Heat treatable coated glass pane

0001The present invention relates to a method for producing a heat treatable coated glass plate having a low emissivity (low-e) and / or a solar controlled coating. The present invention also relates to a coated glass plate produced by this method.

0002Heat-treated glass plates that are reinforced and / or bent to provide safety properties are required for a number of application areas, such as glass windows in buildings or motor vehicles. In order to heat-strengthen and / or bend the glass plates, the glass plates are processed by heat treatment at or above the softening point of the glass used, and then quenching to strengthen them or of the bending means. It is known that it is necessary to bend them with the help. A suitable temperature range for soda lime silica type standard float glass is typically about 580-690 ° C, and the glass plates are numbered in this temperature range prior to the start of the actual strengthening and / or bending process. Maintained for minutes.

0003In the following description and claims, "heat treated", "heat treated", and "heat treatable" refer to the thermal bending and / or strengthening steps as described above, as well as other thermal steps. During the process, the coated glass plate reaches a temperature in the range of about 580 to 690 ° C for a few minutes, for example, up to about 10 minutes. A coated glass plate is considered heat treatable if it survives the heat treatment without noticeable damage, but typical damage caused by this heat treatment is high haze values, pinholes, or spots.

0004"Haze", a parameter commonly referred to when characterizing the heat treatment properties of low-e and / or photovoltaic control coatings, is all that can occur during coating, heat treatment, processing, and / or handling of coated glass plates. It is worth noting that it is often inadequate, as it does not adequately reflect the types of defects in. Some of the known heat-treatable coated glass plates exhibit noticeable and apparently noticeable changes in their optical properties and in particular their reflected color during the heat treatment. It is also appropriate to maintain the thermal properties of the plate during the heat treatment, which may be characterized by maintaining similar sheet resistance and, in some cases, obtaining low levels of sheet resistance.

0005Low-e and / or solar control coatings can be deposited by physical vapor deposition (PVD) steps, such as sputtering. Sputtered low-e and photovoltaic control coating laminates are substrate / base dielectric layer array / (Ag / dielectric layer array)ⁿIt is usually composed of a repeating array of, and it is not necessary for each of the n dielectric layer arrays to have the same thickness or composition. Sputtered coated laminates are more complex in nature due to the need for extra layers in the reinforceable coating and the potential migration to triple silver solar controlled laminates. Therefore, it is now more common in industry that n is equal to 2 or 3. Dielectric layers are generally thicker and slower to deposit than metal layers, so laminates with a significant number of such layers require a large number of cathodes in the coating generation facility.

0006Previously, complex coated laminates required additional coating equipment to obtain a sufficient number and order of sufficient number of cathodes to produce different materials. An extra pumping section must be included in the extension to allow multiple reaction steps to be carried out in sequence. This is a huge expense and a great deal of confusion, as the coating line needs to be shut down for a long period of time to introduce the technology. Each new cathode and pump transport section also requires instrumentation and integration into ancillary power supplies, vacuum pumps, conveyor sections, services and control systems. It is likely to cause the restructuring of downstream logistics and possibly even new civil engineering works or building extensions. Triple silver (n = 3) and even quadruple silver (n = 4) laminates will become more common and these problems are likely to be exacerbated.

0007Prior art has attempted to alleviate these problems. WO 2012052749A1 is to deposit a chemical vapor deposition (CVD) coating on at least one surface of a glass substrate to produce a CVD coated glass and to reflect at least three layers on the surface of the CVD coated glass. The steps for producing a coated glass with spatter deposition of a further coating containing a metal layer are described. The undercoated CVD is preferably a layer of silicon oxide coated from above with a layer of titanium oxide. However, the examples show high levels of haze during heat treatment and high levels of visible light transmission both before and after heat treatment (see page 7, Table 3).

0008WO 00/32530A1 deposits a reflective metal layer by a vacuum deposition method characterized by a) depositing a lower layer on a glass substrate and b) subsequently depositing the lower layer by a thermal decomposition deposition process. The steps for producing a heat-treatable low-e coated glass, including, are described. In the examples, the lower layer of silicon oxycarbide is used, and the visible light transmittance value of 73.2 to 76.3% before the heat treatment (HT) and 74.9 to 78.2% after the HT is shown. The emissivity values of the examples are in the range of 0.060 to 0.076 before HT and 0.065 to 0.072 after HT.

0009It would be desirable to provide a method for the manufacture of coated glass windows that alleviates the above problems and results in glass windows that exhibit improved optical properties compared to prior art steps.

0010According to the first aspect of the present invention, the following steps, in order, a) Steps to provide the glass substrate, b) A step of depositing at least one CVD coating on the surface of a glass substrate by chemical vapor deposition (CVD) using titanium tetraisopropoxide (TTIP) as a precursor. c) Provided is a method of manufacturing a coated glass plate, comprising the step of depositing at least one PVD coating on at least one CVD coating by physical vapor deposition (PVD).

0011Surprisingly, the use of TTIP as a precursor in the methods of the present invention shows improved optical features both before and after heat treatment compared to the plates obtained by the prior art steps described above. It was found to enable the generation of. Moreover, the use of TTIP as a precursor provides a CVD coating that can be easily heat treated, while a titanium oxide-based layer (TiO)._x) Is deposited by PVD, this is a plate with a layer thicker than about 5 nm, which will result in unacceptable haze during HT. Furthermore, the present invention can avoid the need to use a nitride-based layer as the base layer of the lower antireflection layer due to the alkali barrier performance. This is advantageous because the deposition of the nitride layer requires a nitrogen atmosphere and therefore the subsequent deposition of the oxide layer requires a longer coater to ensure gas separation. Moreover, using TTIP as a precursor is TiCl to glass.₄In addition to avoiding the disadvantages associated with the deposition of chlorides such as, it can result in the formation of NaCl, and thus the formation of pinholes, resulting in the formation of pinholes.

0012The method of the present invention also has the advantage of allowing the base coating of the multilayer coating laminate to be made via CVD rather than PVD, which reduces the number of cathodes required. Therefore, the present invention avoids the need for at least most of the cathodes for low dielectric layers used in low-e and / or solar control coatings. This may release the cathode used to deposit other layers at a high rate or to add extra layers to the laminate to increase its complexity.

0013In the following discussion of the invention, unless otherwise stated, disclosure of alternative values for upper or lower limits of the permissible range of parameters, in combination with the indication that one of the values is more preferred than the other, said the alternative. Each intermediate value of the parameter, between a more preferred value and a less favorable value of the thing, is greater than the less favorable value, and more than each intermediate value between the less favorable value and the intermediate value. Should also be interpreted as a statement that implies preference in itself.

0014When a layer is referred to as a particular material (s) "system" in the context of the present invention, this means that the layer is predominantly composed of the corresponding material (s). This means that it typically contains at least about 50 atomic% of the material (s).

0015Preferably, the CVD coating is deposited in the presence of one or more oxygen-containing materials. Preferably, the one or more oxygen-containing substances include one or more of organic oxygen-containing compounds, water, or oxygen gas. Preferably, the organic oxygen-containing compound is an alcohol, or a carbonyl compound such as an ester. Particularly good results were obtained using esters with alkyl groups containing β-hydrogen. Alkyl groups containing β-hydrogen preferably contain 2 to 10 carbon atoms. Such compounds are preferred because larger molecules tend to be less volatile and are therefore less convenient to use in the deposition of CVD coatings. Preferably, the ester is ethyl formate, ethyl acetate, ethyl propionate, isopropyl formate, isopropyl acetate, n-butyl acetate, and / or t-butyl acetate.

0016Preferably, the deposition of the CVD coating involves the preparation of a precursor gas mixture that may contain TTIP and oxygen-containing materials. The precursor gas mixture may further comprise a carrier gas or diluent such as nitrogen, air, and / or helium.

0017Preferably, the CVD coating is at least 5 nm, more preferably at least 10 nm, even more preferably at least 20 nm, most preferably at least 25 nm, but preferably at most 60 nm, more preferably at most 50 nm, even more preferably at maximum. However, it can have a thickness of 40 nm, most preferably at most 30 nm.

0018Preferably, the CVD coating is titanium oxide (TiO)._x) Includes at least one layer (doped or undoped) of the system. In some embodiments, x can be 1.5-2.0. The titanium oxide-based layer is preferably at least 5 nm, more preferably at least 10 nm, even more preferably at least 20 nm, most preferably at least 25 nm, but preferably at most 60 nm, more preferably at most 50 nm, even more. It can have a thickness of at most 40 nm, most preferably at most 30 nm. This layer acts as a glass-side diffusion barrier, among other uses.

0019Preferably, at least one layer of titanium oxide is deposited using TTIP as a precursor. Preferably, at least one layer of titanium oxide system deposited using TTIP as a precursor is located in direct contact with the PVD coating.

0020The CVD coating may further include at least one layer that is not titanium oxide based. The CVD coating is at least in a system of silicon oxide (eg, silicon carbide, silica nitride or silicon), tin oxide (doped or undoped), zinc oxide (doped or undoped), or a mixture of these materials. It may further include one layer.

0021In some preferred embodiments, the CVD coating comprises at least one layer, each of which is titanium oxide (TiO)._x) System layer.

0022Preferably, the main surface of the CVD coating farthest from the glass substrate is at most 3 nm, more preferably at most 2 nm, even more preferably at most 1 nm, even more preferably at most 0.7 nm, and most preferably at most 0.5 nm. Has a surface arithmetic mean height value (Sa) of. The main surface of the CVD coating can have a Sa of at least 0.3 nm. Sa gives an index of surface roughness. A smoother CVD coating is considered advantageous as it can facilitate the deposition of a smoother PVD coating and the resulting coating will exhibit low absorption and low sheet resistance (Rs).

0023It is particularly advantageous if the CVD coating is deposited during the glass forming process. If the glass substrate comprises a float glass substrate, the CVD coating is conveniently deposited during the float glass deposition process in either the float bath, the slow cooling kiln, or the slow cooling kiln gap. The method of CVD coating is any chemical vapor deposition technique, in particular atmospheric chemical vapor deposition (eg, online CVD performed during the float glass deposition process).

0024The CVD coating is preferably on the glass substrate when the glass substrate has a temperature in the range of 450 ° C to 800 ° C, more preferably when the glass substrate has a temperature in the range of 550 ° C to 700 ° C. Can be deposited. Depositing the CVD coating when the glass substrate is at these preferred temperatures gives the coating a greater crystallinity, which can improve the strengthening capacity (HT resistance).

0025Preferably, the CVD coating is deposited on the glass ribbon during the float glass forming process at substantially atmospheric pressure. Alternatively, the CVD coating can be deposited by low pressure CVD or ultra high vacuum CVD. The CVD coating can be deposited using aerosol-assisted CVD or direct liquid injection CVD. Moreover, the CVD coating can be microwave plasma assisted CVD, plasma facilitated CVD, remote plasma facilitated CVD, atomic layer CVD, combustion CVD (flame thermal decomposition), heat ray CVD, organic metal CVD, rapid thermal CVD, vapor phase epitaxy, or. It can be deposited using photo-initiated CVD. Glass ribbons are usually cut into sheets after CVD coating (and before deposition of other coatings) for convenient transport from storage or float glass production facilities to vacuum deposition facilities.

0026Preferably, the surface of the glass substrate on which the CVD coating is deposited is the gas side surface. Coating glass manufacturers typically prefer deposition of coatings on gas-side surfaces (as opposed to tin-side surfaces of float glass), as deposition on gas-side surfaces can improve coating properties.

0027Preferably, the PVD coating is deposited by sputter deposition. It is particularly preferred that the PVD coating applies magnetron cathodic sputtering in either DC mode, pulse mode, intermediate or radio frequency mode, or any other suitable mode, thereby making the metal or semiconductor target , Reactively or non-reactively sputtered in a suitable sputtering atmosphere. Planar or rotating tubular targets may be used, depending on the material to be sputtered. The coating process keeps any oxygen (or nitrogen) deficiency in any oxide (or nitride) layer of any antireflection layer of the coating low and of the visible light transmittance and color of the coated glass plate during the heat treatment. It is preferably carried out by setting suitable coating conditions so as to achieve high stability. The light transmittance value referred to herein is generally 89% light transmittance T without coating._LSpecified for coated glass plates with 4 mm thick standard float glass plates.

0028Preferably, the PVD coating comprises at least one functional layer of reflective metal based. Preferably, the functional layer is a silver-based functional layer.

0029Preferably, the cladding further includes a lower antireflection layer located between the glass substrate and at least one functional layer. The functional layer closest to the glass substrate can be deposited directly on the CVD coating, i.e., optically, the CVD coating will act as a lower antireflection layer or a first dielectric. Alternatively, the PVD coating may preferably further comprise at least one layer of dielectric material system deposited between the CVD coating and at least one functional layer.

0030Preferably, the PVD coating further comprises an upper antireflection layer located above the functional layer.

0031In some embodiments, the board comprises two or more functional layers. For example, a board can contain two, three, or more functional layers. When the board contains two or more functional layers, each functional layer may be separated from the adjacent functional layer by a central antireflection layer. By providing two or more functional layers, the functional layers can be separated by interposing a dielectric layer (= central antireflection layer).

0032PVD coatings are doped or undoped NiCr, Ti, Zn, Zr, Sn, Nb, ITO, TiO_x, Zn_xSn_yO_z, ZnO, SnO_x, Zn_xAl_xO_z, AlN_x, SiN_x, Si_xAl_yN_z,Or it may further comprise at least one layer of their mixture system. Functional layers are usually deposited between such layers.

0033The lower antireflection layer of the coating containing at least one functional layer is the following layer, With a base layer of titanium oxide, silicon oxide (eg, silicon carbide, silica nitride or silicon), tin oxide (doped or undoped), zinc oxide (doped or undoped), or a mixture of these materials. , Metal oxide-based layers such as Zn and Sn oxides and / or Sn oxides, With metal oxides and / or Si (acid) nitrides and / or Al (acid) nitrides and / or alloy-based separation layers of them, The top layer of the oxide system of Zn and Can include at least one combination of one or more of the above.

0034Preferably, the lower antireflection layer is at least in order from the glass substrate. Base layer of titanium oxide, silicon oxide (eg silicon carbide, silica nitride or silicon oxynitride), tin oxide (doped or undoped), zinc oxide (doped or undoped), or a mixture of these materials. When, Metal oxide-based layers such as Zn and Sn oxides and / or Sn oxides, Includes the uppermost layer of Zn oxide.

0035The lower antireflection layer may be composed of three layers in the order as described above.

0036In some embodiments, the lower antireflection layer is in order from the glass substrate. Base layer of titanium oxide, silicon oxide (eg silicon carbide, silica nitride or silicon oxynitride), tin oxide (doped or undoped), zinc oxide (doped or undoped), or a mixture of these materials. When, Metal oxide-based layers such as Zn and Sn oxides and / or Sn oxides, Metal oxides and / or Si (acid) nitrides and / or Al (acid) nitrides and / or their alloy-based separation layers, Includes the uppermost layer of Zn oxide.

0037Metal oxide-based layers, such as the Zn and Sn oxides and / or Sn oxides of the lower antireflection layer, provide a dense and thermally stable layer and reduce haze after heat treatment. By contributing, it functions to improve stability during heat treatment. Metal oxide-based layers, such as Zn and Sn oxides and / or Sn oxides in the lower antireflection layer, are at least 0.5-10 nm, more preferably 0.5-9 nm, even more preferably 1-8 nm. It can have a thickness of even more preferably 1 to 7 nm, even more preferably 2 to 6 nm, even more preferably 3 to 6 nm, and most preferably 3 to 5 nm. A thickness upper limit of about 8 nm is preferred by the optical interference conditions, which may be necessary to maintain the optical interference boundary conditions for the antireflection functional layer due to the resulting decrease in heat treatment due to the decrease in base layer thickness.

0038Metal oxide-based layers, such as Zn and Sn oxides and / or Sn oxides of the lower antireflection layer, can be located directly on the base layer.

0039Oxide of Zn and Sn in the lower antireflection layer (ZnSnO_x) System layers are preferably about 10 to 90% by weight Zn and 90 to 10% by weight Sn, more preferably about 40 to 60% by weight Zn and about 40% by weight of the total metal content by weight. It contains 40-60% by weight Sn, preferably about 50% by weight Zn and Sn, respectively. In some preferred embodiments, the Zn and Sn oxide-based layers of the lower antireflection layer are at most 18% by weight Sn, more preferably at most 15% by weight Sn, even more preferably at most 10. May contain% by weight Sn. The oxide layer of Zn and Sn is O₂Can be deposited by reactive sputtering of mixed ZnSn targets in the presence of.

0040The separating layers of metal oxides and / or silicon (acid) nitrides and / or aluminum (acid) nitrides and / or alloys thereof are at least 0.5 nm, preferably 0.5-6 nm, more preferably 0.5-. It can have a thickness of 5 nm, even more preferably 0.5-4 nm, most preferably 0.5-3 nm. These preferred thicknesses allow for further improvement in haze during heat treatment. The separation layer provides protection during the deposition process and subsequent heat treatment. The separation layer is either essentially completely oxidized immediately after its deposition, or during the subsequent deposition of the oxide layer it is oxidized to an essentially completely oxidized layer. ..

0041Separation layer is O₂By reactive sputtering of Ti-based targets in the presence of, or by depositing a thin layer of Ti-based targets that will be oxidized later, for example, a slightly quasi-stoichiometric titanium oxide-based ceramic target, such as TiO_1.98It can be deposited as an essentially stoichiometric or slightly quasi-stoichiometric oxide using non-reactive sputtering from the target. In the context of the present invention, "intrinsically stoichiometric oxide" means an oxide that is at least 95% but at most 105% of the stoichiometric amount, while "slightly quasi-stoichiometric." "Stoichiometric oxide" means an oxide that is at least 95% but less than 100% of the stoichiometric amount.

0042When the separation layer is a metal oxide-based layer, the separation layer includes an oxide-based layer of Ti, NiCr, InSn, Zr, Al, and / or Si.

0043The term "Si (acid) nitride" refers to Si nitride (SiN)._x) And Si nitride (SiO)_xN_y), On the other hand, the term "Al (acid) nitride" refers to Al nitride (AlN)._x) And Al Nitride (AlO_xN_y) Includes both. Si nitrides, Si nitrides, Al nitrides, and Al nitride layers are preferably stoichiometric in nature (eg, Si nitride = Si).₃N₄, X = 1.33), but can be quasi-stoichiometric or even superstoichiometric, as long as the heat treatment of the coating is not adversely affected by it. One preferred composition of such a layer is essentially a stoichiometric mixed nitride Si.₉₀Al₁₀N_xIs.

0044Layers of Si (acid) nitrides and / or Al (acid) nitrides and / or their alloys are reactive from Si and / or Al-based targets, respectively, in a sputtering atmosphere containing nitrogen and argon. Can be sputtered into. The oxygen content of the Si (acid) nitride and / or Al (acid) nitride and / or alloy-based layers thereof depends on the controlled content of residual oxygen in the sputtering atmosphere or additional oxygen in the atmosphere. It can be caused. If the oxygen content of the Si (acid) nitride and / or Al (acid) nitride is significantly lower than its nitrogen content, i.e., the atomic ratio O / N in the layer is kept significantly lower than 1. If so, it is generally preferable. Most preferably, Si nitrides and / or Al nitrides are used with minimal oxygen content. This feature can be controlled by ensuring that the index of refraction of the layer does not differ significantly from the index of refraction of the oxygen-free Si nitride and / or Al nitride layer.

0045It is within the scope of the invention to use mixed Si and / or Al targets, or to otherwise add metals or semiconductors to the Si and / or Al components of this layer. Mixing Al with Si targets is well known and well established, but other mixed targets are not excluded. The additional ingredients can typically be present in an amount of up to about 10-15% by weight. Al is typically present in mixed Si targets in an amount of about 10% by weight.

0046In addition to its metal oxides and / or silicon (acid) nitrides and / or aluminum (acid) nitrides and / or alloys thereof, the separation layer contains the following elements, Ti, V, Mn, Co, From at least one of Cu, Zn, Zr, Hf, Al, Nb, Ni, Cr, Mo, Ta, Si, or at least one of these materials used, for example, as a dopant or alloyer. It may further contain one or more other chemical elements selected from alloys based on.

0047The top layer of the zinc oxide system mainly functions as a growth promoting layer for the functional layer to be deposited thereafter. The top layer of the zinc oxide system is optionally mixed with a metal such as Al or Sn in an amount of up to about 10% by weight (% by weight with respect to the target metal content). The typical content of the metal, such as Al or Sn, is about 2% by weight, but Al is actually preferred. ZnO and mixed Zn oxides have proven to be extremely effective as growth-promoting layers that help achieve low sheet resistance at a given thickness of the functional layer that is subsequently deposited. The top layer of the lower antireflection layer is O₂Reactively sputter from a Zn target in the presence of a ceramic target, eg, ZnO: Al, in an oxygen-free or generally less than about 5% by volume, oxygen-containing atmosphere. It is preferable when the system is deposited by sputtering. The top layer of the zinc oxide system can have a thickness of at least 2 nm, preferably 2 to 15 nm, more preferably 4 to 12 nm, even more preferably 5 to 10 nm, even more preferably 5 to 9 nm.

0048The silver-based functional layer (s) can be silver-based, without any additives, as is common in the field of low-e and / or solar controlled coatings. However, the characteristics of the silver-based functional layer (s) required for its (s) function as a highly translucent and low light absorbing infrared reflective layer (s) are not substantially impaired by it. As long as it is possible to modify the characteristics of the silver-based functional layer (s) by adding a dope, an alloy additive, etc., or in some cases, adding an ultrathin metal or metal compound layer, it is possible to modify the characteristics of the silver-based functional layer (s). It is within the scope of application.

0049The thickness of the silver-based functional layer is dominated by its technical purpose. For normal low-e and / or solar controlled coating purposes, the preferred layer thickness of the single silver layer is 5-20 nm, more preferably 5-15 nm, even more preferably 5-12 nm, even more preferably. It is 7 to 11 nm, most preferably 8 to 10 nm. With such a layer thickness, a light transmission of greater than 86% and a vertical emissivity of less than 0.05 after heat treatment can be easily achieved for a single silver coating. Increasing the thickness of the silver-based functional layer may be sufficient, or several separated functional layers may be provided, if better solar control characteristics are to be aimed at.

0050When the plate contains two silver-based functional layers, the silver-based functional layer located farthest from the glass substrate is preferably 5 to 25 nm, more preferably 10 to 21 nm, even more preferably 13 to 19 nm, and even more. It may have a thickness of preferably 14-18 nm, most preferably 15-17 nm.

0051When the plate contains three silver-based functional layers, the two silver-based functional layers located farthest from the glass substrate are each independently, preferably 5 to 25 nm, more preferably 10 to 21 nm, and even more preferably 13. It can have a thickness of ~ 19 nm, even more preferably 14-18 nm, most preferably 15-17 nm.

0052Preferably, the top layer of the Zn oxide system in the lower antireflection layer is in direct contact with the functional layer.

0053The central antireflection layer (s) includes the following layers, Zn oxide and / or Ti oxide-based layers, and NiCr oxide layer and Metal oxide-based layers such as Zn and Sn oxides and / or Sn oxides, Si (acid) nitrides and / or Al (acid) nitrides and / or alloys thereof, and / or oxide-based layers of Al, Si, Ti, and / or Zr, Can include at least one combination of one or more of the above.

0054In some preferred embodiments, each functional layer is separated from the adjacent functional layer by a central antireflection layer. Each central anti-reflective layer is at least In order from the functional layer located closest to the glass substrate outside the functional layer with the central antireflection layer in between. Zn oxide-based barrier layer and Metal oxide-based layers such as Zn and Sn oxides and / or Sn oxides, Si (acid) nitrides and / or Al (acid) nitrides and / or alloys thereof, and / or oxide-based layers of Al, Si, Ti, and / or Zr. Includes the top layer of the oxide system of Zn.

0055In some other preferred embodiments, each functional layer is separated from the adjacent functional layer by a central antireflection layer. Each central anti-reflective layer is at least In order from the functional layer located closest to the glass substrate outside the functional layer with the central antireflection layer in between. NiCr oxide barrier layer and Zn oxide-based barrier layer and Si (acid) nitrides and / or Al (acid) nitrides and / or alloys thereof, and / or oxide-based layers of Al, Si, Ti, and / or Zr, Metal oxide-based layers such as Zn and Sn oxides and / or Sn oxides, Includes the top layer of the oxide system of Zn.

0056The oxide-based layer of NiCr is preferably at least 0.3 nm, more preferably at least 0.4 nm, even more preferably at least 0.5 nm, most preferably at least 0.6 nm, but preferably at most 5 nm, more preferably at maximum. However, it can have a thickness of 2 nm, even more preferably at most 1 nm, and most preferably at most 0.9 nm. These preferred thicknesses allow for further facilitation of deposition and improved optical properties such as haze, while preserving mechanical durability.

0057The Zn oxide and / or Ti oxide-based layers (s) of the central antireflection layer are independently, preferably at least 1 nm, more preferably at least 2 nm, even more preferably at least 3 nm, and most preferably at least. Although it is 3.5 nm, it can have a thickness of at most 10 nm, more preferably at most 7 nm, even more preferably at most 5 nm, and most preferably at most 4 nm. These preferred thicknesses allow for further facilitation of deposition and improved optical properties such as haze, while preserving mechanical durability.

0058Metal oxide-based layers, such as Zn and Sn oxides and / or Sn oxides in the central antireflection layer, are preferably at least 5 nm, more preferably at least 10 nm, even more preferably at least 13 nm, most preferably. Can have a thickness of at least 14 nm, but preferably at most 40 nm, more preferably at most 30 nm, even more preferably at most 25 nm, and most preferably at most 21 nm.

0059The central antireflection layer contains Si (acid) nitrides and / or Al (acid) nitrides and / or alloys thereof, and / or Al, Si, Ti, and / or Zr oxide-based layers. , Preferred at least 5 nm, more preferably at least 15 nm, even more preferably at least 25 nm, most preferably at least 30 nm, but preferably at most 60 nm, more preferably at most 50 nm, even more preferably at most 45 nm, most. Preferably it can have a thickness of up to 40 nm.

0060The upper antireflection layer is the following layer, NiCr oxide layer and With an oxide-based layer of Zn oxide and / or Ti, Si (acid) nitrides and / or Al (acid) nitrides and / or alloys thereof, and / or oxide-based layers of Al, Si, Ti, and / or Zr. Metal oxide-based layers such as Zn and Sn oxides and / or Sn oxides, Can include at least one combination of one or more of the above.

0061In some preferred embodiments, the upper antireflection layer is at least in order from the functional layer located farthest from the glass substrate. Zn oxide-based barrier layer and Si (acid) nitrides and / or Al (acid) nitrides and / or alloys thereof, and / or oxide-based layers of Al, Si, Ti, and / or Zr. Includes a metal oxide-based layer, such as an oxide of Zn and Sn and / or an oxide of Sn.

0062In some other preferred embodiments, the upper antireflection layer is at least in order from the functional layer located farthest from the glass substrate. NiCr oxide barrier layer and Zn oxide-based barrier layer and Si (acid) nitrides and / or Al (acid) nitrides and / or alloys thereof, and / or oxide-based layers of Al, Si, Ti, and / or Zr. Includes a metal oxide-based layer, such as an oxide of Zn and Sn and / or an oxide of Sn.

0063The Zn oxide and / or Ti oxide-based barrier layer of the upper antireflection layer is preferably at least 1 nm, more preferably at least 2 nm, even more preferably at least 3 nm, and most preferably at least 3.5 nm. It can have a thickness of preferably at most 10 nm, more preferably at most 7 nm, even more preferably at most 5 nm, and most preferably at most 4 nm. These preferred thicknesses allow for further facilitation of deposition and improved optical properties such as haze, while preserving mechanical durability.

0064When the barrier layer contains a layer of mixed metal oxide sputtered from the mixed metal oxide target, excellent protection of the functional layer (s) during the deposition process and high optical stability during heat treatment can be achieved. I found that. When the barrier layer is a Zn oxide system, the oxide can be a mixed metal oxide such as ZnO: Al. Good results are especially achieved when the ZnO: Al-based layer is sputtered from a conductive ZnO: Al target. ZnO: Al can be completely oxidized or deposited to be a slight suboxide. Preferably, the ZnO: Al barrier layer is stoichiometric in nature. The use of essentially stoichiometric ZnO: Al barrier layers rather than metallic or less than 95% stoichiometric ZnO: Al barrier layers provides high optical stability of the coating during heat treatment and heat treatment. It is an effective help in keeping the optical correction inside small. In addition, the use of essentially stoichiometric metal oxide-based barrier layers offers advantages in terms of mechanical robustness.

0065When the barrier layer is an oxide system of NiCr, the layer is preferably deposited as a quasi-stoichiometric oxide. This allows the layer to act as an oxygen trap / absorber during the heat treatment.

0066It is preferred that at least a portion of the barrier layer in direct contact with the functional layer be deposited using non-reactive sputtering of the oxide target to avoid damage to the functional layer.

0067Preferably, the barrier layer is deposited by non-reactive sputtering. Preferably, the barrier layer is sputtered from the ceramic target. In the context of the present invention, the term "non-reactive sputtering" refers to oxides in a low oxygen atmosphere (anoxic or up to 5% by volume oxygen) to provide an essentially stoichiometric oxide. Includes target sputtering.

0068Barrier layer is TiO_xIf it is a system, x can be 1.5 ~ 2.0.

0069The upper antireflection layer contains Si (acid) nitride and / or Al (acid) nitride and / or their alloys, and / or Al, Si, Ti, and / or Zr oxide-based layers. , Preferred at least 2 nm, more preferably at least 5 nm, even more preferably at least 10 nm, most preferably at least 15 nm, but preferably at most 40 nm, more preferably at most 35 nm, even more preferably at most 30 nm, most. Preferably it can have a maximum thickness of 25 nm. Such thickness provides a further improvement in terms of mechanical robustness of the cladding. The layers of Si (acid) nitrides and / or Al (acid) nitrides and / or alloys thereof, and / or Al, Si, Ti, and / or Zr oxides are preferably barriers. It is in direct contact with the layer.

0070Si (acid) nitrides and / or Al (acid) nitrides and / or alloys thereof, and / or Al, Si, Ti, and / or Zr oxide-based layers are in some cases. Can form most of the upper antireflection layer and provide stability (better protection during heat treatment) and diffusion barrier properties. The layer is preferably N₂Si, Al or mixed SiAl targets in the containing atmosphere, eg Si₉₀Al₁₀By reactive sputtering of the target, it is deposited as an Al nitride and / or Si nitride layer. The composition of the layers of Al (acid) nitride and / or Si (acid) nitride system is essentially stoichiometric Si.₉₀Al₁₀N_xIs.

0071Metal oxides and / or Sn oxide-based layers, such as the Zn and Sn oxides of the upper antireflection layer, are preferably at least 1 nm, more preferably at least 5 nm, even more preferably at least 7 nm, most preferably. Has a thickness of at least 9 nm, but preferably at most 20 nm, more preferably at most 15 nm, even more preferably at most 13 nm, and most preferably at most 11 nm. Such thickness provides a further improvement in terms of mechanical robustness of the cladding. When the layer is an oxide of Zn and Sn, it is preferably about 10-90% by weight Zn and 90-10% by weight Sn, more preferably about 10% by weight of its total metal content. It contains 40-60% by weight Zn and about 40-60% by weight Sn, preferably about 50% by weight Zn and Sn, respectively. In some preferred embodiments, the oxide-based layer of Zn and Sn in the upper antireflection layer has a maximum of 18% by weight Sn, more preferably a maximum of 15% by weight Sn, and even more preferably a maximum. But it contains 10% by weight Sn. The layer is O₂Can be deposited by reactive sputtering of mixed ZnSn targets in the presence of, contributing to the antireflection properties of the upper antireflection layer.

0072The upper antireflection layer contains Si (acid) nitrides and / or Al (acid) nitrides and / or alloys thereof, and / or Al, Si, Ti, and / or Zr oxide-based layers. , As defined herein, can be in direct contact with the metal oxide-based layer of the upper antireflection layer without any additional dielectric layer intervening.

0073Preferably, the metal oxide-based layer of the upper antireflection layer includes an oxide-based layer of Zn and Sn and / or an oxide-based layer of Sn.

0074The upper antireflection layer may have a total thickness of 20-60 nm, preferably 25-50 nm, more preferably 30-50 nm, even more preferably 35-45 nm.

0075The protective layer may be deposited as the top layer (outermost layer) of the upper antireflection layer to enhance mechanical and / or chemical robustness, such as scratch resistance. The protective layer can be an oxide-based layer of Al, Si, Ti, and / or Zr.

0076In order to reduce the increase in light transmittance during the heat treatment, it is preferable to deposit all the individual layers of the upper, middle and lower antireflection layers in an essentially stoichiometric composition.

0077To further optimize the optical properties of the cladding, the upper and / or lower antireflection layers are generally known for the dielectric layers of low-e and / or solar control coatings, especially Sn, Ti, Selected from one or more of the oxides of Zn, Nb, Ce, Hf, Ta, Zr, Al and / or Si and / or Si and / or Al (acid) nitrides, or combinations thereof. It may include an additional partial layer composed of suitable materials. However, when adding such additional sublayers, it should be ensured that this does not impair the heat treatment properties targeted herein.

0078It is understood that any additional sublayer may include additives that modify its properties and / or facilitate its production, such as a doping agent or a reaction product of a reactive sputtering gas. For oxide-based layers, nitrogen can be added to the sputtering atmosphere to lead to the formation of oxynitrides rather than oxides. For nitride-based layers, oxygen can be added to the sputtering atmosphere to lead to the formation of oxynitrides rather than nitrides.

0079When adding any such additional sublayers in the order of the basic layers of the plate of the present invention, by making appropriate material, structure and thickness selections, for example, high thermal stability is primarily targeted. Care should be taken to ensure that the specified properties are not significantly impaired by it.

0080According to the second aspect of the present invention, there is provided a coated glass plate manufactured by a method according to the first aspect of the present invention.

0081According to the third aspect of the present invention a) With a glass substrate b) At least one coating on the surface of the glass substrate, the coating containing at least one titanium oxide-based crystal layer, and the main surface of at least one crystal layer farthest from the glass substrate is at most 3 nm. With a coating, which has a surface arithmetic mean height value (Sa), c) With the additional coating, which is at least one additional coating on at least one coating, wherein the at least one additional coating comprises at least one functional layer of reflective metal system. Covered glass plates are provided.

0082Surprisingly, these cladding plates were found to exhibit improved optical properties both before and after heat treatment compared to known plates. Furthermore, the present invention avoids the need to use a nitride-based layer as the base layer of the lower antireflection layer. The cladding also has the advantage of allowing the base coating of the multilayer coating laminate to be made via CVD rather than PVD, which reduces the number of cathodes required.

0083Preferably, the at least one coating was deposited using CVD (ie, the coating is a CVD coating). Preferably, at least one layer of titanium oxide system was deposited using TTIP as a precursor.

0084Preferably, the at least one additional coating was deposited using PVD (ie, the additional coating is a PVD coating).

0085Preferably, at least one layer of titanium oxide is located in direct contact with at least one additional coating.

0086Preferably, the main surface of the at least one crystal layer farthest from the glass substrate is at most 2 nm, more preferably at most 1 nm, even more preferably at most 0.7 nm, and most preferably at most 0.5 nm. It has an average height value (Sa). Preferably, the main surface of at least one crystal layer has a Sa of at least 0.1 nm.

0087Preferably, the cladding further includes a lower antireflection layer located between the glass substrate and at least one functional layer. The at least one additional coating may preferably further comprise at least one layer of dielectric material system deposited between the at least one coating on the surface of the glass substrate and the at least one functional layer.

0088Preferably, at least one additional coating further comprises an upper anti-reflective layer located above the functional layer.

0089According to a fourth aspect of the present invention, there is provided a double glazing window incorporating a coated glass plate according to the present invention. For example, the double glazing window can be layered glass or insulating glass.

0090According to a fifth aspect of the invention, chemical vapor deposition (CVD) of at least one CVD coating on the surface of a glass substrate precedes physical vapor deposition (PVD) of at least one PVD coating on the at least one CVD coating. ), The use of titanium tetraisopropoxide (TTIP) as a precursor is provided.

0091It will be appreciated that the optional features applicable to one aspect of the invention can be used in any combination and in any number. Moreover, they can also be used with any combination, any number of other aspects of the invention. This includes, but is not limited to, the dependents of any claim that are used as dependents on any other claims of the application.

0092The reader's attention covers all documents and documents submitted at the same time or prior to this specification and published with this specification, which are incorporated herein by reference. ..

0093All of the features disclosed herein (including any appended claims, abstracts, and drawings) and / or any method or process so disclosed are such. It can be combined in any combination, except for combinations in which at least some of the features and / or steps exclude each other.

0094Each feature disclosed herein, including any of the appended claims, abstracts, and drawings, is by alternative feature that serves the same, equal, or similar purpose, unless otherwise stated. Can be replaced. Therefore, unless otherwise stated, each disclosed feature is merely an example of a set of comprehensive equal or similar features.

0095The present invention will be further described by the following specific embodiments, which are illustrated but not limited.

0096For all examples, the coating was deposited on a 4 mm thick standard float glass plate (10 cm x 10 cm) with a light transmittance of about 88%. Prior to coating, the glass was washed twice with a Benterer (RTM) washer.

0097All layers of Comparative Example 1 were deposited using PVD. TiO for Example 2_xThe base layer was deposited using CVD and the other layers were deposited using PVD. Compared to Comparative Example 3, SiO_xAnd TiO_xThe base layer was deposited using CVD and the other layers were deposited using PVD.

0098For the CVD coating, the glass was heated in a conveyor furnace to simulate the coating reaction conditions of the float glass process. The furnace used in-line rollers to transport the glass substrate through the heating zone prior to CVD. In contrast to Comparative Example 3 where the glass substrate was initially provided with a silica coating, the coating was deposited on float glass by a known CVD process using a monosilane precursor in an oxygen-enriched atmosphere.

0099The titanium oxide coating was deposited by CVD at a substrate temperature of approximately 630 ° C. TTIP or TiCl to deposit titanium oxide₄A precursor gas mixture containing, was generated with ethyl acetate, oxygen, and helium. Helium was included in the precursor mixture as a carrier for the reactants. The precursor mixture was prepared by introducing four gases simultaneously through a manifold system. An in-line static mixer was used to ensure a homogeneous precursor mixture.

0100TTIP or TiCl₄And to prevent the addition reaction of ethyl acetate, the temperature of the precursor mixture was maintained above 150 ° C. The precursor temperature was also maintained in the ethyl acetate pyrolysis temperature range below 510 ° C to 610 ° C to prevent the mixture from pre-reacting. The precursor mixture was introduced into the reactor directly above the moving substrate. The temperature of the precursor column was 120 ° C. The temperature of the reactor surface was 175 ° C. Higher substrate temperatures initiated the thermal decomposition of ethyl acetate, which in turn resulted in the deposition of titanium oxide.

0101The resulting coated glass was cooled in air and the coating was analyzed prior to PVD coating.

0102PVD coatings were deposited using AC and / or DC magnetron sputtering equipment and intermediate frequency sputtering was applied when appropriate.

0103Oxide of Zn and Sn (ZnSnO)_x, Weight ratio Zn: Sn 50: 50) All dielectric layers are Ar / O₂Sputtering was carried out reactively from the zinc-tin target in a sputtering atmosphere.

0104ZnO: Al growth promotion top layer of lower antireflection layer is Ar / O₂Sputtering was performed from an Al-doped Zn target (Al content of about 2% by weight) in a sputtering atmosphere.

0105The functional layer essentially composed of sterling silver (Ag) in all examples adds no oxygen 10^-5Sputtering was performed from a silver target in an Ar sputtering atmosphere with a residual oxygen partial pressure of less than mbar.

0106The barrier layer of Al-doped zinc oxide (ZnO: Al, ZAO) is conductive ZnO in a pure Ar sputtered atmosphere without the addition of oxygen._xSputtering was performed from the: Al target.

0107Mixed Silicon Aluminum Nitride (Si₉₀Al₁₀N_x) Layer contains Ar / N containing only residual oxygen₂Mixed Si in a sputter atmosphere₉₀Al₁₀Sputtering was carried out reactively from the target.<tables num="1"><img id="000002" he="244" wi="123" file="JP2016530202A_D0001.tif" img-format="tif" img-content="drawing" /></tables>

0108Table 1: Haze score, light transmission, sheet resistance, emissivity, and oil friction test scores of some comparative coated glass plates and coated glass plates according to the present invention AD = as deposited, HT = after heat treatment, T_L% = Light transmittance ratio, A% = Absorption ratio, Rs = Sheet resistance, ε = Emissivity, and Sa = Surface arithmetic mean height value. The techniques used to collect the data in Table 1 are shown below. In each of the examples in Table 1, the layers were deposited on the glass plate in the order starting from the first layer shown.

0109Heat treatment test After depositing the coatings of Examples 1-3, T_L, A, Rs, and emissivity were measured and the sample was heat treated at about 650 ° C for about 5 minutes. Then haze, T_L, A, Rs, and emissivity were measured. The results are listed in Table 1 above.

0110Light transmittance% (T) of the coated glass plates of Examples 1 to 3_LThe values stated for%) were obtained from the measurements taken by EN140.

0111A visible haze scoring system was applied to the examples. The quality evaluation system described below may be necessary to successfully discern the visual quality of the coating under bright light conditions, a property that is not completely reflected by the standard haze values measured according to ASTM D1003-61. Do you get it.

0112Specular haze (sometimes called red haze or white haze to describe a particular color cast associated with it) can be thought of as a milky white or finely mottled spot pattern that covers most of the coated glass surface. As the name suggests, its nature appears to be specular, rather than scatterable, primarily, but not completely. This is because the specular haze is strongly apparent when the pattern often has a strong angular component for their behavior, i.e. the illumination and the observer's viewing angle is vertical incident. On the other hand, it may not be obvious if the lighting moves at a very different angle, such as 45 °.

0113The evaluation system considers the more macroscopic effect of visible defects in the coating, which causes local color variability when the coating is damaged or incomplete (Haze Score in Table 1). The macroscopic effect of visible defects in the coating after heat treatment (all examples did not show haze before heat treatment) was subjectively evaluated by viewing the sample in bright light. The rating is a completeness score (deep haze, often visible to the naked eye) with a score of the highest 5 (dark haze, often visible to the naked eye) from 0 (complete, flawless) to 3 (some clearly visible defects and / or spots). Rating) Based on the system, each visual appearance of the coated glass sample after heat treatment is given. A heat-treated coated glass plate with an arbitrary score greater than 3 is considered to have failed the test. It is common to get a non-zero specular haze score, but this is not a problem at low values as long as the haze is evenly and randomly distributed. If you are focused on the pattern or have a fairly high haze area, this is visually disturbing and unacceptable (ie, failing). These local and / or non-uniform patterns of haze can take the form of patches, spots, or stains.

0114A visual assessment uses a 2.5 million candela power beam (torch) and is approximately (for right-angled incidence) in two orthogonal planes (ie, rotating the torch first in a horizontal plane and then in a vertical plane). The angle of incidence was between -90 ° and about + 90 °, and the angle of incidence was directed toward the coated glass plate placed in front of the black box. The black box is large enough to allow several coated glasses to be evaluated at the same time. By directing a light beam through the coated glass plate from the observer, the coated glass plates were observed and their visual quality was evaluated by varying the angle of incidence as described above. The coated glass plates were placed in front of the black box so that their coatings faced the observer.

0115Mechanical robustness test The oil friction test serves to simulate the effects of cutting oil used to cut glass plates with the mechanical robustness of the coating. A coated glass plate that cannot withstand the oil friction test is difficult to process and is not suitable for most practical use. The coated sample was immersed in microscopic oil with a refractive index of 1.515 to 1.517 1.2 * 1.2 cm.²Rubbing using a felt pad with an area of. The sample receives 500 cycles with a 900 g load at a rate of 37 cycles per minute. Oil friction samples are evaluated using an internal evaluation system on a completeness scale from 0 (complete, intact) to 9 (complete delamination of the coated laminate). Scores of 1 or less are considered acceptable.

0116As described below, the coated glass plate of Example 2 not only proved to be heat treatable, as reflected in the low haze score after heat treatment, but also simulated the treatment and handling of the coated glass plate. In the oil friction test, the results were better than those of the covering plate of Comparative Example 1. The results are shown in Table 1.

0117Robustness Data-Surface Arithmetic Mean Height (Sa) Sa values were obtained using an atomic force microscope according to ISO25178.

0118Summary of results Table 1 shows that the plates of Example 2 were all the same as those of Comparative Example 1 sputtered before and after the heat treatment, and were TiO._xTiCl as a precursor in the base layer₄It is shown that the high visible light transmittance is higher than that of Comparative Example 3 using the above (in the case of the heat-treated sample, it is considerably high).

0119Example 2 shows low absorption both before and after the heat treatment, lower absorption than Comparative Example 1 before the heat treatment, and the same absorption after the heat treatment. Moreover, the absorption shown by Example 2 is significantly lower than that of Comparative Example 3 both before and after the heat treatment.

0120After the heat treatment, the haze exhibited by the plate of Example 2 is acceptable, while the plate of Comparative Example 3 exhibits an unacceptably high level of haze.

0121Moreover, as described above, the plate of Example 2 performed better than Comparative Example 3 and even better than Comparative Example 1 in the oil friction test.

0122Table 1 also shows that the plate of Example 2 corresponds to the plate of Comparative Example 1 both before and after the heat treatment, and shows considerably better (lower) sheet resistance and emissivity value than the plate of Comparative Example 3.

0123Base TiO of Example 2_xThe layer is SiN of Comparative Example 1._xCorresponds to that of the sputtered base layer of, and the base TiO of Comparative Example 3_xIt shows a Sa value much lower than that of the layer. As detailed on page 6, paragraph 3 above, a smoother CVD coating can facilitate the deposition of a smoother PVD coating, resulting in a cover plate showing low absorption and low sheet resistance (Rs). Therefore, it is considered to be advantageous. In addition, the plate of Example 2 of the present invention has better sheet resistance (lower) both before and after heat treatment than any of the three examples of WO 2012052749A1 (page 7, see Table 3). And visible light transmittance (higher), as well as good haze.

0124In addition, the plate of Example 2 of the present invention shows better light transmittance both before and after the heat treatment than any of the four examples of WO 00/32530A1 (page 9, see Table 3). Moreover, the emissivity values of the plates of Example 2 of the present invention are similar to those of the four examples of WO 00/32530A1.

0125The present invention is not limited to the details of the embodiments described above. The present invention discloses any novel one, or any novel combination of features disclosed herein, including any accompanying claims, abstracts, and drawings, or as such. It extends to any new one or any new combination of steps in any method or process made.