on a glass substrate made of soda lime silicate glass (clear glass) by a float method having a plate thickness of 5.8 mm. A zinc oxide layer formed from a Zn target is formed on the first layer and the third layer, an Ag layer formed from an Ag target is formed on the second layer and the fourth layer, and an Sn target is formed on the fifth layer. In each example, the geometric thickness of the metal layer and the optical thickness of the dielectric layer were adjusted. The film configuration of each example is as shown in Table 1.

Further, before forming the third zinc oxide layer and before forming the fifth tin oxide layer, an Al-doped ZnO (ZnO containing 3% by mass of Al ₂ O ₃ ) target having a geometric thickness of 6 nm is formed. A sacrificial layer made of the aluminum doped zinc oxide film was formed. The film forming conditions for each layer are as shown in Table 2.

2. Evaluation of Sample Optical properties of the obtained sample were measured by measuring light from the glass substrate side using a spectrophotometer (U-4000, manufactured by Hitachi, Ltd.) and compliant with JIS R 3106 (1998). Then, the visible light transmittance, solar transmittance, solar reflectance, vertical emissivity, main wavelength of reflection, and stimulus purity were determined. Further, the reflection color tone on the glass substrate side was measured using an instantaneous multi-photometry system (MCPD-3000 manufactured by Otsuka Electronics Co., Ltd.) and a variable incident angle measurement jig, and CIE L * at incident angles of 0 ° and 60 °. a * in the a * b * chromaticity coordinate diagram was obtained. The results are shown in Table 3. As a representative example of the reflectance spectrum, FIG. 1 shows the reflectance spectra of Example 1 and Comparative Example 1 (measurement light is measured from the glass substrate side). The glass laminate obtained in the present invention was excellent in various indices as shown in Table 3 and FIG.

  Each glass laminate in the comparative example is inferior in any index such as a visible light transmittance of less than 70%, a solar reflectance of less than 30%, or a * exceeding 3. It was.

It is a figure which shows the reflectance spectrum of Example 1 and Comparative Example 1.

Claims (5)

A glass laminate for a window comprising a glass substrate and a thin film laminate formed on the glass substrate, wherein the thin film laminate comprises, sequentially from the glass substrate side, a first layer comprising a dielectric, Ag A second layer made of a metal containing as a main component, a third layer made of a dielectric, a fourth layer made of a metal containing Ag as a main component, and a fifth layer made of a dielectric, The total geometric thickness of the fourth layer 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, The sum of the optical thicknesses of the three and five layers is 220 to 380 nm, the optical thickness of the third layer is 140 to 200 nm, and the optical thickness of the first layer is 0.4 to the optical thickness of the fifth layer. 1.5 times
Glass for windows characterized in that the reflection color tone from the glass substrate side has an incident angle in the range of 0 ° to 60 °, and a * in the CIE L * a * b * chromaticity coordinate diagram is less than 3. Laminated body. The first, third, and fifth layers made of a dielectric are zinc oxide, aluminum oxide, silicon oxide, titanium oxide, tantalum oxide, tin oxide, zirconium oxide, zinc-tin alloy oxide, silicon nitride, aluminum nitride, and oxynitriding The glass laminate for a window according to claim 1, comprising a layer made of at least one dielectric selected from the group consisting of silicon, aluminum oxynitride, titanium oxynitride, zirconium oxynitride, and tin oxynitride. 3. The window according to claim 1, wherein the second layer and the fourth layer containing Ag as a main component are in contact with an oxide layer containing Zn as a main component of a cationic metal on the glass substrate side. Glass laminates. The oxide containing Zn as the main component of the cation metal shows a diffraction peak due to the (002) crystal plane of zinc oxide by an X-ray diffraction method using CuKα rays, and the diffraction angle 2θ of the peak is 33. It is 9 degrees or less, The glass laminated body for windows in any one of the Claims 1 thru | or 3 characterized by the above-mentioned. A double glazing having the window glass laminate according to any one of claims 1 to 4.