JP2002529356A - Solar control coatings and coated articles - Google Patents

Abstract

  (57) [Summary] Multilayer coating composites on transparent or glass substrates include alternating layers of coatings having high and low refractive indices, primarily from inorganic coatings, that at least block UV light by a combination of thin film interference and absorption effects. The multilayer coated article has a transparent glass, tinted glass, solar control glass or colored glass substrate that is somewhat transparent in appearance. A first metal-containing inorganic coating layer, mainly an inorganic coating layer, having a degree of transparency in appearance and having a refractive index selected from the group of high and low is on the substrate. Above the first coating layer is a second metal-containing inorganic coating layer, mainly an inorganic coating layer, which is somewhat transparent in appearance and has a refractive index opposite to that of the first coating. Above the second coating layer is a third metal-containing inorganic coating layer, mainly an inorganic coating layer, which is somewhat transparent in appearance and has a refractive index in the range of the refractive index of the first coating. Additional coating layers may be above, below, or in the middle of these first three layers, providing different reflective and / or absorbing properties.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001] This application is a related application of the US application Ser. No. 60 / 107,677, filed Nov. 9, 1998, entitled “Solar Control Coatings and Coated Articles”. Claiming benefits, this application is incorporated herein by reference.

[0002] The present invention relates to a solar control for transparent articles for improving ultraviolet and / or near-infrared reflection and / or for increasing the visible light transmission of coated articles.
solar control) coating.

BACKGROUND OF THE INVENTION Transparent such as glass, certain plastics, and glass and plastic laminates used in such industries for commercial and / or residential construction and reshaping and for the manufacture of automobiles and aircraft. Articles include those specific industrial specific solar
Performance characteristics are required. For example, in the automotive industry, designers incorporate transparency into their designs as windows and windshields that are both functional and attractive. The heat that builds up in the passenger compartment of a car due to exposure to solar energy can be successfully handled by an air conditioning system. Of course, the greater the heat buildup, the greater the demands on such a system. Reducing heat build-up through windows has been a concern of designers. The interest in increasing the complex nature of the interior design within the passenger compartment of a vehicle also results in ultraviolet ("UV") and IR solar energy into such interiors. In addition, another factor to consider is meeting government-regulated visible light transmission requirements for certain transparent-like windshields. Thus, clarity, which provides lower infrared transmission and lower total solar energy transmission, is desirable to reduce heat gain inside the vehicle, but should be somewhat consistent with the windshield transparency color.
Glasses with these properties would be highly desirable not only for automotive applications but also for architectural applications. It would further be desirable if the glass was also compatible with flat glass manufacturing methods for easy manufacturing.

[0004] For example, in some automotive markets, glass clarity with less than 10% UV light transmission and less than 50% total solar energy transmission ("TSET") is required.
Attempts to serve this market include titanium dioxide, TiO ₂ ,
And cesium dioxide, includes a substrate which is not covered to block UV light by CeO _2, is added. These additives substantially increase the cost of the substrate. This product is only effective as a green glass. It is possible to develop an organic coating having additives to absorb UV and near infrared ( "NIR") in order to achieve the specifications targeted without using CeO _2. These organic coatings lack the durability normally obtained with uncoated glass substrates.

[0005] It is an object of the present invention to obtain a coated transparency or glass with a reduced UV transmission, especially below 10%, for certain automotive markets, and at the same time obtain the transparency of a solar control glass if possible To reduce the NIR transmittance by a production method on a more economical scale than the production method.

DISCLOSURE OF THE INVENTION [0006] Multilayer coating composites on transparent (transparent) or glass substrates provide high and low refractive index, mainly inorganic coatings, that block at least UV light by combining thin film interference and absorption effects. Including alternating layers. The amount of UV light transmission is a function of the properties of the substrate and the number of layers. For example,
UV reduction can be obtained with as little as three layers on solar control glass. This is possible with alternating layers of silica and titania to reject ultraviolet light. In such a case, the thickness of the layer is about 30 each for titania and silica.
0 and 550 °.

[0007] Alternatively or additionally, to reject NIR, the multilayer coated composite can have a thickness of about 1041-1725 ° in titania and silica, respectively. The TSET of the coated glass can be reduced if the layer thickness of the multilayer is selected appropriately. For example, 4 on green solar control glass
The layer coating can have a TSET of less than 37%, while at the same time achieving low international standard ("ISO") UV targets. This type of coating, which reduces both UV and NIR light transmission, is ideally suited for other substrates that do not have good solar control properties. The present invention can also include a four-layer multi-layer composite on a transparent or glass substrate. Four layers of titania / silica / titania / silica coating on a green solar control glass about 4.0 mm thick achieve UV transmission of less than 10% of ISO, while visible light transmission of more than 70% To maintain. This coating will also reduce visible light reflection to about 8.0% and total solar energy transmission ("TSET") to less than about 45%. Also, the transparency of such four layers can achieve an ISO UV transmission of less than 10%, while maintaining a visible light transmission of greater than 70% and reducing the total solar energy transmitted to about 36%. Can be reduced. The multilayer coating can also reduce visible light reflection to less than 8%. When used as a windshield, four layers of multi-layer coating on solar control glass can be used at approximately 65 °
Windshield installation (installation) angle. This means
Visible light reflection will be reduced to about 13%.

[0008] Other suitable multilayer coating composites on transparent or glass substrates can have coatings with additional materials such as fluorine- or antimony-doped tin oxide. Coatings with these materials can impart other properties such as electrical conductivity or solar absorption. Antimony-doped (antimony-doped) tin oxide, prepared in an appropriate manner, can absorb green color, thereby allowing PPG Industries, Inc.
The transmitted light of a green glass, such as Solex® or Solargreen® glass, commercially available from. Can be changed from green to gray. The change in the optical properties of the coating with antimony-doped tin oxide due to heat treatment of the coated substrate, such as tempering or annealing, can be achieved by controlling the specific composition and deposition conditions of the antimony-doped tin oxide coating. Is possible.

[0009] Optional additional features for the coated transparency or glass are realized by including additional materials or coatings. For example, any of the multilayer coating composites on the substrate discussed above can include self-cleaning or easy-cleaning properties imparted to the coating by depositing titania in the anatase phase. Self-cleaning properties can still work through the surface silica layer. The transmitted light of the solar control coating can also be modified by replacing some or all of the high refractive index coating layer or titania with a transition metal oxide. In the three-layer coating composite described above,
The fourth coating layer adds options for anti-reflective properties and aesthetics. The thickness of these multilayer coatings can also be controlled to maintain the reflected light within a desired range.

In FIG. 1, Curve A is a plot of the theoretical light reflectance (%) for a titania coating with a refractive index of 2.55 on transparent glass versus wavelength in nanometers (nm) and the visible spectrum. Shows the reflectance at. Here, the light source is white in an air medium and the substrate is a transparent glass at 0.0 ° and a reference wavelength of 380 nm with an ideal detector. Curve B is a reflectance vs. wavelength curve for a three-layer SHLH coating of titania, H (high refractive index), and silica, L (low refractive index) on float glass.

In FIG. 2, curves A and B are plotted on a green glass, both sold as SOLARGREEN®, for the SHLH-coated stack and the SHLHLL-coated stack, respectively.
3 shows a plot of theoretical reflectance versus wavelength. The light source, medium detector and angle were the same as in FIG.

In FIG. 3, curves A and B show a plot of theoretical reflectance versus wavelength for a stack of SLHL coatings on a transparent glass substrate having a design wavelength of 330 nm. With and without absorption in the TiO ₂ coating and without absorption in the SiO ₂ coating. Other conditions are shown in Figure 1.
Was the same as

In FIG. 4, curves A and B represent the S3H3L3H3 coating stack and S3H3L3H3, respectively.
3 shows a plot of theoretical reflectance versus wavelength for H3L3H3LL. The last coating layer of the coating stack in Curve B has a 1/8 (1/8) wavelength visible in NIR
It is SiO ₂ at four (quarter) wavelengths. Other conditions were the same as those in FIG. 1 except that the design wavelength was 350 nm.

In FIG. 5, curves A and B show plots of theoretical reflectance versus wavelength, where curve A is
FIG. 4 is a plot of an S3H3L3H3 coating stack as in FIG.
FIG. 4 is a plot with the fluorine-doped tin oxide replaced as part of the intermediate third layer of the inner silica coating. Other conditions were the same as FIG.

In FIG. 6, curves A and B show plots of theoretical reflectance versus wavelength, where curve A is
5 is a plot of the S3H3L3H3LL coating stack as in FIG.
Is a plot with the substituted fluorine-doped tin oxide as the intermediate third portion of the inner silica coating. Other conditions were the same as FIG.

In FIG. 7, curves A and B show plots of theoretical reflectance versus wavelength, where curve A is
TiO ₂ shows the NIR reflectance peak resulting from the SHLH stacking, where the high refractive index coating layer and the fluorine-doped tin oxide are the low refractive index coating layer. Curve B is SMHMH
With a TCO coating layer added below the SHLH coating stack to have a coating stack. Other conditions are the same as those in FIG. 1 except that the design wavelength is set to 1000 nm.

FIG. 8 shows a plot of theoretical reflectance versus wavelength comparing a coated stack without a color suppression layer to one having a SM / 2HLH stacked structure. The former is curve A, which is also curve A in FIG. 7, and the latter is curve B. Other conditions are the same as those in FIG.

FIG. 9 shows a coating stack without a color suppression layer (curve A and also curve A in FIG. 7).
3) shows a plot of theoretical reflectance vs. wavelength comparing SHGHLH with a graded coating layer (“G”) as a color suppression coating stack (curve B). Other conditions are the same as those in FIG.

FIG. 10 shows a plot of theoretical reflectance vs. wavelength comparing curve A of FIG. 7 as curve A and the coating stack of SGLHLH as curve B. Other conditions are the same as those in FIG.

FIG. 11 shows a plot of theoretical reflectance vs. wavelength comparing curve A of FIG. 7 as curve A and a coating stack of SHMHLH as curve B. Other conditions are the same as those in FIG.

FIG. 12 shows a plot of theoretical reflectance vs. wavelength comparing curve A of FIG. 7 as curve A and a coating stack of SHLMMLMH as curve B. Other conditions are the same as those in FIG.

FIG. 13 shows a plot of theoretical reflectivity versus wavelength comparing curve A of FIG. 7 as curve A and curve B of the SHLMH coating stack. Other conditions are the same as those in FIG.

FIG. 14 shows a plot of solar absorption versus wavelength for various antimony-doped tin oxide coatings. This indicates that as the amount of antimony increases, the electrical conductivity decreases and the coating begins to absorb solar radiation significantly.

FIG. 15 shows a plot of theoretical transmittance (%) vs. wavelength comparing curve A of FIG. 7 as curve A and a coating stack of a single coating of antimony tin oxide as curve B. Other conditions are the same as those in FIG.

FIG. 16 shows the curve A of FIG. 7 as curve A and the theoretical light transmission from antimony-doped and fluorine-doped tin oxide via a coating stack of G and a plot of transmittance versus wavelength as curve B. The rate curves are shown in comparison. Other conditions are the same as those in FIG.

FIG. 17 shows a theoretical light transmission curve from a coating stack similar to that of curve B of FIG. 16, but curve A has a thicker layer of antimony-doped tin oxide and curve B is TiO _2. Having an outer coating layer of Other conditions are the same as those in FIG.

FIG. 18 shows the curve A of FIG. 17 for a coating stack having a graded layer without fluorine-doped tin oxide, a coating stack of antimony-doped tin oxide, and TiO ₂ .
And the theoretical light transmittance curve of the curve B. Other conditions are the same as those in FIG.

FIG. 19 shows a theoretical light transmittance curve, wherein curve A is for a single antimony-doped tin oxide coating on a transparent glass substrate similar to curve B in FIG.
A stack of antimony-doped tin oxide of reduced thickness to 1800 angstroms with an overcoat of titanium dioxide. The latter is
Quarter wavelength optical thickness at 1000 nm. Other conditions are the same as those in FIG.

FIG. 20 shows the theoretical light transmittance with two curves. Curve A is for a five layer coating having the structure SHLHLH where H is TiO ₂ and L is silica. Curve B is for a coating stack of the same structure where the fluorine-doped tin oxide is L. Other conditions are the same as those in FIG.

DETAILED DESCRIPTION OF THE INVENTION The transmittance of light through a transparent substrate can be modified by applying an inorganic coating. Inorganic coatings can absorb light and, through thin film physics, can reject light by reflection as well as absorption. Generally, a thin film means a film (film) thickness of 1 micron or less.

The automotive and building markets often require different levels of light transmission depending on the wavelength of light. For example, in a car, it is important to have a relatively high transmission of visible light so that the driver can simultaneously see out of the car but rejects solar radiation that is not in the visible spectrum. The substrate will ideally function as a bandpass filter that transmits all visible light equally, but rejects the UV and NIR portions of the solar spectrum well. . The occupants will feel more comfortable in cars with this glass.
And the car would have better fuel efficiency because smaller air conditioners could be used.

A compromise is usually made between glass aesthetics, solar performance, and manufacturing constraints. Solar control glasses reflect or absorb rather than transmit a portion of the light spectrum. For example, reflect and / or absorb some portion of the ultraviolet and / or infrared and / or visible spectrum, thereby reducing the transmission of that particular portion of the spectrum.
For example, tinted products are solar control glasses in which the total iron content in the final product can be generally in the range of about 0.5 to about 2% by weight. It is. Usually at least 20%, preferably in the range of 30 to 45% by weight of the total iron content of the final glass is made up of ferrous iron. In general, the balance of iron present in glass as ferrous oxide (FeO) or ferric oxide (Fe ₂ O ₃ ) directly and substantially affects the color and transmission properties of the glass. Effect. Solar control glasses also include those that reduce direct solar thermal transmission (DSHT) and / or reduce ultraviolet radiation transmission while allowing some desired transmission of visible light. Although such solar control glass can be privacy glazings (private glazings), this solar control glass reduces the problems associated with excessive heat on a sunny day and reduces the desired amount of heat. Visible light can be transmitted.
It is also possible that these glasses can maintain a private setting for the interior of the vehicle. The glass used as the substrate in the present invention has a certain degree of visible transmittance, or the glass has at least some degree of transparency so that a person can visually identify the opposite object through the glass. have. This transparency is less with glass privacy glazing. The popularity of the three types of solar control glass has grown because they have as great a solar performance as from aesthetic concerns. They are SOLARGREEN® glass and SOLEXTRA® glass, respectively green and blue. SOLARGREEN glass substrate is a solar control glass commercially available from PPG Industries, Inc. with an LTA level of 71%, 42.9% TSET and a performance ratio of 1.65. The dominant wavelength of this glass substrate is 512 nm and CIEL
The colors described in the AB color system are L ^* = 88.3, a ^* =-8.7, b ^* =
3.5, and C ^* = 9.4. Further, the hue angle of the substrate is 158 °. Although the color of a particular substrate is characterized as "green", this glass has its a ^*
It should be noted that b ^* contains a slightly yellowish tint as evident from the harmony. Manufacturing constraints on visible light transmission and federal regulations have hampered the commercialization of other aesthetic solar control glasses (TSET = 50%). Generally, solar control glass is less than 50% (TSET <50%
) Has a total solar energy transmission. Examples of such glasses are commercially available or Solargreen® glass, Solextra® glass, and US Pat. Nos. 5,830,812, 5,023, all of which are incorporated herein by reference. , 210, 4,873
, 206 is disclosed.

Attention is drawn to the fact that Solargreen® and Solextra® glass minimize the total transmitted solar energy (TSET) rather than targeting specific parts of the spectrum, such as UV light. Have been. Recently, the Japanese automotive market has begun to shift towards the demand for glass that has a UV light transmission of less than 10%, but maintains a level of TSET comparable to Solargreen®. A commercial version of this glass is known as Solarblock® glass, commercially available from PPG Industries Inc. The low UV light transmission is due to the high level of expensive additives, CeO ₂
,caused by. By applying the coatings of the present invention, it is possible to achieve their UV transmission targets and to impart features while at the same time providing a cost advantage compared to an uncoated substrate essentially free of CeO _2. Become.

The various thin film coatings of the present invention that have some degree of transparency have anti-reflective, lower T
SET and / or will provide additional properties, such as self-cleaning properties and different reflection or transmission colors, while reducing the transmission of UV light. This combination of various coatings provides several properties together in one coated glass product that can provide advantageous performance as well as advantageous cost. The thin film structures described below have one to five layers made from several, preferably one to four, materials. This material is selected from different characteristics. To take full advantage of the physics of thin films, materials with different refractive indices (RI) are used. In addition, the material should be physically and chemically durable, yet lead to other properties, such as absorption of light in different parts of the solar spectrum where possible.

In general, a refractive index simply means that a high refractive index is higher than a low refractive index,
The same applies to the opposite low refractive index. Preferably, the high index is greater than 1.9 and the low index is less than 1.6, and the medium index is between 1.6 and 1.9.
The boundaries of these ranges are not strict lines, and RI in extremely adjacent ranges may crossover to some extent in adjacent ranges.

Examples of suitable materials for the high and low refractive index coating layers include various metal oxides, nitrides and
And their alloys and mixtures, but are not limited thereto. High refractive index material
As materials, zinc oxide (refractive index = 1.90), titanium oxide (TiO 2)_Two) (Refractive index
= 2.3-2.7), CeO_Two(Refractive index = 1.95), antimony oxide (Sb)_TwoO _Five ) (Refractive index = 1.71), SnO_Two, ITO (refractive index = 1.95), Y_TwoO_Three(Crown
Folding ratio = 1.87), La_TwoO_Three(Refractive index = 1.95), zirconium oxide (ZrO) _Two ) (Refractive index = 2.05) and tin oxide and indium oxide. this
These alloys and mixtures can also be used. The doped oxide is free in the material
Has a very low refractive index in the near-infrared range due to electrons. Fluorine and / or
Indium-doped tin oxide is higher than antimony-doped tin oxide
Has a high refractive index. Examples of materials for the low refractive index coating layer include silicon dioxide, SiO _Two (About 1.45), Al_TwoO_Three(About 1.65), B_TwoO_Three(About 1.60), silicon
Polymers, magnesium oxide, and cryolite.
Not.

The preferred coatings discussed below consist of four different coatings. The first layer may be a titania or TiO _2. This material has a very high refractive index, absorbs UV light, is chemically inert and durable, and has a photocatalytic effect when deposited in anatase form. The second material is silica or SiO _2. This material is also chemically inert and durable, it has a very low refractive index.

Most of the structures described below can be made of only these two materials, but two additional materials can be used due to their unique properties. The first is fluorine-doped tin oxide. This material is electrically conductive and has a high refractive index in the UV and visible portions of the spectrum and a low refractive index in the NIR portion of the spectrum. This property allows unique features to be designed in various coatings. A fourth material is antimony-doped tin oxide. This material absorbs light throughout the solar spectrum, and more importantly, control of the relative absorption at different wavelengths can be achieved by altering the deposition process. The coating can be tailored to absorb relatively more visible or UV or NIR light. A very unique property of this material is that it can have a very high absorption of green light. By placing this coating on a green glass we can turn it into a gray glass, thus creating a high performance solar control glass with a neutral aesthetic.

By being completely treated with a durable oxide coating, these structures should be suitable for tempered automotive parts.

Other materials can be used with this basic set and they will be considered as required. However, these four materials can be used to produce many different coatings with substantially different optical properties. One on-line float glass process, as is well known to those skilled in the art, can be used to produce all these products simply by choosing which materials to deposit and in what order and at what thickness.

All these basic coatings are generally applied in a manner similar to conductive coatings on windshields as described in US Pat. No. 4,610,771, which is incorporated herein by reference. Applicable. This on-line approach makes it possible to produce these new coatings on solar control glass substrates using similar equipment. Any other method known in the art for depositing any of these coating layers can be utilized, for example, by sputtering at high frequency under vacuum. Other techniques can also be used, such as cathodic sputtering, particularly by CVD plasma from a suitable siliceous precursor or by gas phase pyrolysis at ambient pressure.

This section follows a detailed analysis of the specific coating structure, optical model results, and sensitivity. Without being limited to the present invention, as more functionality is formed in the coating, the theory behind various structures is introduced.

UV blocking coatings are the simplest of the solar control coatings discussed here, and the physics behind them is common with many other designs.

The interaction of light rays on any coated or uncoated substrate must obey the following formula:

A + R + T = 100% Formula 1

The percentage of absorbed light (A) plus the percentage of reflected light (R) plus the percentage of transmitted light (T) must total 100%. If more light is reflected by the coating,
Less light is absorbed and / or transmitted. The function of the UV reflective coating is to reflect as much UV light as necessary to meet the target transmission of less than 10% for the coated glass article. Some UV light will be absorbed by the coating and the glass substrate, but most of the transmission loss is due to the high reflection achieved through proper selection of layer materials and thickness. Some layers may be required depending on the UV absorption properties of the substrate. Specific examples will be discussed below.

The maximum reflection achieved by a single high refractive index layer on a substrate is easily calculated,
And this type of layer is known as a quarter wave layer.
The thickness of the quarter wavelength layer is calculated according to the following equation:

H = lambda / (multiply 4 by n ₁ ) Equation 2

Here, h is the thickness of the layer, lambda is the wavelength at which the maximum reflection occurs (design wavelength), and n ₁ is the refractive index of the coating at the design wavelength.

If the refractive index from the material or the material of the coating is large or high,
The layer is designated as "H", if it has a low refractive index, it is designated as "L", and if it is medium or between, it is designated as "M". Coating stacks can be easily shortened in this term. For example, a quarter-wave medium index material next to the glass, a half-wave (two quarter-wave) high index material next to the glass, and a four-wave material at the top. An anti-reflective coating having a one-wavelength low index material is denoted as SMHHL, where S indicates the substrate. It should be noted that each layer is only a quarter wavelength at the wavelength that reflects maximally in the desired portion of the light spectrum.

The reflection intensity is calculated using Equation 3.

R = [(n ₁ ² −n _{0 ns} ) / (n _{0 ns} + n ₁ ² )] ² Equation 3

Here, R is the reflectance, n _s is the refractive index of the substrate, n ₀ is the refractive index of the incident medium, and n ₁ is the refractive index of the coating. The incident medium is in the environment in which the substrate is present, ie, for air or otherwise a laminated structure. For a titania coating with a refractive index of 2.55 at a wavelength of 380 nanometers (nm) on a transparent substrate with a refractive index of 1.51, the quarter-wave thickness of the titania layer is 372 ° and the reflectivity is 26. .5%. This reflectivity is only from the coated surface. Absorption at the coating is ignored in the next few examples, but will be noted when included.

The reflection in the visible spectrum is shown as curve A in FIG. It can be seen from curve A of FIG. 1 that the maximum reflection occurs at the design wavelength of 380 nm, and the reflection decreases at any other wavelength over the solar spectrum.

The reflection from the first surface of the substrate at normal incidence is given by:

[0056] _{R = [(n 0 -n s} ) / (n 0 + n s)] 2 Formula 4

Here, n ₀ and n _s are the refractive indexes of the incident medium and the substrate, respectively. Applying a quarter-wave layer to the substrate yields a coated substrate having an equivalent refractive index, n _le , given by:

[0058] ^{_{n le = n 1 2 / n}} s formula 5

Then, the new reflectance of the coated substrate is calculated by substituting the new substrate with the new equivalent refractive index instead of the refractive index of the formula 4. This new equation is shown below.

R = [(n ₀ −n _le ) / (n ₀ + n _le )] ² Equation 6

Equation 6 is equivalent to Equation 4 above.

The equivalent refractive index of the substrate and the coating stack, expressed as SH (LH) ^m , can be calculated using the following equation:

[0063] ^{_{n e = (n H 2)}} m + 1 / (n L 2) m n S type 7

The reflectivity of any number of layers can be calculated using Equations 6 and 7, where “m” is the number of HL or LH pairs in the coating stack.

The three-layer SHLH coating of titania, H, and silica, L on float glass,

[0066] _{^{n e = (2.6 2) m}} + 1 /(1.45 2) m 1.51 = 14.1 the equivalent refractive index and R = [(1-14.4) / ( 1 + 14.4 )] ² = 75.6% reflectivity.

The reflectance vs. wavelength curve for this coating is shown as curve B in FIG.

Table 1 shows the transparent and Solex® solar control glass and S
The performance of some exemplary and predicted examples of one, three and five layer coatings on OLARGREEN glass is summarized.

[0069]

[Table 1]

S = substrate H = TiO ₂ , quarter wavelength at 380 nm L = SiO ₂ , quarter wavelength at 380 nm ^{1 The} substrate thickness is 4 m. ^{(2) The} thickness of the substrate is 3.6 mm.

The optical constants versus wavelength of silica and other materials were developed in an art-recognized manner taking into account the composition of the coating composition, the method of arrangement, and the thickness of the coating. The reflectance curve in the figure is So
It was created using TFCalc, a commercial software application for thin film calculations available from ftware Spectra Inc.

UV Reflection with Anti-Reflection A characteristic of the simple SHLH structure described above is its relatively high visible light reflectance. This high reflectivity may limit the usefulness of this approach when applied to solar control glasses with uncoated visible light transmission close to the 65-70% range.
This high reflectivity will reduce visible light transmission below the 70% limit, for example when applied to SOLARGREEN® glass for windshield applications.

This limit can be mitigated by applying a half-wave layer on top of the SHLH stack. The half-wave layer at the design wavelength is a non-existent layer because it is sometimes invisible at the design wavelength. Therefore, at the design wavelength, the SHLHLL substrate and coating stack behaves the same as the stacked SHHLH and does not change the UV rejection performance. In our case with a design wavelength in the UV, the top half wave of silica LL
Is a quarter wavelength in the visible spectrum. This layer then serves as the visible spectrum reflectivity reduction layer. And the design wavelength and / or layer thickness can be optimized for the desired UV reflectance and visible light transmission requirements. The SHLH and SHLHLL coatings are shown in FIG. These coatings have a design wavelength of 330 nm. This design wavelength minimizes ISO UV, while 3.6 mm Solargreen (
TM glass maintains a visible light transmission well above 70%. Curve B is the stack SHLHLL, and curve A is the stack SHLH.

In addition, LH pairs can be added between the top H and LL layers to further reduce the UV light rejection properties of the coating stack. Table 2 shows the visible light reflectivity of this stack on Solargreen® glass at various design wavelengths. As can be seen from this table, the selection of an appropriate design wavelength can have a significant effect on the properties of the resulting coating. These predictions were made using TFCalc software.

[0075]

[Table 2]

In Table 2, the last example is illustrative and the others are predictions.

From FIG. 2, it can be seen that the reflectivity of both coatings is the same at the design wavelength (330 nm) and the reflectivity curves are substantially modified throughout the rest of the spectrum. Since the half wavelength of silica acts as an anti-reflection ("AR") layer,
Maintain or increase visible light transmission, thereby increasing this UV on more substrates
Improve the availability of rejection coatings. If the transmission of light through the coated substrate increases, the substrate can be modified to absorb more solar radiation while simultaneously maintaining its visible light transmission requirements. The glass composition of the solar control glass can be modified to reduce TSET to about 40% and visible light transmission is increased from the average running AR coating.

The examples given above have been performed using optical constants with coatings without absorption coefficients to easily illustrate the effect of interference coatings on the optical properties of glass. But actually,
The coating absorbs some light and therefore has a non-zero absorption coefficient. Some of the above examples will be repeated using coatings with different optical constants to illustrate the effect of absorption on the transmission spectrum of the coating. In practice, those skilled in the art will select the appropriate materials and design structures to best satisfy all the desired properties required for the coated glass.

FIG. 3 shows the transmittance curves for the SLHL stack with and without absorption in the TiO ₂ layer. The SiO ₂ layer has no absorption. Curve B shows the case without absorption, and curve A shows the case with absorption.

The addition of UV and NIR blocking solar controls or a reduction in the TSET of the coated substrate can be achieved by means other than those described above. This section describes several routes to reduce TSET and simultaneously reduce the UV transmission of the coated substrate.

A. HLH The previous example in Table 2 showed how a half wavelength could be added at the design wavelength without performance change. Therefore, the first SHLH stack designed at 350 nm and having a half-wave layer for each layer is S3H3L3H (HHHLLLLHHH).
). This coating behaves equally at the design wavelength of 350 nm,
SHLH stacking occurs at around 1050 nm. Since the refractive index of the coating is smaller at longer wavelengths, the maximum reflectance does not occur exactly at 1050 nm. therefore,
The peak shifts to shorter wavelengths in the near infrared (IR) ("NIR") portion of the spectrum. In this way, we now have a coating that reflects at two design wavelengths. The example uses TiO _{2 for} absorption and SiO ₂ for non-absorption, the coating of which is on 4.0 mm clear glass. The curve is shown as curve A in FIG.

B. The reflection intensity in the HLHL / 2 visible spectrum can be changed by applying a quarter (quarter) wavelength in the visible spectrum. This layer has a 1 / NIR at 1050 nm.
Eight wavelengths, and at 350 nm would be 1.5 wavelengths in the UV. The reflection intensity at the NIR will be slightly reduced as a trade-off to reduce visible light reflectance and high visible light transmission. The curve for this coating is shown as curve B in FIG. The reflectivity at the coating on the clear glass drops from about 17% to about 6%. Curve B has a SiO ₂ top layer and curve A does not.

C. Additional Properties The previous two aspects have been directed to three-layer coatings that reflect light in both the UV and NIR portions of the spectrum. Earlier, it was shown that the light reflection intensity was a function of the number of alternating high and low refractive index layers. More layers mean higher reflectivity. However, as more layers are added to the dual reflectivity coating, the overall thickness becomes an issue. Increasing costs and more coaters are needed to produce coatings in a float line environment.

The UV reflectance intensity can be measured without increasing the total stack thickness or NI
It can be increased without sacrificing R reflectance intensity. This is achieved by replacing the middle third portion of the inner silica layer with fluorine-doped tin oxide. Otherwise, the interlayer is some combination of layers. Fluorine, such as the most transparent conductive oxide - doped SnO ₂ is a UV and visible spectrum has unique properties having a high refractive index, having a low refractive index in NIR. The current coating with UV is S3HLHL3H and NIR with SHLH. The coating is effectively a five-layer coating for UV and visible light, but reduces to a three-layer coating for NIR. The coating and the reflectance at S3H3L3H are shown in FIG. 5, and this coating with a visible quarter-wave silica layer and the S3H3L3HLL are shown in FIG. Curves "B" in these figures
Shows the one with an additional layer of fluorine-doped tin oxide, curve "A" without it.

Transparent Conductive Oxide ("TCO") Transparent conductive oxide is used in HLH stacks to increase near infrared (IR) light reflectivity with high refractive index materials as indicated above. it can. Because they have a low index of refraction in the NIR range, which is believed to result from free electrons in the crystal lattice and their mobility. Therefore, they are combined UV / N
It has utility beyond the examples cited above for IR blocking designs. Curve A in FIG. 7 shows the NIR reflectivity peak resulting from the SHLH stack (where TiO ₂ is the high refractive index layer and fluorine-doped tin oxide is the low refractive index layer).

As can be seen in this FIG. 7, curve A, the stack of coatings will reflect about 58% at a design wavelength of 1 micron. The refractive index in the visible range is still different, which results in interference peaks and reflected colors. This property is considered undesirable and the means of maintaining the reflectance peak while minimizing the reflection can be achieved by either of two methods, namely, coating over or under the stack. The key is to add a layer that will change the visible light reflection properties without significantly weakening the NIR peak. One way to do this is to add a coating that is optionally active in the visible range and optionally inert in the NIR range. Conductive transparent oxide ("T
CO ") are suitable for this purpose. As mentioned above, the refractive index of TCO is
Compared to TiO _2, it is lower in the NIR and moderate in the visible spectrum. When added below the SHLH stack, we obtain in the visible spectrum the stack of substrates, medium index, high index, medium index and high index structures, and in the NIR spectrum SL / 3HLH. . The designation SMHMH for this coating was not used. This is because the layer is not a quarter wavelength optical thickness in the visible range. The L
The / 3 layer is optionally inert, as shown in curve B of FIG. 7 (where the plot of this stack is compared to the stack of curve A). Curve A is a normal line and curve B is a bold line at L / 3 containing the stack. One skilled in the art will recognize that the NIR peak is relatively unchanged while the visible light peak is substantially attenuated. This stack is about 57% TSET
And about 76% visible light transmission. This coating will also have a low emissivity due to the long wavelength reflection of light by the transparent conductive oxide. This reflectivity peak can be increased by an additional pair of LH layers, as described above.

Another means of attenuating reflected color is by adding a medium refractive index coating to both the visible and NIR spectra. The intermediate refractive index layer between the substrate and the first high refractive index layer will disturb the proper sequence of HLH needed to enhance reflection, so that the NIR reflection will be reduced by the intermediate refractive index layer. That would be expected by those skilled in the art. Surprisingly, the reflectivity peak intensity does not diminish, and the peak merely shifts slightly in wavelength. The peak may be restored by adapting another layer to the stack. This result allows for adjustment of the stack color without sacrificing NIR reflectivity performance. FIG. 8 shows the stacking of the coating without the color suppression layer as curve A (this is curve A in FIG. 7) by SM
This is compared with those having a stacked structure of / 2HLH. It can be seen that the visible reflectance peak attenuates, but the NIR peak shifts slightly.

Yet another way to attenuate color is to add a graded index layer below the stack of coatings. This layer generally has a refractive index that increases (or decreases) with increasing film thickness through the film layer. This type of color suppression is well known for suppressing the color of a single layer. (See U.S. Patent Nos. 5,356,718 and 5,599,387, which are incorporated herein by reference.
2.) This type of color suppression has not been considered for use in suppressing the color of a coating stack. And more importantly, the NIR from such a stack
Its effect on reflection remained unexamined. The gradient index coating can suppress color and, in some cases, improve the performance of the HLH stack. The gradient layers used in these examples were such that each layer had a thickness of 10 nm and the refractive index changed from 1.55 at the glass interface to 2.0 at the top of the gradient layer. Here, it is modeled as a 10-layer coating denoted G. The reflectivity curve, again compared to the SHLH stack of curve A in FIG. 7, is shown in FIG. Our stack is now SGHLH. In curve B with a gradient layer, the reflectance peak is slightly reduced and the wavelength is shifted, and the visible light reflectance is substantially attenuated.

The gradient layer creates a higher interface than glass, and is optionally activated by the addition of the first high refractive index layer and another fluorine-doped tin oxide layer in the center of the gradient layer, which increases the reflectivity. Since the peak will increase, the reflectance peak can be further increased. The stack is SGLHLH. The color will still decay, but performance will increase. This stack will be very good when lower emissivity is required. The reflectance spectrum compared to curve A in FIG. 7 is shown below in FIG.

The fluorine-doped tin oxide coating also absorbs some NIR light, making it ideally suited for solar control applications. They contribute to reducing NIR light transmission through both reflection and absorption.

Also, unexpectedly, high / low refractive index pairs, much smaller than quarter-wave optical thickness, can be used to attenuate reflected colors. They also have substantially no effect on NIR reflection.

[0092] Adding a layer on top of the stack will reduce reflections as described above. And this method is again appropriate here. By adding layers above and below the stack of coatings, we can achieve both reflected color and reduced intensity. The stack has a medium refractive index, high, medium, high, and then low (MHM
HL). The resulting stack of coatings is shown in FIG. 11 in comparison to curve A in FIG. Visible light intensity is substantially attenuated and the color is grayish (neutral). There are some shifts in the intensity of the reflectivity peak,
It can be modified by adjusting the thickness of the LH layer.

The combination of SiO ₂ and TCO can be used in combination with a low refractive index layer as described above for a dual NIR / UV rejection coating. Fluorine has an optical thickness which is bound by the quarter-wavelength of the NIR - with doped tin oxide and SiO _2, the substrate, TiO _2, SiO ₂
, Fluorine-doped tin oxide, SiO ₂ , fluorine-doped tin oxide, and a stack with TiO ₂ (SHLMMLMH) are shown in FIG. 12 along with curve A in FIG. 7 for comparison. As can be seen from FIG. 12, the reflectance peak is increased with this multilayer low refractive index quarter wavelength approach. Note also that the visible light reflectance peaks are somewhat weakened.

The new ability to attenuate the visible light reflectance spectrum with this multilayer approach at low index layers can be used for the visible light reflectance spectrum for the reflected color while maintaining the NIR reflectance peak but with reduced reflectance. By way of example, substrates, TiO ₂ , SiO ₂ , SnO ₂ : F
And the TiO ₂ stack (SHLMH) will have no reflection color and will have an increased reflection peak as shown in FIG. Again, the reflectance curve A of FIG. 7 is included for comparison. By including layers that are optionally active in visible light and have a low refractive index in the NIR spectrum, any visible light optical effect desired by the designer can be achieved and is not limited to color suppression alone.

The addition of antimony at the doping level to tin oxide will provide electrical conductivity. As the amount of antimony increases, the electrical conductivity decreases,
The coating begins to absorb solar radiation significantly. FIG. 14 shows the solar absorption of various antimony-doped tin oxide coatings. The chemical vapor deposition ("CVD") that produced these coatings
)) Method parameters are listed in Table 3. Of course, other known deposition methods such as pyrolysis coating techniques and sputter coating techniques such as MSVD magnetron sputter vacuum deposition can also be used. Spray coating was performed as a 5 wt% mixture.

[0096]

[Table 3]

The mixture was of antimony trichloride in monobutyltin trichloride (MBTC), and the mixture was sprayed by hand onto a transparent glass substrate heated to about 1150 ° F. Antimony was used in CVD experiments 1 to 20% by weight based on MBTC
11 was supplied. The coater had a central entrance slot with upstream and downstream discharge slots. The width of the coating zone (coating zone) was 4 inches and the contact length between discharges was 5 inches. Air was used as the carrier gas.

In Table 3, coatings 4 and 8 absorb more NIR light than visible light, which makes them good for solar control when high visible light transmission is required. Coatings 2 and 6 have an absorption peak at about 550 nm. These coatings are
x (registered trademark) glass and Solargreen (registered trademark) glass
Well suited for). Coating 10 absorbs more visible light than NIR light and coating 1
Absorbs a relatively constant amount over the solar spectrum, and coatings 9 and 11 absorb significant UV light.

A significant problem with coatings that may be encountered in the annealed and tempered state is the color fastness or color that does not change when the coated glass is heated. The appearance and performance are preferably the same before and after the heat treatment. Antimony-doped tin oxide coatings studied for this scheme may or may not change upon heating, depending on the deposition parameters. Table 4 lists the properties of the various samples and how certain properties change with heat treatment. H after the sample number indicates the sample after the heat treatment.

[0100]

[Table 4]

[0101]

[Table 5]

[0102]

[Table 6]

The H samples in Table 4 were exposed to 1200 ° F. for about 4 minutes and then cooled to room temperature. Table 5 below shows the optical constants of Sample 8 before the heat treatment. These optical constants are
It was used in other examples below.

[0104]

[Table 7]

The NIR reflector shown above is to help control sunlight transmission through the window. The amount of solar rejection is a function of many layers with large total thickness. Many layers are needed to further reduce the transmission of light through the glass. The application of a coating that selectively or preferentially absorbs NIR sunlight as opposed to visible light will help to produce a good solar control stack. A monolayer of antimony-doped tin oxide having the optical properties listed above and having a thickness of 800 Å has a visible light transmission of about 69% and a TS of 58%.
Will have ET. The transmittance curve is compared with the curve A in FIG. 7 and shown in FIG. The coating has a transmission as high as in visible light, but TSET is comparable. When the visible / TSET ratio does not need to be high, such as for reducing glare, or when the transmittance of light through the window does not need to be low, it is good to add an antimony layer to the stack. The antimony-doped tin oxide layer can be combined with fluorine-doped tin oxide or other TCO to obtain both low emissivity and reduced transmittance. FIG. 16 shows the theoretical light transmission from the gradient layer, antimony-doped tin oxide and fluorine-doped tin oxide coatings. TSET is reduced to 51% and visible light transmission remains at about 69%. TSET and visible light transmission can be changed with this design by changing the thickness of the antimony-doped tin oxide layer or by changing the concentration of antimony in the coating.

[0106] Government regulations are driving the performance of windows. A new performance target in the southern United States is for windows that have a light blocking factor of about 0.45. This is about 37% T
It can be realized by SET. The coating described in FIG. 16 can be varied to achieve this goal by increasing the thickness of the antimony-doped tin oxide layer. The transmittance curve for this coating is shown as curve A in FIG.

This coating has a visible light transmission of about 52% and a TSET of about 37%. A fluorine-doped tin oxide coating as the top layer will give this coating an emissivity of less than about 0.35. The thickness of the gradient layer is 800 Å, and
The doped tin oxide is 1800 Å and the fluorine-doped tin oxide is 1800 Å.

The TSET of this coating is achieved by applying a quarter-wave high refractive index layer, such as TiO ₂ , on top of the graded antimony-doped tin oxide, fluorine-doped tin oxide discussed above. , Can be further reduced. TSET is 32.5
%, But the visible light transmittance only drops to 51%. The transmittance curves of these stacks with and without TiO ₂ are shown in FIG. 17 as curves A and B, respectively, below.

If a low emissivity is required for the coating, a fluorine-doped tin oxide or other suitable transparent conductive oxide leaves a gradient layer, antimony-doped tin oxide and TiO ₂ . Can also be removed. The transmittance curve of this coating is shown in FIG.
At 8, compare with the coating with fluorine-doped tin oxide.

An antimony-doped tin oxide coating having a thickness of 2100 Å on clear glass would have a visible light transmission of 49% and a TSET of about 37%. Antimony - thickness of the doped tin oxide may be 1800 Å additional TiO ₂ layer is an optical thickness of one quarter wavelength at 1000 nm, reducing. TSET remains the same, but visible light transmission increases to 54%. Two curves are shown in FIG. Bold curves antimony with TiO ₂ layer - a doped tin oxide.

The position of the high refractive index layer or TiO ₂ with respect to the gradient color suppression layer and the antimony-doped tin oxide and fluorine-doped tin oxide layers was studied. The gradient layer was first on the glass in all cases. The structure of the stack is shortened as follows. S-substrate, G-800 angstrom thick refractive index gradient color suppression layer, Sn-1600 angstrom thick fluorine-doped tin oxide, T
TiO ₂ layer of i-1100 angstroms in thickness, Sb-1800 angstroms thick antimony - doped tin oxide layer. Table 6 shows the results. The addition of a high refractive index layer or TiO ₂ improves TSET in all cases.

[0112]

[Table 8]

Two different five-layer coatings were made to show what is needed for the absorbing layer to achieve low TSET with minimum coating thickness. Curve A is a five layer coating of structure SHLHLH with TiO ₂ as the high refractive index layer and silica as the low refractive index layer. Curve B is of the same structure with F: SnO ₂ as the low refractive index layer. Its design, including SiO ₂ , has a total thickness of about 6747, preferably 6747 Å, and preferably has a TSET of about 60% and a visible light transmission of preferably about 85%.
The design with the fluorine-doped tin oxide preferably has a total thickness of preferably about 6461 Å, preferably about 50% TSET and preferably about 71.1 Å.
% Visible light transmittance. Obviously, adding additional layers would reduce NIR transmission, but this approach would significantly increase manufacturing costs due to the many thick layers. Additional coating thickness is 2700 Angstroms fluorine - even by adding additional pairs of doped tin oxide and TiO ₂ layer, at the expense of visible light transmittance of 3.5%, TSET is reduced 5% only Will.
It is very clear that the novel antimony-doped tin oxides described here are preferred to achieve the desired TSET with a minimum coating thickness.

A. Colorants Two specific examples are discussed in detail. The first case is a coating to mask the green color of the Solex® glass or Solargreen® glass and turn the glass gray. Here, a thin layer of antimony-doped tin oxide containing coating is applied to the glass or coated glass. As the thickness of the coating increases, the transmitted color will change from green to gray. And if the coating increases sufficiently, the transmitted color will change to magenta. Based on the heat treated coating, the transmitted and reflected colors will vary to some extent.

The reflectance increases as the installation angle of the solar control and antireflection windshield for the windshield increases. Anti-reflection (AR)
The coating has an installation angle of about 65 ° and a reflectivity of 1 for Solargreen® glass.
It will drop from 8% to about 12-13%. These traditional AR coatings are
While not providing any additional solar control properties, the increase in visible light transmission due to the AR properties can be used to darken the substrate and reduce TSET. Alternative approaches to AR can be used to further reduce TSET while providing AR performance comparable to traditional designs. This alternative approach does not require changing the substrate composition to achieve a lower TSET. The UV / NIR coating with the upper quarter wavelength of silica described above is used as the basis for this application (SHLHL / 2 tailored for NIR). As the installation angle increases, the optical thickness of the coating decreases. To compensate for this effect, the physical thickness of the layer can be increased. The reflectivity drops to 13% and the TSET is calculated to be about 37%.

With the application of these solar control coatings, the windshield TSE
A unique opportunity is provided to further reduce T. If AR coating is not required, sun reflections can be placed between the windshield lights. Conceivably, two coatings, one on each light, tailored to reflect different wavelengths can reduce the TSET all below 37% while maintaining the target visible light transmission. AR coatings are available from Sungate (as disclosed in US patents).
It could also be applied to the internal light of a registered trademark windshield. N of this coating
IR reflector properties could further improve the properties of this product while also imparting anti-reflective properties.

Self-cleaning properties When titania is deposited in the anatase phase and exposed to UV light, it becomes self-cleaning. Titania can be used as a high refractive index layer in such a design. This will give the design self-cleaning properties as well as improved solar control properties. These self-cleaning coatings are incorporated herein by reference, September 2, 1998.
It is applicable as disclosed in the Patent Cooperation Treaty (PCT) publication WO 98/41480, issued on the 4th.

The NIR transition metal oxide in a colored coating can be used to change the reflection and transmission colors of glass for automotive applications. The coating provides a wide variety of colors but can improve the TSET of the coated glass. This can be achieved by combining transition metal oxides with the above design to also achieve solar control with a wide variety of colors.

[0119] Transition metal oxides having a high refractive index can be used as the high refractive index layer in these designs. If the color is too intense, exclusively using transition metal oxides,
The transition metal oxide can be used as a single high refractive index layer, or even as part of a high refractive index layer. Alternatively, the colored transition metal oxide can be combined with an uncolored oxide to reduce the color of the coating. Using either one of these techniques, one skilled in the art can also achieve solar control with various colors. One of ordinary skill in the art could even have different coloring materials for the various high refractive index layers, giving the designer even more options for controlling the color of the coated glass.

[Brief description of the drawings]

FIG. 1 shows a plot of theoretical light reflectance versus wavelength for a titania coating on clear glass and a three-layer SHLH coating on float glass.

FIG. 2 shows plots of theoretical reflectance versus wavelength for SHLH coating stacks and SHLHLL coating stacks on green glass.

FIG. 3 shows a plot of theoretical reflectance versus wavelength for a SLHL coating stack on a transparent glass substrate.

FIG. 4 shows a plot of theoretical reflectance versus wavelength for S3H3L3H3 coating stacks and S3H3L3H3LL.

FIG. 5 shows a plot of theoretical reflectance versus wavelength for those with an S3H3L3H3 coating stack and fluorine-doped tin oxide.

FIG. 6 shows a plot of theoretical reflectance versus wavelength for those with an S3H3L3H3LL coating stack and fluorine-doped tin oxide.

FIG. 7 shows a plot of theoretical reflectance versus wavelength for SHLH stacks and TCO coatings.

FIG. 8 shows a plot of theoretical reflectance versus wavelength comparing a coated stack without a color suppression layer to one having an SM / 2HLH stacked structure.

FIG. 9 shows a plot of theoretical reflectance vs. wavelength comparing a coating stack without a color suppression layer to a SGHLH color suppression coating stack with a graded coating layer.

FIG. 10 shows a plot of theoretical reflectance versus wavelength comparing curve A of FIG. 7 as curve A and curve B of the SGLHLH coating stack.

FIG. 11 shows a plot of theoretical reflectance vs. wavelength comparing curve A of FIG. 7 as curve A and the coating stack of SHMHL as curve B.

FIG. 12 shows a plot of theoretical reflectance versus wavelength comparing curve A of FIG. 7 as curve A and curve B of the SHLMMLMH coating stack.

13 shows a plot of theoretical reflectance versus wavelength comparing curve A of FIG. 7 as curve A and curve B of SHLMH coating stack.

FIG. 14 shows a plot of solar absorption versus wavelength for various antimony-doped tin oxide coatings.

FIG. 15 shows a plot of theoretical transmittance (%) vs. wavelength comparing curve A of FIG. 7 as curve A and the coating stack of a single coating of antimony tin oxide as curve B.

FIG. 16 shows theoretical light from a coating stack of G and antimony-doped and fluorine-doped tin oxide via curve A of FIG. 7 as curve A and plot of transmittance versus wavelength as curve B. The transmittance curves are shown for comparison.

FIG. 17 shows a theoretical light transmission curve from a coating stack similar to that of curve B of FIG. 16, but curve A has a thicker antimony-doped tin oxide layer and curve B is TiO. _{It has two} outer coating layers.

FIG. 18 shows the curve A of FIG. 17 for a coating stack having a graded layer without fluorine-doped tin oxide, a coating stack of antimony-doped tin oxide, and TiO ₂ .
And the theoretical light transmittance curve of the curve B.

FIG. 19 shows theoretical light transmittance curves for a single antimony-doped tin oxide coating on a transparent glass substrate and for an antimony-doped tin oxide coating stack with a titanium dioxide overcoat. .

FIG. 20 shows a five-layer coating having the structure of SHLHLH, where H is TiO ₂ and L is silica, and a coating stack of the same structure where the fluorine-doped tin oxide is L. 1 shows the theoretical light transmittance of the sample.

──────────────────────────────────────────────────続 き Continuation of front page (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE ), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SL, SZ, TZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AE, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN , IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, UZ, VN, YU, ZA, ZWF terms (reference) 4G059 AA01 AB11 AC06 AC08 EA02 EA04 EA05 EA18 GA02 GA04 GA12

Claims (37)

[Claims] 1. a) a transparent substrate selected from the group of transparent glass, tinted glass, solar control glass and colored glass; b) transparent in appearance and having a refractive index selected from the group of high and low. A first metal-containing inorganic coating layer, mainly of an inorganic coating layer; c) a second inorganic coating layer, which is transparent in appearance and has a refractive index opposite to that of said first coating. And d) a third metal-containing inorganic coating layer, mainly an inorganic coating layer, which is transparent in appearance and has a refractive index within the range of the refractive index of the first coating. Multilayer coated articles. 2. The coating layer having a high refractive index has a higher refractive index than the low refractive index of another coating layer, and the coating layer having a low refractive index has a high refractive index. The article of claim 1, wherein the article has a lower refractive index than the high refractive index of the coating layer. 3. The coating having a high refractive index has a refractive index greater than about 1.75, and the coating having a low refractive index has a refractive index less than about 1.75. An article according to claim 1. 4. The coating layer having a high refractive index has a refractive index of more than 1.9, and the coating layer having a low refractive index has a refractive index of less than 1.6.
An article according to claim 1. 5. The method according to claim 1, wherein the first coating layer is selected from titania and silica, the second coating layer is silica when the first coating layer is titania, and the first coating layer is silica. The method of claim 1, wherein the time is titania and the third coating layer is the same as the first coating layer. 6. Having an intermediate layer consisting of various combinations of coating layers,
A transparent conductive oxide coating as an intermediate third part in the inner silica coating layer, said transparent conductive oxide having a high refractive index in the UV and visible spectrum but a low refractive index in the NIR and S3HLHL3H in the UV NIR provides a stack of SHLH three-layer coatings, and the coating is effectively a five-layer coating for UV and visible light, but is reduced to a three-layer coating for NIR, Without increasing the total thickness of the coating stack and without sacrificing NIR reflectance intensity,
6. The article of claim 5, which will increase V reflectance intensity. 7. The method of claim 1, wherein the coating layer absorbs more NIR than visible light.
A multilayer coated article according to claim 1. 8. The multilayer coated article of claim 1, wherein the coating layer absorbs equally in the NIR and visible portions of the light spectrum. 9. The method of claim 1, wherein the coating layer absorbs more visible light than NIR.
A multilayer coated article according to claim 1. 10. At least one of said coating layers comprises antimony-doped tin oxide having a dopant concentration and a coating layer thickness to absorb about 500 nanometers of light, whereby a green substrate is provided. The multi-layer coated article according to claim 1, wherein the multi-layer coated article changes a transmission color of the article. 11. The method of claim 1, wherein the coating layer having a high refractive index is from a material having a high refractive index in the UV and visible portions of the light spectrum and a low refractive index in the NIR portion of the spectrum. Articles as described. 12. The article of claim 1, wherein the refractive index is from tin oxide doped with fluorine. 13. The relative absorption at different wavelengths by altering the deposition method to match the coating to absorb relatively more light selected from the group consisting of visible light, UV light and NIR light. An article according to claim 1, comprising a fourth coating layer that absorbs light throughout the solar spectrum for control of the light. 14. The article of claim 13, wherein said fourth coating layer is antimony-doped tin oxide. 15. The SHLHLL stack behaves the same as the SHLH stack and has a UV
2. The at least 1.5 wavelength coating layer, optionally invisible, on top of the SHLH stack so that there is no change in rejection performance.
Articles described in. 16. For the design wavelength in UV, the half-wavelength above silica LL (to
p half wave) is the quarterwave of the visible spectrum, which acts as a visible spectrum reflectivity reducing layer by having a layer thickness for blocking UV and transmitting visible light. An article according to claim 15. 17. The design wavelength is 330 nm, which is defined by ISO UV
The article of claim 1, wherein the glass thickness of 3.6 mm for a green glass retains greater than 70% transmission of visible light while minimizing. 18. The first S designed for a 350 nm half-wave coating in each layer.
Intermediate layering during HLH stacking, S3H3L3H is obtained and refraction of the coating layer so that the coating stack behaves identically at 350 nm design wavelength but near the maximum reflectivity of 1050 nm is a SHLH stack. The article of claim 1, wherein the fraction is smaller at longer wavelengths and the peak shifts to shorter wavelengths in the NIR portion of the spectrum such that the coating stack reflects at the two design wavelengths. 19. The visible spectrum has a quarter wavelength and N at 1050 nm.
2. The article of claim 1 having a coating layer that is 1/8 wavelength in the IR and 1.5 wavelengths in the UV at 350 nm to alter the reflection intensity in the visible spectrum. 20. The article of claim 1 having a transparent, conductive oxide coating on at least one side of the HLH coating stack. 21. The article of claim 20, wherein said transparent conductive oxide is fluorine-doped tin oxide and said high refractive index coating is titanium dioxide. 22. The article of claim 20, comprising at least one LH refractive index coating layer pair to increase the reflectance peak. 23. The article of claim 1, further comprising a coating layer that dampens the reflected color with a coating layer having an intermediate refractive index between the substrate and the high refractive index first coating layer. 24. The article of claim 1, comprising a coating layer that attenuates reflected colors with a coating layer having an intermediate refractive index over the last high refractive index coating layer. 25. The article of claim 1, comprising a graded coating layer of varying refractive index through the thickness of the coating layer with at least one HLH coating stack layer. 26. The article of claim 1, wherein the article is tempered. 27. The article of claim 1 having a dual NIR and UV rejection coating stack with silica and a transparent conductive oxide coating acting as a low refractive index layer. 28. A coating stack on a glass substrate comprising titanium oxide, at least one pair of silica and a transparent conductive oxide coating layer, and titanium dioxide, wherein said pair of silica and the transparent conductive oxide 28. The article of claim 27, wherein the coating with the object has an optical thickness coupled by quarter wavelength NIR. 29. The article of claim 27, wherein said transparent conductive oxide is fluorine-doped tin oxide. 30. The article of claim 27, wherein the coating stack layer is a gradient index layer, antimony-doped tin oxide, and fluorine-doped tin oxide. 31. An SHLHLH structure having TiO ₂ as a high refractive index layer and silica as a low refractive index layer, and having a total thickness of about 6747 Å and a T
A stack of coatings having a SET of about 60% and a visible light transmission of about 85%; and, of the same construction, F: SnO ₂ having a total thickness of about 6461 Å and a TS
The article of claim 1, wherein the article has a low refractive index layer having an ET of about 50% and a visible light transmission of about 71.1%. 32. The glass substrate has a green color and the glass substrate has a thin layer of antimony-doped tin oxide containing a coating having a coating thickness that changes the transmission color from green to magenta. 2. The article according to 1. 33. The high-refractive-index coating layer comprises a high-refractive-index transition metal oxide used as the high-refractive-index layer, and the color intensity is the only high-refractive-index layer in the coating stack. Alternatively, the transition metal oxide used as part of the high-refractive index layer can be reduced, and the transition color oxide can be combined with an uncolored oxide to mute the coating to provide various colors and solar control. The article of claim 1, which achieves both. 34) a) a transparent substrate selected from the group of tinted glass, solar control glass and colored glass; b) a first metal-containing coating layer having a refractive index selected from the group of high and low; c. A) a second metal-containing coating layer having a refractive index opposite to that of the first coating layer; and d) having a refractive index in the range of the refractive index of the first coating layer, A third metal-containing inorganic coating layer of an inorganic coating layer, having an ultraviolet transmittance of less than 10% and a total solar energy transmittance of less than 50%;
On the other hand, a multilayer-coated windshield having a visible light transmittance of more than 70% (
windshield). 35. Increasing the mounting angle of the windshield in the opening of the motor vehicle, reducing the optical thickness of the coating, and increasing the physical thickness of the layer to further reduce the windshield TSET. UV / NIR coating with a quarter wavelength on silica is SHLHL tailored for NIR
35. The article of claim 34 having a / 2 structure. 36. The solar reflective coating is disposed on a different substrate surface to be between a plurality of substrates as lites of a windshield without an anti-reflective coating. 35. The article according to 34. 37. The article of claim 1, wherein the substrate is essentially free of CeO ₂ .