Glass or glass-ceramic pane comprising at least one coating applied to at least one region of at least one side of the glass or glass-ceramic pane and glass-ceramic material for coating such a glass or glass-ceramic pane, composite comprising such a pane and use thereof

Abstract

The present invention relates to a glass-ceramic material for coating a glass or glass-ceramic pane and to the pane coated with the material. The pane has high optical density, a high breaking strength and a high bending strength.

Description

[0001] 1 22 September 2025

[0002] P06253 WO

[0003] Glass or glass-ceramic sheet comprising at least one coating applied to at least one area of ​​at least one side of the glass or glass-ceramic sheet and glass-ceramic material for coating such a glass or glass-ceramic sheet, composite comprising such a sheet and its use

[0004] Description

[0005] Field of invention

[0006] The present invention relates generally to glass or glass-ceramic sheets, in particular to glass or glass-ceramic sheets which have a coating in at least one region of at least one side of the glass or glass-ceramic sheet. The invention further relates, according to a further aspect, to a glass-ceramic material for coating such a glass or glass-ceramic sheet, to a composite comprising such a glass or glass-ceramic sheet, and its use.

[0007] Background of the invention

[0008] Glass panes made of or comprising borosilicate glass, especially those that are at least partially coated, have been known for a long time and are used, for example, as oven viewing windows in oven doors. The advantages of borosilicate glass here are its thermal resistance compared to conventional soda-lime glass, which is why, for example, oven viewing windows for pyrolytic ovens often consist of such borosilicate glass panes.

[0009] However, borosilicate glasses can also be advantageous for other applications, as such glasses offer inherent advantages over conventional soda-lime glasses, for example, in terms of scratch resistance, general mechanical strength, and chemical resistance. Therefore, borosilicate glass panes are increasingly being used in windshields. 2 22 September 2025

[0010] P06253 WO

[0011] It is well known that borosilicate glass, such as that commercially available under the trade name Borofloat®, is used in the exterior glazing of vehicles. This type of glass is particularly well-suited for laminated glazing and is characterized by very high transmission in the visible light range. Furthermore, borosilicate glass offers excellent heat resistance, high chemical resistance, and good mechanical strength.

[0012] Glass-ceramic panels offer several advantages over glass panels: They exhibit high temperature resistance and can withstand large temperature fluctuations without breaking or deforming. Therefore, glass-ceramic panels are used, for example, as cooktops or (fireplace) stove glazing. They are also used in laminated glazing, such as safety glazing for mobile applications, e.g., in vehicles, or static applications, e.g., in architecture.

[0013] Windshields are designed as laminated glass for the safety of vehicle occupants and typically have a coating at the edges. This coating serves two purposes: firstly, to visually conceal adhesives or components such as antennas, and secondly, to protect them from UV radiation. This coating is usually located between the two glass panes of the laminate. The laminate also includes a polymeric layer between the two glass panes, bonding them together. The glass panes, with the coating applied between them in at least one area, particularly at the edges, are placed on top of each other and bent using a thermal forming process.Subsequently, a polymer layer is placed between the two panes, and the curved glass panes are bonded together, resulting in a laminated glass pane (which, within the scope of this disclosure, is also simply referred to as a "laminate"). 3 22 September 2025.

[0014] P06253 WO

[0015] For example, oven windows often have a coating at the edges to limit the view into the interior.

[0016] A number of requirements are therefore placed on glass or glass-ceramic panes and their coatings used in these applications. Since the bending processes for composite production are thermal, the glass panes and the coating applied to them must be able to withstand these temperatures. The glass panes and the coating must be able to bond with the polymer layer in such a way that a stable composite is formed and delamination between the glass and polymer does not occur. Finally, the coating must have sufficient optical density so that, for example, components located in the frame area of ​​windshields are not distractingly visible. This prevents driver distraction and thus increases driving safety. Microcracks or other defects in the coating should also be avoided or at least minimized wherever possible.

[0017] In addition to the temperature resistance of glass and coating or glass-ceramic and coating, the aforementioned compatibility of glass, glass-ceramic or coating with a polymeric material for the formation of a bond, the optical density and the minimization of possible defects, the mechanical strength, characterized for example by the fracture or bending strength, of a coated glass pane also plays a role.

[0018] EP 4166519 Al describes glass panes with coatings containing binders, pigments, and additives, and exhibiting sufficient flexural strength. WO 2020247194 Al describes additives for frits based on the AhTiOs system, but these do not achieve the desired color impressions for the uses described here. 4 22 September 2025

[0019] P06253 WO

[0020] Therefore, there is still a need for improvement regarding the overall required property profile of the coating materials and ultimately also of the coating itself, namely the simultaneous presence of both sufficient fracture and flexural strength as well as sufficiently high optical density and a sufficiently dark color impression.

[0021] Object of the invention

[0022] The object of the present invention is to provide glass and glass-ceramic discs that are coated at least in certain areas, which at least partially reduces the aforementioned weaknesses of the prior art.

[0023] Further aspects of the invention relate to a glass-ceramic material, in particular for the production of a coating of such a glass or glass-ceramic disc, a composite comprising such a glass or glass-ceramic disc, and its use.

[0024] Summary of the invention

[0025] The object of the invention is achieved by the subject matter of the independent claims. Preferred and specific embodiments are found in the dependent claims, the description, and the drawings of this disclosure.

[0026] The invention relates to a glass-ceramic material.

[0027] The glass-ceramic material comprises a glass phase.

[0028] The proportion of the glass phase is 1 wt.% to 50 wt.%.

[0029] In some embodiments, the proportion of the glass phase is in the range of 2 wt.% to 40 wt.%, preferably in the range of 5 wt.% to < 40 wt.%. The proportion of the glass phase can then be, in particular, at least 2 wt.% or at least 5 wt.%. (September 22, 2025)

[0030] P06253 WO

[0031] The proportion of the glass phase can then be, in particular, a maximum of 40% by weight or a maximum of < 40% by weight.

[0032] The glass-ceramic material comprises a crystalline phase.

[0033] The proportion of the crystalline phase is 50 wt.% to 99 wt.%.

[0034] In some embodiments, the proportion of the crystalline phase is in the range of 60 wt.% to 98 wt.%, preferably from > 40 wt.% to 95 wt.%. The proportion of the crystalline phase can then, in particular, be at least 60 wt.%, or at least > 60 wt.%. The proportion of the crystalline phase can then, in particular, be at most 98 wt.% or at most 95 wt.%.

[0035] The crystalline phase comprises or consists of at least two crystal phases. Depending on the number and proportion of the crystal phases present, they can be primary or secondary crystal phases.

[0036] One of the crystal phases, referred to as the first crystal phase, comprises crystallites of mixed crystals from the pseudobrookite system.

[0037] Pseudobrookite can be described as Fei+ xTi2- x O5, where x can take values ​​between 0 and 1.

[0038] The two final compositions of this solid solution series, namely FeT Os with x = 0 and Fe2TiO5 with x = 1, are called iron(II) pseudobrookite and iron(III) pseudobrookite.

[0039] In pseudobrookite solid solution, some of the iron ions can be replaced by other metal ions, e.g., manganese, magnesium, cobalt, zinc, nickel. The pseudobrookite system can thus be described in general form by the following idealized formulas:

[0040] Fei-y MyTiCh, where M is selected from the group Mn, Mg, Co, Zn, Cr, where Mn is preferred, or

[0041] (Fei-yMy)Ti2O5, where M is selected from the group Co, Ni or

[0042] (Fei- y M y )2TiO4, where M is selected from the group Zn, Mg and combinations of two or more of these. 6 22 September 2025

[0043] P06253 WO where y can take values ​​from 0 to 0.8.

[0044] It is preferred that y > 0.

[0045] Furthermore, within the pseudobrookite system, titanium ions, preferably not more than 50%, can be replaced by chromium ions. Cr 3+ the place of Ti 3+ and Cr 4+ the place of Ti 4+ take.

[0046] Preferably the first crystal phase consists of crystallites of pseudobrookite mixed crystals Fei+xT -xCh, where x can take values ​​between 0 and 1.

[0047] Preferably, the pseudobrookite solid solution contains more iron(II) than iron(III).

[0048] In glass-ceramic material, in addition to the first crystal phase, at least one further crystal phase, referred to as the second crystal phase, is present in the crystalline phase.

[0049] Preferably it comprises or consists of β-spodumene and / or high-quartz solid solution and / or ilmenite solid solution and / or spinel solid solution.

[0050] If ilmenite mixed crystal is present, it preferably exists at a maximum of 18 wt. %.

[0051] The terms "first" and "second" crystal phase say nothing about the proportion of each crystal phase within the crystalline phase. Thus, the second crystal phase can be the main crystal phase.

[0052] Thus, β-spodumene or high-quartz mixed crystal or ilmenite mixed crystal can also be the main crystal phase.

[0053] It is preferred that β-spodumene and / or high-quartz solid solution are the main crystal phase. In such embodiments, the pseudobrookite system is a secondary crystal phase. Preferably, it is present at least 4 wt.%, more preferably at least 5 wt.%.

[0054] In some embodiments, ilmenite mixed crystal and / or spinel mixed crystal represent further secondary crystal phases. 7 22 September 2025

[0055] P06253 WO

[0056] In some embodiments, the average crystal size of the crystallites present in the crystalline phase of the glacial ceramic material is in the range of 0.06 to 5 pm, preferably in the range of 0.1 to 5 pm, and more preferably in the range of 0.5 to 1.2 pm. The average crystal size of the crystallites can, for example, be at least 0.06 pm, at least 0.1 pm, or preferably at least 0.5 pm. The average crystal size of the crystallites can, for example, be at most 5 pm, or preferably at most 2 pm.

[0057] When crystal sizes are mentioned, the average principal diameter is meant, which results from measuring the dimensions of the crystallites in an image taken with a scanning electron microscope (SEM). For this purpose, the crystallites visible in the image are analyzed using image analysis software. The maximum extent of the crystallites is interpreted as the individual principal diameter, and then the arithmetic mean diameter is calculated from the sum of the individual principal diameters.

[0058] The glass-ceramic material has a linear coefficient of thermal expansion CTE20-300 of -2.0 * 10' 6 / K up to 4.0 * 10' 6 / K is, preferably 0 * 10' 6 / K to < 4.0 * 10' 6 / K, especially preferred 0 * 10' 6 / K to 3.6 * 10' 6 / K, especially preferred 0 * 10' 6 / K to 3.5 * 10' 6 / K on.

[0059] Where reference is made to the coefficient of thermal expansion within the scope of this application, this refers to the linear coefficient of thermal expansion α. ​​Unless otherwise specified, this is given in the range of 20-300°C. The designations α and 0120-300 and CTE and CTE20-300 are used synonymously within the scope of this invention. This can be determined, in particular for glassy materials, using a method according to ISO 7991. The coefficient of thermal expansion of the coating is understood to be the resulting coefficient of thermal expansion of the respective coating, which is derived from the coefficients of thermal expansion of the 8 22 September 2025

[0060] P06253 WO yields individual components of the coating, taking into account their proportion of the coating. Where the present application refers to the coefficient of thermal expansion of the glass pane, this always refers to the coefficient of thermal expansion of the glassy material (or glass) of the glass pane (i.e., the substrate).

[0061] In some embodiments, the starting glass for the glass-ceramic material and / or the glass-ceramic material of the present invention contains TiCh in a proportion of 0.03 to 40 wt.%, for example, 0.5 to 20 wt.%, 0.5 to 32 wt.%, 0.5 to 15 wt.%, or 1 to 12 wt.%. The proportion of TiCh can then, in particular, be at least 0.03 wt.%, at least 0.5 wt.%, or at least 1.0 wt.%. The proportion of TiCh can then, in particular, be at most 40 wt.%, at most 32 wt.%, at most 20 wt.%, at most 15 wt.%, or at most 12 wt.%.

[0062] In some embodiments, the starting glass for the glass-ceramic material and / or the glass-ceramic material of the present invention contains Fe₂O₃ in a proportion of 0.07 to 44 wt.%, for example, 0.5 to 20 wt.% or 1 to 15 wt.%. The proportion of Fe₂O₃ can then, in particular, be at least 0.07 wt.%, at least 0.5 wt.%, or at least 1 wt.%. The proportion of Fe₂O₃ can then, in particular, be at most 44 wt.%, at most 20 wt.%, or at most 15 wt.%.

[0063] In some embodiments, the starting glass for the glass-ceramic material and / or the glass-ceramic material of the present invention contains MnCh in a proportion of 0.03 to 25 wt.%, for example, 0.5 to 15 wt.% or 1.0 to 10 wt.%. The proportion of MnCh can then, in particular, be at least 0.03 wt.%, at least 0.5 wt.%, or at least 1 wt.%. The proportion of MnCh can then, in particular, be at most 25 wt.%, at most 15 wt.%, or at most 10 wt.%. 9 22 September 2025

[0064] P06253 WO

[0065] In some embodiments, the starting glass and / or the

[0066] The glass-ceramic material of the present invention comprises the following components in the specified amounts (in weight percent on an oxide basis): The term RO stands for the alkaline earth metal oxides MgO, CaO, SrO, BaO.

[0067] The term R2O stands for the alkali metal oxides LiO, NaO, K2O.

[0068] Sugar, for example, can be used as a reducing agent.

[0069] In some embodiments, the starting glass for the glass-ceramic material and / or the glass-ceramic material of the present invention contains the following components in the specified amounts (in weight percent on an oxide basis): 10 22 September 2025

[0070] P06253 WO

[0071] In some embodiments, the starting glass for the glass-ceramic material and / or the glass-ceramic material of the present invention contains the following components in the specified amounts (in weight percent on an oxide basis): 11 22 September 2025

[0072] P06253 WO

[0073] In some embodiments, the starting glass for the glass-ceramic material and / or the glass-ceramic material of the present invention contains no SrO and / or no B2O3 and / or no EfcCh and / or no CI and / or no CoO and / or no CnCh and / or no F and / or no P2O5 and / or no V2O5

[0074] The glass-ceramic material of the invention is obtained by ceramizing suitable starting glasses. The composition of the starting glasses is not substantially altered by the ceramization. The composition of the glass-ceramic material therefore essentially corresponds to the composition of the starting glass.

[0075] The glass-ceramic material of the invention can be produced by a process comprising the following steps: a) providing a starting glass, wherein the starting glass has been melted under reducing conditions for 30 min to 2.5 h at 1600 °C to 1650 °C; b) melting the starting glass by thermal treatment at a temperature of more than 1050 °C to 1270 °C for a duration of 3 minutes to 12 hours, preferably from 3 min to 5 h, particularly preferably from 3 min to 1 h.

[0076] Step b) can optionally be preceded by a thermal treatment at 700 °C to 735 °C for a duration of 4 to 6 hours. 12 22 September 2025

[0077] P06253 WO

[0078] The step of providing a starting glass may include, in particular, melting glass raw materials under reducing conditions (especially under a reducing atmosphere) and / or quenching the melt. Quenching may, in particular, involve rapid roller quenching, water quenching, or

[0079] Air deterrence methods or a combination of two or more of these methods.

[0080] The process for producing a glass-ceramic material as a filler can further include the step of grinding the glass-ceramic material. The grinding step can be carried out in such a way that the grains preferably have a grain size d50 in the range of 0.1 pm to 5 pm, from 0.5 pm to 3.0 pm, or only up to 1.5 pm. A grain size d50 of less than 1 pm is preferred.

[0081] The designation d50 for grain size is generally known in the measurement of grain size distribution and requires no further explanation here.

[0082] The glass-ceramic material according to the invention, in particular the glass-ceramic material produced by this method, has a high optical density in the VIS range, preferably OD > 40 / mm, preferably > 50 / mm, and an advantageous color appearance.

[0083] The glass-ceramic material produced using this method has a linear coefficient of thermal expansion CTE20-300 of -2 * 10' 6 / K up to 4.0 * 10' 6 / K is, preferably 0 * 10' 6 / K to < 4.0* 10' 6 / K, especially preferred between 0 * 10' 6 / K to +3.5 * 10' 6 / K on.

[0084] The invention also relates to a glass or glass-ceramic disc comprising a glass or a glass-ceramic comprising SiCh and Al2O3 and at least one component from the group Li2O, B2O3.

[0085] The glass or glass-ceramic disc comprises at least one coating applied in at least one area of ​​at least one side of the disc, with a first coating designed as an enamel layer, wherein the first coating 13 22 September 2025

[0086] P06253 WO comprises at least one glass-based binder comprising SiCh and, as a filler, at least one of the glass-ceramic materials according to the invention, and optionally includes one or more pigments. The presence of one or more pigments is preferred.

[0087] Such a glass or glass-ceramic disc has a number of advantages.

[0088] In certain embodiments, the glass pane preferably comprises a glass consisting of SiCh, Al₂O₃, and B₂O₃, i.e., a so-called borosilicate glass. This type of glass material (or simply glass) is a chemically very resistant material that is also mechanically resistant and, compared to conventional glasses such as soda-lime glass, exhibits good thermal resistance and good mechanical strength even in an unstressed state. It has also been shown that the scratch resistance of such borosilicate glasses is higher than that of soda-lime glass.

[0089] In embodiments, the glass-ceramic sheet preferably comprises a glass-ceramic sheet containing SiCh, Al₂O₃, and IÜ₂O, i.e., a so-called LAS glass-ceramic. This type of glass-ceramic material (or simply glass-ceramic) is a thermally very resistant material that is also mechanically resistant and, compared to glasses such as soda-lime glasses, exhibits good thermal resistance and good mechanical strength even in an unstressed state.

[0090] In embodiments, the glass pane preferably comprises a glass containing SiCh, CaO and 2O, i.e. a so-called soda-lime glass.

[0091] The coating is formed in at least one area on at least one side of the glass or glass-ceramic pane. Preferably, the coating is formed in the form of a frame over the entire edge area of ​​one side of the glass pane, and it is further possible that towards the middle area of ​​the glass pane the coating is no longer opaque, but rather forms a so-called dot matrix. 14 22 September 2025

[0092] P06253 WO is applied. This can be particularly advantageous if the glass pane is used as part of a composite material, for example as a windshield.

[0093] The coating is designed as a chemically and thermally resistant coating. This means that the coating comprises a binder consisting of SiCh. SiCh exhibits good chemical resistance and is also temperature-stable.

[0094] The coating comprises the glass-ceramic material according to the invention as a filler. All disclosed embodiments of the glass-ceramic material are hereby also disclosed for use as a filler in the coating.

[0095] The coating can contain one or more additional fillers besides the glass-ceramic material. These fillers typically have a medium grain size ranging from the nanometer to the millimeter range.

[0096] Other fillers may include, in particular:

[0097] Silicas, for example pyrogenic or precipitated silicas,

[0098] Quartz glass, e.g. as spherical particles, e.g. high-purity spherical quartz glass, porous fillers, for example porous glasses such as those available under the name “CoralPor®”, or porous crystalline materials, in-situ generated fillers, for example by decomposition of a metal-organic or silicon-organic component.

[0099] Due to the low coefficient of thermal expansion of the glass-ceramic material of CTE20-300 between 0 * 10' 6 / K and 4.0 * 10' 6 / K, preferably 0 * 10' 6 / K to < 4.0 * 10" 6 / K, the coating can be made without other fillers that have the purpose of lowering the coefficient of expansion of the coating and adapting its expansion behavior to that of the disc.

[0100] Due to their high optical density and their color impression describable by LAB values, the coating does not require the addition of pigments. 15 22 September 2025

[0101] P06253 WO will be used, which is advantageous because conventional pigments have a rather high coefficient of thermal expansion. Therefore, their use would increase the low coefficient of thermal expansion of the coating, which is due to the low coefficient of thermal expansion of the glass-ceramic material used as filler. For example, the black pigment CuCnCh has a CTE20-300 of 10 x 10' 6 / K.

[0102] In particular, to increase opacity and / or variation of the color impression, the coating preferably comprises at least one pigment. For the purposes of this disclosure, a pigment is understood to be a particle-based colorant. Advantageously, the pigment according to this disclosure is also temperature-stable and is preferably a ceramic colorant. In general, for the purposes of this disclosure, a colorant (or pigment) is understood to be a colorant consisting of particles, which may also be referred to here as pigment particles. Therefore, whenever it is stated in this disclosure that a coating comprises a pigment, it is understood that the coating comprises particles of a specific pigment or colorant, i.e., particles with the composition of the pigment or colorant.

[0103] Ceramic colorants or ceramic pigments as such are familiar to those skilled in the art. These can include, for example, metallic mixed oxides such as hematites and spinels, or pure oxides such as TiO₂ or Fe₃Ü₄. Typical pigment sizes can range from an average of 0.15 pm to 5 pm, with the dw value, based on the equivalent diameter, reaching up to 15 pm. Finer particle sizes may be preferred, however, as they are easier to print.

[0104] When pigments are used in the coating, their concentration can be kept low due to the high optical density of the glass-ceramic material used as a filler. This hardly increases the coating's already low coefficient of thermal expansion, which is due to the low coefficient of thermal expansion of the glass-ceramic material used as a filler. 16 22 September 2025

[0105] P06253 WO

[0106] According to a preferred embodiment, the coating of the glass or glass-ceramic disc is designed to have a porosity gradient, wherein the porosity of the coating decreases from the glass disc towards the surface of the coating.

[0107] The terms glass pane and glass-ceramic pane are used for panes with or without a coating, depending on the context. Whenever reference is made in this application to a "glass pane per se" or a "glass-ceramic pane per se", this expressly refers to an uncoated pane, and the information concerns, for example, the properties of the pane without a coating.

[0108] The coated glass or glass-ceramic sheet exhibits good strength. According to embodiments, the coated glass or glass-ceramic sheet generally exhibits, particularly in the area where the coating disclosed herein is applied, a flexural strength of at least 5 MPa and at most 60 MPa, for example, between 5 MPa and at most 55 MPa. Preferred values ​​are at least 20 and at most 50 MPa, preferably at least 25 MPa. In this way, sufficient strength of the coated glass sheet is achieved for use, for example, as a sheet in a composite.Mechanical strength, such as flexural strength, is a statistical value, so naturally the same pane would not be tested for flexural strength before and after coating; rather, the above statement refers to tests carried out on uncoated and coated glass panes of the same composition and design. Flexural strength, or tensile flexural strength, is a defined parameter and denotes the maximum tensile stress a body or material can withstand when subjected to bending. Flexural strength is defined by how a specimen bends in a test until it breaks at 17°C (September 22, 2025).

[0109] P06253 WO behaves under maximum stress. Within the scope of this disclosure, flexural strength is understood to be the strength of the glass pane, also referred to as double-ring flexural tensile strength, which was determined in each case according to DIN 1288-5. Within the scope of this disclosure, the arithmetic mean is given as the strength value. The so-called MOR (Modulus of Rupture) is an index for flexural strength.

[0110] According to one embodiment, the coverage of at least one side of the glass pane with the coating is at least 10% and at most 80%, preferably at least 15% and at most 65% of the total surface of the side of the pane on which the coating is applied.

[0111] In the context of this disclosure, a disc is generally understood to be a plate-shaped body. A glass disc (which may be coated or uncoated) is a disc comprising or made of glass. A body is plate-shaped if its spatial dimensions in one direction of a Cartesian coordinate system are at least one order of magnitude smaller than the spatial dimensions in the two other directions perpendicular to the first direction of the Cartesian coordinate system. In other words, the thickness of the body is at least one order of magnitude smaller than its length and width. The two principal surfaces of the disc, i.e., those whose size is determined by length and width, are also referred to simply as sides in this disclosure.

[0112] The coating can be applied to the glass pane in at least one area as a solid, uninterrupted layer, or it can be arranged, for example, in a dot matrix pattern. Combinations of these variations are also possible. For instance, a coating applied to the entire surface of the glass pane, without any interruptions, can transition into a dot matrix pattern at the edges, typically towards the center of the pane. This is a common coating configuration, as seen on September 22, 2025.

[0113] P06253 WO

[0114] The trap is structured and arranged on the glass pane, for glass panes used in vehicle windshields.

[0115] The binder is glass-based.

[0116] A glass-based coating is generally understood to be a coating that contains at least a predominantly (i.e., more than 50 wt.%) inorganic, amorphous binder. In particular, such a glass-based coating may also contain a binder that is essentially (i.e., at least 95 wt.%) or even entirely inorganic and amorphous. In addition to the binder, a glass-based coating may generally include other components.

[0117] The binder is in the form of a glass frit.

[0118] The coating is designed as an enamel layer.

[0119] For the purposes of this disclosure, enamel coatings or enamel layers are understood to be coatings that incorporate glass frit or glass flux as a binder. During the firing of such coatings, the components of the glass flux, i.e., the glass frit, melt, and a melting reaction zone can form on the surface of the substrate, for example, the glass sheet. For the purposes of this disclosure, the terms frit, glass frit, and glass flux are used synonymously. Furthermore, the molten glass flows and encapsulates any additional components contained within the enamel color or the coatings resulting from such a color, such as pigment particles and / or filler particles. In this way, particularly mechanically resistant coatings can be obtained.Furthermore, the surface of such a layer is glass-like and, depending on the exact composition of the glass frit, can even be quite similar to the composition of the glass pane. In this way, it is advantageously possible, according to one embodiment, for the strength of the bond between the two glass panes of a laminate to not differ significantly in different areas, but rather for the bond to be uniform across the entire surface of the glass pane. 19 22 September 2025.

[0120] P06253 WO

[0121] In the context of this disclosure, a glass flux or (synonymously) a glass frit is understood to be a glass-based binder suitable for forming a glaze and / or enamel layer. In particular, it may be a glass powder suitable and intended for application to a substrate by means of a printing process, and the glass powder may also be mixed with other components, such as pigments. Preferably, such glass fluxes / glass frits have a lower melting point and / or softening point than the corresponding substrate material, in particular than the material of a glass sheet to be coated.

[0122] Preferably, the coating has a thickness between 1 pm and 30 pm, more preferably between 2.5 pm and 20 pm, more preferably between 3 pm and 10 pm, and most preferably not more than 7.5 pm. Therefore, the coating thickness is preferably at least 1 pm, more preferably at least 2.5 pm, and more preferably at least 3 pm. Therefore, the coating thickness is preferably at most 30 pm, more preferably at most 20 pm, more preferably at most 10 pm, and most preferably at most 7.5 pm.

[0123] According to a further embodiment, in at least a partial area of ​​the region of at least one side of the glass pane where the first coating is applied, a further coating, in particular as an intermediate layer between the glass pane and the first coating, is arranged. In this further embodiment, the entire coating disclosed herein thus comprises the first coating and the further coating. For the sake of brevity, the entire coating will subsequently be referred to simply as the coating in some instances.

[0124] Such an additional coating, arranged as an intermediate layer between the glass pane and the coating, can be advantageous for certain designs. September 22, 2025

[0125] P06253 WO

[0126] The terms "additional coating" and "first coating" do not refer to the order of application, but merely to the fact that the "first coating" is always present, while the additional coating is optional, depending on the specific embodiment. If only the first coating is present, it can also be referred to as a "coating".

[0127] In general, the paste used for coating with the first coating can contain between 50 vol.% and 99.5 vol.% binder, for example glass frit, based on the solid content of the paste.

[0128] The binder content in the first coating is, in some embodiments, between 99.5 vol% and 40 vol% binder, preferably between 99.5 and 50 vol% binder, and particularly preferably between 95 and 55 vol% binder, for example between 80 and 60 vol% binder, wherein a glass frit preferably forms the binder. According to a further preferred embodiment, the binder content in the first coating can generally be between 78 vol% and 50 vol%.

[0129] The filler content in the first coating is preferably between 3.5 vol.% and 50 vol.% filler, preferably between 7.5 vol.% and 40 vol.% filler, particularly preferably between 10 vol.% and 35 vol.% filler, for example between 15 vol.% and 30 vol.% filler.

[0130] The glass-ceramic material used as a filler according to the invention is not colorless, unlike conventional fillers.

[0131] The glass-ceramic material used as a filler according to the invention has a low coefficient of expansion, unlike conventional fillers and especially unlike conventional colored additives such as pigments.

[0132] Due to the advantageous properties of the glass-ceramic material according to the invention, the coating of the coated glass or glass-ceramic disc preferably has a coating thickness of 3.5 pm. September 22, 2025

[0133] P06253 WO optical density, which is at least 0.1, preferably at least 0.2, and at most 4.5, for example at most 3, preferably at more than 2.

[0134] The optical density is determined in an area where the coating is applied over the entire surface.

[0135] According to one embodiment, the coated glass pane preferably has an optical density in the at least one area in which the coating is arranged, with a coating thickness of 3.5 pm, of at least 0.1, preferably at least 0.2, and at most 4.5, for example at most 3, preferably more than 1, particularly preferably more than 2.

[0136] Optical density, or color density, is used to characterize the absorption behavior of a coating compared to "absolute white." The denser the color layer, the less light can pass through it. Optical density is calculated using the following formula:

[0137] R is the reflectance. The optical density is determined using densitometers, specifically within the scope of this disclosure, in the direction perpendicular to the largest surface area of ​​the coating and thus the coated surface of the glass pane. The higher the optical density, the less transparent the coating appears.

[0138] According to a preferred embodiment, the first coating comprises between 0.5 vol.% and 40 vol.% pigment, preferably between 0.5 and 30 vol.% pigment, particularly preferably between 10 and 25 vol.% pigment, and most preferably between 5 vol.% and 20 vol.% pigment. Preferably, black pigments, e.g., Fe3Ü4 or CuCr2O4, or also Cr-Fe oxides or Fe-Mn oxides, are used.

[0139] With a pigment content in the specified range, the optical density can be further increased. September 22, 2025

[0140] P06253 WO

[0141] Due to the advantageous properties of the glass-ceramic material according to the invention, the coating of the coated glass or glass-ceramic sheet exhibits a particularly advantageous color impression at a given coating thickness. According to the knowledge of those skilled in the art, the color impression can be determined using the CIELAB color space, particularly under illumination with illuminant type D65, a viewing angle of 10°, and a thickness of 3.5 pm. The thickness can, in particular, be the thickness of the enamel layer. The L* value, the a* value, and the b* value of the CIELAB color space can be determined according to the knowledge of those skilled in the art, particularly using the KONICA MINOLTA CM-700d spectrophotometer, with the enamel layer facing upwards. Within the scope of this disclosure, the L* value, a* value, and b* value were determined using the SCE (Specular Component Excluded) method.This method corresponds better to the visual impression than the SCI (Specular Component Included) method.

[0142] The L* coordinate of the coating can be in a range of 5 to 75, particularly preferably from 5 to 15. The L* coordinate can be at most 75, at most 50, at most 30, at most 20, preferably at most 15.

[0143] The a* coordinate of the coating can be in a range of -4 to 1, preferably from -3 to 0, and particularly preferably from -2.5 to 0.

[0144] The b* coordinate of the coating can be in a range of -2 to 13, preferably from -2 to 1.5, particularly preferably from -2 to 1.

[0145] Particularly preferred is a coating with L* of at most 75, preferably of at most 15, and with a* = 0.5 ± 1 and / or b* = 5 ± 7.5.

[0146] According to one embodiment, the coated glass or glass-ceramic sheet preferably exhibits, in the at least one region where the coating is arranged, the values ​​specified above for the coating thickness given above. 23 22 September 2025

[0147] P06253 WO

[0148] With a pigment content in the aforementioned range, the LAB values ​​can be shifted further towards a darker black, depending on the selection of pigments.

[0149] Since ceramic pigments commonly used in coatings, for example spinel-based pigments, have relatively high coefficients of thermal expansion compared to the materials of the discs being coated, such as borosilicate glasses or glass ceramics, it is advantageous that the presence of the glass ceramic material according to the invention in the coating allows the pigment content of the coating to be limited to the aforementioned low proportions. In some embodiments, pigments are even omitted entirely.

[0150] Another criterion for the visual impression is the gloss.

[0151] The gloss can be measured from the side of the coating or from the other side, the "viewer's side," i.e., from the side of the substrate and thus through the substrate. In some embodiments, the gloss at 60°, measured from the side of the coating according to the invention, is in a range of 1 GU to 100 GU, in particular from 10 GU to 100 GU, from 45 GU to 100 GU, or from 45 GU to 70 GU. The gloss at 60° can, in particular, be at least 1 GU, at least 10 GU, or at least 45 GU. The gloss at 60° can, in particular, be at most 100 GU or at most 70 GU. The gloss at 60° can be determined according to the knowledge of a person skilled in the art, in particular with the RHOPOINT gloss meter according to known established measurements. The gloss is expressed in "gloss units" (GU). Measured through the coating, the gloss at 60° has advantageous GU values ​​of 45 to 100.

[0152] In some embodiments, the coating passes the sclerometer test at a force of 10 N, particularly with a coating thickness in the range of 2.5 to 20 pm, such as 3 to 10 pm, especially 3.5 pm. The sclerometer test can be carried out according to the knowledge of a person skilled in the art, in particular with the Elcometer 3092 and a force of 10 N in accordance with AS3894.4, EN 438-2 and / or ISO 4586-2. "Passing" the test means that the tested samples with 0 24 22. September 2025

[0153] P06253 WO or 0.5 according to the sclerometer scale, which ranges from 0 to 2 in increments of 0.5. "0.5" means that only slight pressure marks are visible on the enamel side in the tested area. "0" means that no changes are visible on the enamel side.

[0154] In some embodiments, the coating passes the spring hammer test with a drop weight of 248.12 g and a polyamide impact hemisphere, particularly with a coating thickness in the range of 2.5 to 20 pm, such as 3 to 10 pm, especially 3.5 pm. The spring hammer test is a measure of fracture toughness and can be carried out according to the knowledge of a person skilled in the art. Testing is performed up to the maximum possible test height of 50 cm. For non-prestressed materials, results of just a few centimeters are already satisfactory, so that, within the scope of the disclosure, a result of 4 cm or more is considered a passing grade for the coating.

[0155] The fact that optical parameters (such as the CIELAB parameters or the optical density) are preferably determined at a coating thickness of 3.5 pm does not mean that the coating on the disk necessarily has such a thickness. The coating on the disk may have a thickness of 3.5 pm, but it does not have to. The thickness of 3.5 pm merely indicates the preferred reference thickness for optical measurements.

[0156] For example, the transmittance depends on the thickness of the coating. Therefore, it is useful to specify a reference thickness. For instance, the optical density might be 3.5 pm² for a given enamel layer thickness. However, the actual coating thickness of the coated disc might be, for example, 7 pm. Thus, the invention also includes, for example, discs with a coating thickness of 7 pm, wherein the optical density is 3.5 pm² for a reference coating thickness. September 22, 2025

[0157] P06253 WO

[0158] Due to the advantageous properties of the glass-ceramic material according to the invention, the coating of the coated glass or glass-ceramic disc preferably has a linear coefficient of thermal expansion CTE20-300 between 3 * 10' 6 / K and 7 * 10' 6 / K is preferably 3.5 * 10' 6 / K to 6* 10' 6 / K, especially preferred between 3.5* 10' 6 / K to 5.5 * 10' 6 / K on

[0159] It has been shown that for the mechanical properties of the coated pane, it is advantageous if the coefficients of thermal expansion of the pane and the coating are matched, and in particular, as similar as possible. This is the case, for example, when using a borosilicate glass pane.

[0160] It can also be advantageous if the coefficient of thermal expansion of the coating is lower than that of the glass pane. In this way, compressive stress can be generated by the coating. This is referred to as "prestressing without a process." This is the case, for example, when using a soda-lime glass pane. The low-expansion fillers in the coating according to the invention are therefore also decisive for the final mechanical properties of the coated pane.

[0161] According to one embodiment, the glass of the glass pane, which preferably comprises SiCh and Al2O3 and B2O3, has a linear coefficient of thermal expansion between 2 * 10' 6 / K and 6 * 10' 6 / K. This is advantageous because it allows the glass pane to be designed using known, low-expansion borosilicate glasses, which inherently possess quite high glass strength. Furthermore, such glasses also exhibit quite good thermal resistance and are chemically quite resistant.

[0162] Preferably, the glass of the glass sheet according to one embodiment comprises at least 60 wt.% SiCh up to a maximum of 85 wt.% SiCh and / or at least 7 wt.% B₂O₃ up to a maximum of 26 wt.% B₂O₃. Such glasses are particularly advantageous because they offer a good compromise between good mechanical, chemical, and thermal resistance on the one hand and good meltability on the other, without segregation tendencies and / or excessively high viscosity of the glass melt having a detrimental effect. 26 22 September 2025

[0163] P06253 WO

[0164] According to one embodiment, the glass ceramic of the glass ceramic disc, which preferably comprises SiCh and Al2O3 and Li2Ü, has a linear coefficient of thermal expansion CTE20-700 between -0.5 * 10' 6 / K and 1 * 10' 6This is advantageous because it allows the glass-ceramic sheet to be designed using known, low-expansion glass-ceramics, e.g., LAS glass-ceramics with main crystal phases such as keatite or high-quartz solid solution, or glass-ceramics with lithium disilicate, which already possess intrinsically high strength. Furthermore, such glass-ceramics also exhibit quite good thermal resistance and are chemically quite resistant.

[0165] According to one embodiment, the glass or glass-ceramic disc has a thickness of at least 1 mm and at most 12 mm, preferably between 2 mm and 4 mm.

[0166] The paste used for coating with the first coating comprises, in addition to the glass-ceramic material as filler and the binder and optional pigment, preferably at least one dispersion medium.

[0167] The dispersion medium or medium is advantageous for applying the paste to the glass or glass-ceramic sheet, for example, for applying the paste by means of a screen printing process. For the purposes of this disclosure, a paste is understood to be, in particular, a so-called decorative or color paste.

[0168] The binder comprises or consists of a glass frit, wherein the glass frit comprises at least the following oxide-based components in wt.%:

[0169] SiÜ2 10 to 70

[0170] B2O3 10 to 26

[0171] AI2O3 more than 0 to 9. 27 22 September 2025

[0172] P06253 WO

[0173] In the case of high-bi frits, especially high-bi borosilicate frits, the glass frit may comprise a glass which includes at least the following components in wt.% on an oxide basis:

[0174] The fritters specified in the preceding paragraph may optionally contain a proportion of AI2O3 of more than 0 to 9 wt.%.

[0175] The following values ​​apply to the thermal expansion coefficient a and the density for the aforementioned high-bi-content borosilicate frits:

[0176] In the case of high Zn-content frits, especially high Zn-content borosilicate frits, the glass frit can comprise a glass which includes at least the following components in wt.% on an oxide basis: 28 September 22, 2025

[0177] P06253 WO

[0178] The frits mentioned in the preceding paragraph may optionally contain an Al₂O₃ content of more than 0 to 9 wt.%. The following values ​​apply to the coefficient of thermal expansion α and the density of the aforementioned high-Zn borosilicate frits:

[0179] In borosilicate frits, the glass frit can comprise a glass which contains at least the following components in wt.% on an oxide basis:

[0180] The fritters mentioned in the preceding paragraph may optionally contain an amount of AI2O3 of more than 0 to 9 wt.%.

[0181] The following applies to the coefficient of thermal expansion a and the density for the above borosilicate frits: 29 22 September 2025

[0182] P06253 WO

[0183] The paste is formulated to produce an enamel coating, with the glass frit advantageously comprising borosilicate glass. The frit compositions used are preferably tailored to the material of the glass pane to be coated.

[0184] The following coatings are preferably used for borosilicate glass panes

[0185] French fry mixtures used:

[0186] The following are preferably used for coating glass-ceramic discs

[0187] French fry mixtures used: 30 22 September 2025

[0188] P06253 WO

[0189] The following are preferably used for coating soda-lime glass panes

[0190] French fry mixtures used: Solvents with a vapor pressure of less than 10 bar, particularly less than 5 bar, and especially less than 1 bar, are preferably used as the medium for screen-printable coating solutions. These can be, for example, combinations of water, n-butanol, diethylene glycol monoethyl ether, tripropylene glycol monomethyl ether, terpineol, or n-butyl acetate. The viscosity of the paste is adjusted as required. The medium can, in particular, consist of one or more

[0191] Glycol ethers, in particular 2-(2-butoxyethoxy)ethanol and / or 2-butoxyethanol, may be included or consist of. The organic medium may, for example, contain or consist of 50 to 75 vol% 2-(2-butoxyethoxy)ethanol and 20 to 30 vol% 2-butoxyethanol. To adjust the desired viscosity, 31 22. September 2025

[0192] P06253 WO uses corresponding organic and inorganic additives. Organic additives can include, for example, hydroxyethyl cellulose and / or hydroxypropyl cellulose and / or xanthan gum and / or polyvinyl alcohol and / or polyethylene alcohol and / or polyethylene glycol, block copolymers and / or triblock copolymers and / or tree resins and / or polyacrylates and / or polymethacrylates. Generally, commercially available screen printing media based on, for example, glycol or terpineol are suitable, as are others.

[0193] In general, the paste can be used to obtain a glass or glass-ceramic disc with a coating, wherein the coating is an enamel layer and comprises a binder, here designed as glass frit (or glass flux), which includes the following components in wt.% on an oxide basis:

[0194] SiO210 to 70

[0195] B2O3 10 to 26

[0196] AI2O3 more than 0 to 9.

[0197] Preferably, the paste is formulated to have a viscosity, preferably determined by a plate viscometer, between 1500 and 8000 mPas, more preferably between 2000 and 6500 mPas, and most preferably between 2500 and 5000 mPas. This allows the paste to be readily applied on an industrial scale to substrates, particularly glass or glass-ceramic sheets, using conventional application methods. Advantageously, the paste can be applied to the substrate, i.e., the glass or glass-ceramic sheet, by a printing process, particularly screen printing.

[0198] However, it may also be possible to adjust the viscosity differently, so that, for example, a lower viscosity is obtained, such as a viscosity of no more than 1500 mPas.

[0199] The coating can be produced by a) coating a glass or glass-ceramic disc with a paste containing the glass-ceramic material according to the invention. 32 22 September 2025

[0200] P06253 WO

[0201] a) material, wherein the paste also contains an organic medium and optionally one or more pigments, and b) heat treatment of the coated disc at a temperature of 600 °C to 950 °C for a duration of 15 seconds to 30 minutes, preferably 30 seconds to 20 minutes, particularly preferably not more than 15 minutes. The glass-ceramic material may have been produced according to the process of the disclosure.

[0202] If a coated glass pane is heat-treated according to b), the heat treatment of the coated pane preferably takes place between 600 °C and 750 °C.

[0203] If a coated glass-ceramic disc is heat-treated according to b), the heat treatment of the coated disc preferably takes place between 700 °C and 950 °C.

[0204] Another aspect of the present disclosure relates to a composite comprising a glass pane coated at least in certain areas according to one embodiment of the disclosure, and a further glass pane, wherein the coating is preferably arranged between the glass panes. Furthermore, the composite preferably comprises a polymeric layer, which is also arranged between the glass panes and bonds them together. The polymeric layer can, for example, be in the form of a film between the two glass panes, but it is also possible to initially apply the polymeric layer in liquid form, with the polymeric liquid hardening into a polymeric layer when the two glass panes are joined.

[0205] Examples

[0206] The invention will be explained in more detail below using examples.

[0207] The glass pane according to the present disclosure comprises a glass containing SiO₂ and Al₂O₃ and at least one component from the group consisting of Li₂O and B₂O₃. 33 22 September 2025

[0208] P06253 WO

[0209] The glass pane according to the present disclosure preferably comprises a glass comprising SiO₂ and Al₂O₃ and B₂O₃.

[0210] The glass pane preferably comprises a borosilicate glass; it preferably consists of a borosilicate glass.

[0211] The glass pane preferably has a linear coefficient of thermal expansion between 2 * 10' 6 / K and 6 * 10' 6 / K, preferably between 2 * 10' 6 / K and 5.5 * 10' 6 / K on.

[0212] According to a first embodiment, the glass can be given by a composition comprising the following components, each specified in wt.% on an oxide basis:

[0213] SiÜ2 60 to 85, especially preferably up to 82

[0214] B2O3 7 to 26

[0215] Al2O3 0 to 12, preferably larger than 0 to 11, particularly preferably up to 7

[0216] IÜ2O 0 to 1

[0217] Na2Ü 0.5 to 6

[0218] K2O 0 to 3

[0219] MgO 0 to 6

[0220] CaO 0 to 5

[0221] SrO 0 to 4

[0222] ZnO 0 to 3

[0223] ZrÜ2 O to 3.

[0224] Furthermore, other components commonly used in glassmaking may be included, such as refining agents. These are generally present in a concentration of no more than 2% by weight of the glass.

[0225] The following compositions may show deviations from 100% in the total weight percentage due to rounding errors caused by analysis. 34 22 September 2025

[0226] P06253 WO

[0227] An exemplary glass is given in the following composition range in wt.% based on oxides:

[0228] SiO275 - 85

[0229] B2O3 10-15

[0230] AI2O3 1-3

[0231] Na2O 2-5

[0232] K2O 0-1

[0233] NaCl less than 0.5

[0234] An example composition of a glass in this composition range, in wt.%, based on oxides, is given as follows:

[0235] SiCh 80.8

[0236] B2O3 12.7

[0237] AI2O3 2.4

[0238] Na2O 3.5

[0239] K2O 0.6

[0240] NaCl 0.1

[0241] Another glass is given in the following composition range in wt.% based on oxides:

[0242] SiCh 73-83

[0243] B2O3 8-12

[0244] AI2O3 1-4

[0245] Na2O 2-4

[0246] K2O 1-3

[0247] MgO 1-3

[0248] CaO 1-3 35 22 September 2025

[0249] P06253 WO

[0250] Another exemplary composition of a glass in this context

[0251] The composition range in wt.% based on oxides is given as follows:

[0252] SiO278.1

[0253] B2O3 9.8

[0254] AI2O3 2.5

[0255] Na2O 2.8

[0256] K2O 2.5

[0257] MgO 1.8

[0258] CaO 2.5

[0259] Another glass is given in the following composition range in wt.% based on oxides:

[0260] SiO272-74

[0261] B2O3 13-15

[0262] AI2O3 5-6

[0263] Na2O 4-6

[0264] K2O 1-2

[0265] MgO 1-3

[0266] Another exemplary composition of a glass in this composition range, in wt.%, based on oxides, is given as follows:

[0267] SiO272.5

[0268] B2O3 14.0

[0269] AI2O3 5.6

[0270] Na2O 5.1

[0271] K2O 1.4

[0272] MgO 1.1 36 22 September 2025

[0273] P06253 WO

[0274] The glass-ceramic sheet according to the present disclosure comprises a glass-ceramic comprising SiO₂ and Al₂O₃ and at least one component from the group Li₂O₃, B₂O₃. The glass-ceramic sheet according to the present disclosure preferably comprises a glass-ceramic comprising Si₂O₃, Al₂O₃ and Li₂O.

[0275] The glass pane preferably comprises a LAS glass ceramic; it preferably consists of a LAS glass ceramic.

[0276] The glass-ceramic disc preferably has a linear coefficient of thermal expansion CTE20-700 between -0.5 * 10' 6 / K and 1 * 10' 6 / K, preferably between 0* 10' 6 / K and 0.5 * 10' 6 / K on.

[0277] According to one embodiment, the glass ceramic can be given by a composition comprising the following components, each given in mol-% on an oxide basis:

[0278] SiÜ2 60 to 80

[0279] AI2O3 8 to 18

[0280] Li2O 4 to 12

[0281] DO2 0 to 4

[0282] ZrÜ2 0 to 4

[0283] SnÜ2 0 to 2

[0284] The main crystal phases of this system are preferably keatite mixed crystal and high quartz mixed crystal.

[0285] Table 1 lists example frit compositions for various applications. The components are specified in wt.% based on oxides.

[0286] Table 1 37 22 September 2025

[0287] P06253 WO

[0288] Table 2 lists green glass compositions used in the production of the glass-ceramic materials used as fillers in exemplary applications. The components are given in wt.% based on oxides.

[0289] Table 2 38 22 September 2025

[0290] P06253 WO

[0291] These green glass beads were ceramicized into glass ceramics.

[0292] Table 3 lists the various ceramization conditions and key properties, namely the coefficient of thermal expansion (CTE20-300), optical density (OD) in the visible range, grain size (d50) after milling the glass-ceramic material by ball milling with Al₂O₃ balls in isopropanol, the crystal phases and their proportions, and the proportion of residual glass phase for each glass-ceramic GK1 to GK4, which were produced from GG₂. The CTE was measured for example GK₅ (see Table 4), and for the other examples, it was estimated based on the differences in the composition of the crystal phases, whose respective CTE values ​​are known.

[0293] Table 3

[0294] 39 22 September 2025

[0295] P06253 WO

[0296] Table 4 lists the different ceramization conditions and essential properties, namely coefficient of thermal expansion CTE20-300, optical density OD in

[0297] 5 VIS, grain size d50 after grinding the glass ceramic material by ball milling with balls made of Al2O3 in isopropanol, the crystal phases and their proportions and the proportion of the residual glass phase of the respective glass ceramic GK5 and GK6, which were made from GG1, and GK7, which was made from GG2, are specified.

[0298] The CTE was measured for one example (GK5), and for the other examples, it was estimated to be 0 based on the differences in the composition of the crystal phases, whose respective CTEs are known. 40 22 September 2025

[0299] P06253 WO

[0300] Table 4

[0301] Using the glass ceramics GK5 and GK1, various coatings (exemplars Al - A3 (with GK5) and exemplars A4 - A6 (with GK1)) were produced and compared with other coatings (comparative examples VI - V5).

[0302] The coating Al contains as its sole filler 23.5 vol.% of the glass-ceramic material GK5 according to the invention. The remainder is frit.

[0303] The coating A2 contains as its sole filler 16 vol% of the glass ceramic GK5, and it contains 7.5 vol% of the black pigment CuCnCh with a d50 of 0.6 pm. The remainder is frit.

[0304] Coating A3 contains as its sole filler 7.5 vol% of the glass-ceramic material GK5 according to the invention, and it contains 16 vol% of the black pigment CuCnCh with a d50 of 0.6 pm. The remainder is frit. 41 22 September 2025

[0305] P06253 WO

[0306] Coatings A4 to A6 contain as their sole filler the specified amounts of the glass-ceramic material GK1 according to the invention, with A5 and A6 each containing the black pigment CuCnCh with a d50 of 0.6 pm in the amounts specified. Coatings VI to V5 contain no fillers, i.e., no GK1 to GK6. Coating VI consists only of frit. Coatings V2 to V5 contain 23.5 vol% (V2), 20 vol% (V3), 10 vol% (V4), and 7.5 vol% (V5) of the black pigment CuCnCh with a d50 of 0.6 pm. They contain no filler. Table 5 summarizes the compositions.

[0307] Table 5

[0308] The frit shown in Example 3 of Table 1 was used to produce the coatings. The coatings were produced using the pastes listed in Table 6. A commercially available screen printing medium based on 2-(2-)butoxyethanol was used as the medium.

[0309] Table 6 42 22 September 2025

[0310] P06253 WO

[0311] To produce the coatings, the respective paste was applied to the disc and baked in a chamber oven for 4 minutes. A paste with a viscosity of approximately 3500 mPas and a screen printing screen with a thickness of 110-34 were used for the coating. This resulted in a coating thickness of approximately...

[0312] 3.5 pm.

[0313] Table 7 specifies the thickness of the glass pane to be coated. It was a borosilicate glass pane with a coefficient of thermal expansion of 3.3 x 10⁻⁶ / K.

[0314] The table lists the respective firing temperatures. The table also lists the L*, a*, and b* values ​​of the coated panes. The designation "color side" indicates that the colorimeter is pointed at the coated side of the substrate. The values ​​were measured using SCE. 43 September 22, 2025

[0315] P06253 WO

[0316] The table lists the gloss of the coated lenses. The value 60° indicates the angle at which the gloss was measured. The measurement was taken from the coated side.

[0317] The table lists the optical density of the coated lenses. The indication "through the lens" means that the measurement was taken from the side of the lens, not from the side of the coating.

[0318] The table lists the results of the sclerometer measurement with IO N. "0.5" means that only slight pressure marks are visible on the enamel side in the tested area. "0" means that no changes are visible on the enamel side.

[0319] The table lists the results of the spring hammer test. It indicates the maximum drop height in cm that the sample can withstand without damage.

[0320] The table also provides information on the breaking strength [J]. It was derived from the results of the spring hammer test using the formula

[0321] The calculation is 248.12 g / 1000 * 9.81 * fall height (cm) / 100. Here, 248.12 g is the weight of the falling object and 9.81 m / s is the falling speed.

[0322] The table provides information on flexural strength. Within the scope of this disclosure, flexural strength refers to the strength of the disc, also known as double-ring flexural tensile strength, which was determined according to DEN 1288-5. The index given for flexural strength is the MOR (modulus of rupture) [MPa].

[0323] All tests, including the spring hammer test, the determination of flexural strength and the determination of fracture strength, were carried out on non-prestressed samples.

[0324] Table 7 44 22 September 2025

[0325] P06253 WO

[0326] Table 7 illustrates the advantages of the glass-ceramic material and the coated discs according to the invention by providing information on the layer properties.

[0327] A comparison of the embodiments with both VI and V2 to V5 shows the significant increase in strength and the increase in optical density. 45 22 September 2025

[0328] P06253 WO

[0329] Character description

[0330] The invention is further explained below with reference to a figure. Figure 1 shows the crystal phases β-spodumene, Fei+ determined by XRD for GK5. x Ti2- x O5 mixed crystal and spinel mixed crystal.

[0331] Both the glass-ceramic material according to the invention and a glass or glass-ceramic sheet coated with it, in particular partially, are ideally suited for use in household appliances, especially for decorating an oven window or a fireplace viewing window, or in a vehicle, preferably in the automotive sector, particularly in a composite material, especially for decorating a windshield. A glass or glass-ceramic sheet for a vehicle is generally understood to be a glass sheet for mobile applications, for example, for aircraft and / or automobiles.

[0332] The combination of properties including high optical density, the desired dark color impression for the aforementioned applications, high fracture and flexural strength, also due to well-matched coefficients of expansion of the disc and coating, are the advantage of the present invention.

Claims

46 September 22, 2025 P06253 WO Patent claims 1. Glass-ceramic material comprising a glass phase with a proportion of 1 wt.% to 50 wt.% and a crystalline phase with a proportion of 50 wt.% to 99 wt.% with at least two crystal phases, wherein one of the crystal phases comprises crystallites of mixed solutions from the pseudobrookite system, and wherein the glass-ceramic material has a linear coefficient of thermal expansion CTE20-300 of -2.0 * 10' 6 / K up to 4.0 * 10' 6 / K is, preferably 0 * 10' 6 / K to < 4.0 * 10' 6 / K, especially preferred by 0 * 10' 6 / K to 3.5 * 10' 6 / K exhibits.

2. Glass-ceramic material according to claim 1, wherein the crystalline phase contains β-spodumene and / or high-quartz solid solution and / or ilmenite solid solution and / or spinel solid solution.

3. Glass-ceramic material according to claim 1 or 2, wherein the pseudobrookite mixed crystal contains more iron(II) than iron(III).

4. Glass-ceramic material according to one of claims 1 to 3, characterized in that the average crystal size of the crystallites is in a range of 0.06 pm to 5 pm, preferably in the range of 0.1 pm to 5 pm, preferably in the range of 0.5 pm to 1.2 pm.

5. Glass-ceramic material according to one of claims 1 to 4, characterized in that it has an optical density OD in the VIS range of more than 40 / mm, preferably more than 50 / mm.

6. Glass or glass-ceramic sheet comprising a glass or a glass-ceramic comprising SiCh and Al2O3 and at least one component from the group Li2O, B2O3, comprising at least one coating applied in at least one area of ​​at least one side of the glass sheet with a first coating designed as an enamel layer, wherein the first coating comprises at least one glass-based binder 47 22 September 2025 P06253 WO SiCh comprises at least one glass-ceramic material according to one of claims 1 to 4 as a filler and optionally one or more pigments.

7. Glass or glass-ceramic pane according to claim 6, characterized in that the The disc itself has a thickness between 1 mm and 12 mm, preferably between 2 and 4 mm.

8. Glass or glass-ceramic disc according to one of claims 6 to 7, characterized in that the thickness of the coating is in a range of 1 to 10 pm.

9. Glass or glass-ceramic disc according to any one of claims 6 to 8, wherein the optical density of the coated disc is in a range of 0.2 to 3 for light in the VIS range at a coating thickness of 3.5 pm.

10. Glass or glass-ceramic disc according to any one of claims 6 to 9, wherein the L* coordinate of the CIELAB color space of the coated disc is in a range of 5 to 75, wherein the a* coordinate of the CIELAB color space is in a range of -4 to 1 and / or wherein the b* coordinate of the CIELAB color space is in a range of -2 to 13 when measured from the color side at a reference thickness of the enamel coating layer of 3.5 pm.

11. Glass or glass-ceramic disc according to any one of claims 6 to 10, wherein the gloss of the coated disc at 60° is in a range of 45 GU to 100 GU, preferably up to 70 GU, measured from the coated side.

12. Glass pane according to claims 6 to 11, characterized in that the pane comprises a borosilicate glass, preferably consisting of a borosilicate glass. 48 22 September 2025 P06253 WO 13. Glass pane according to claim 12, characterized in that the glass has a linear coefficient of thermal expansion between 2 * 10' 6 / K and 6 * 10" 6 / K, preferably between 2 * 10' 6 / K and 5.5 * 10' 6 / K exhibits.

14. Composite comprising a glass or glass-ceramic sheet according to one of the Claims 6 to 11 and at least one further glass or glass-ceramic disc, wherein the coating is preferably arranged between the discs.

15. Composite according to claim 14, wherein the pane and the further pane are glass panes.

16. A method for producing the glass-ceramic material according to any one of claims 1 to 5, wherein the method comprises the following steps: c) providing a starting glass, wherein the starting glass has been melted under reducing conditions for 30 min to 2.5 h at 1600 °C to 1650 °C; d) melting the starting glass by thermal treatment at a temperature of more than 1050 °C to 1270 °C for a duration of 3 minutes to 12 hours.

17. A method for producing the coated glass or glass-ceramic disc according to any one of claims 6 to 11, the method comprising the following steps: a) coating a glass or glass-ceramic disc with a paste containing the glass-ceramic material according to at least one of claims 1 to 5, preferably produced according to the method of claim 16, the paste further comprising an organic medium and optionally one or more pigments; b) heat-treating the coated disc at a temperature of 600 °C to 950 °C for a duration of 15 seconds to 30 minutes, preferably 30 seconds to 20 minutes, particularly preferably not more than 15 49 22 September 2025 P06253 WO Minutes.

18. Use of the glass ceramic material according to one of claims 1 to 5 and / or the coated glass or glass ceramic sheet according to at least one of claims 6 to 11 in household appliances, in particular for decorating an oven window or a fireplace viewing window, or in a vehicle, preferably in the automotive sector, in particular in a composite according to claim 14 or 15, in particular for decorating a windshield.

Images