Decorative enamels for automotive glass and related methods

Abstract

The decorative glass article has a glass substrate, a first major surface, and a second major surface disposed opposite the first major surface. The decorative glass article includes a decorative layer adhered to at least a portion of the second major surface. The decorative layer includes a glass flux matrix and a plurality of pores such that the decorative layer exhibits a porosity of at least 5%. The porosity of the decorative layer beneficially prevents the decorative layer from reducing the mechanical strength of the glass substrate while also providing optical performance attributes suitable for a variety of decorative applications, such as use in obscuring automotive glazing.

Description

Description of Related Applications

[0001] This application claims the benefit of priority under 35 U.S.C. Section 119 of U.S. Provisional Patent Application No. 63 / 343,226, filed May 18, 2022, and U.S. Provisional Patent Application No. 63 / 428,536, filed November 29, 2022, the contents of which are relied upon and incorporated herein by reference in their entirety. [Technical field]

[0002] This application relates to decorative enamels for automotive glass, and more particularly to porous decorative enamels. [Background technology]

[0003] Enamel layers are commonly used as decorative and tinting elements on automotive glass, such as windshields, sunroofs and rear windows. As decorative, the enamel typically takes the form of dot gradients and borders along the outer edge of the window glass. The decorative layer can function, for example, to both enhance appearance and protect the underlying adhesive from UV degradation.

[0004] Automotive glass has traditionally been made from thermally strengthened soda-lime-silica glass. Thermal strengthening creates surface compressive stresses that strengthen the glass against mechanical damage. However, due to the stresses and inherent risks of the road, traditional automotive glass must be relatively thick and heavy to achieve the desired level of durability. Such soda-lime-silica glass tends to suffer from several deficiencies from a durability standpoint. Examples of such deficiencies of soda-lime silicate include poor chemical weathering performance, crash performance, and scratch performance.

[0005] Borosilicate glass has been considered for automotive window applications because it has several advantages over soda-lime-silica glass, including improved chemical weathering performance, improved scratch resistance, improved crash performance, and favorably low density. One complication associated with borosilicate glass is that such glasses tend to have a lower coefficient of thermal expansion ("CTE") than that associated with soda-lime-silica glass or aluminosilicate glasses. Such a low coefficient of thermal expansion associated with borosilicate glass would not be compatible with commercially available ceramic enamels. The CTE difference between borosilicate glass and commercially available enamels can reduce the mechanical performance of the windshield and prevent the windshield from having the desired appearance. Summary of the Invention [Problem to be solved by the invention]

[0006] Thus, there is a need for improved enamels for use in combination with borosilicate glasses or other suitable low CTE materials. [Means for solving the problem]

[0007] The present disclosure provides decorative enamels that are particularly suitable for use with borosilicate glasses. The decorative enamels described herein have a thermal expansion coefficient comparable to that of the associated borosilicate glass (e.g., 10×10 -7 / K). The decorative enamels described herein further exhibit favorable mechanical performance attributes when deposited on borosilicate glass, since the decorated glass article will exhibit mechanical strength properties comparable to or better than those associated with undecorated glass articles. The decorative enamels described herein may not reduce the strength of the glass.

[0008] The embodiment (1) of the present disclosure is 55 × 10 -7%. The present invention relates to a glass substrate having a coefficient of thermal expansion ("CTE") of less than or equal to 10×10 K, a first major surface, and a second major surface disposed opposite the first major surface; and a decorative layer adhered to at least a portion of the second major surface, the decorative layer comprising a glass flux matrix, a plurality of low CTE additive particles, and a plurality of pores, the decorative layer comprising greater than 15% by weight of the low CTE additive particles, each of the plurality of low CTE additive particles being greater than 10×10 -7 / K or less, and the decorative layer has a CTE of 15×10 -7 The present invention relates to a decorative glass article having a decorative layer having a CTE within 1 / K.

[0009] Aspect (2) of the present disclosure relates to a decorated glass article according to aspect (1), wherein the decorated glass article has a probability of breakage of less than 10% when subjected to a ring-on-ring test at a load of 60 MPa with a ring diameter of 32 mm.

[0010] In the embodiment (3) of the present disclosure, the CTE of the decorative layer is 55×10 -7 / K or less.

[0011] An embodiment (4) of the present disclosure relates to a decorative glass article according to any of embodiments (1)-(3), wherein each of the plurality of low CTE additive component particles is made from a glass, a glass frit, a glass enamel, a ceramic enamel, a glass ceramic, or a ceramic material.

[0012] An embodiment (5) of the present disclosure relates to a decorated glass article according to any of embodiments (1)-(4), wherein the decorative layer comprises 20% by weight or more and 40% by weight or less of low CTE additive component particles.

[0013] An embodiment (6) of the present disclosure relates to the decorated glass article according to any one of embodiments (1) to (5), wherein the decorative layer comprises 5% by mass or more and 30% by mass or less of a pigment.

[0014] In an embodiment (7) of the present disclosure, the decorative glass article has an L chromaticity in the CIELAB color coordinate system of less than 15.0 when illuminated from a first main surface with a D65 light source.* The present invention relates to a decorative glass article according to any one of aspects (1) to (6), which exhibits a value.

[0015] The eighth aspect of the present disclosure is L * The decorative glass article according to embodiment (7), wherein the value is 10.0 or less.

[0016] Aspect (9) of the present disclosure relates to a decorated glass article according to any of aspects (1) to (8), wherein the decorated glass article exhibits an integrated visible transmittance of 2.0% or less for light from 400 nm to 700 nm normally incident on the first principal surface in the area where the decorative layer covers the second principal surface.

[0017] An aspect (10) of the present disclosure relates to a decorative glass article according to aspect (9), having an integrated visible transmittance of 1.0% or less.

[0018] An embodiment (11) of the present disclosure relates to a decorated glass article according to any one of embodiments (1) to (10), wherein the decorative layer has an average thickness of 20 μm or less.

[0019] An embodiment (12) of the present disclosure relates to a decorated glass article according to any of embodiments (1)-(11), wherein at least one of the plurality of pores has a maximum diameter greater than 1.0 μm.

[0020] An embodiment (13) of the present disclosure relates to a decorated glass article according to any one of embodiments (1) to (12), in which the glass substrate is a curved sheet having a concave surface and a convex surface, and the decorative layer is adhered to the concave surface.

[0021] An embodiment (14) of the present disclosure relates to a decorative glass article according to any of embodiments (1)-(13), wherein the glass flux matrix is ​​made from oxides of Bi, B, Zn, Si, or any combination thereof.

[0022] In an embodiment (15) of the present disclosure, the glass substrate is formed from a borosilicate glass composition, and the borosilicate glass composition is preferably SiO 2 , B 2 O 3 , Al2 O 3 , one or more alkali metal oxides, and one or more divalent cation oxides selected from the group consisting of MgO, CaO, SrO, BaO, and ZnO; 11 mol % or more and 16 mol % or less of B 2 O 3 , 2 mol% or more and 6 mol% or less of Al 2 O 3 and a total amount of Na of 7.0 mol% or more 2 OK 2 O, MgO and CaO, SiO 2 , B 2 O 3 , one or more alkali metal oxides, Al 2 O 3 and the concentration, on an oxide basis, of one or more alkaline earth metal oxides is expressed by the relationship: (R 2 O+R'O)≧Al 2 O 3 , 0.80<(1-[(2R 2 O+2R'O) / (SiO 2 +2Al 2 O 3 +2B 2 O 3 )])<0.93, wherein R 2 The decorative glass article according to any of the aspects (1) to (14), wherein O is the sum of the concentrations of one or more alkali metal oxides and R'O is the sum of the concentrations of one or more alkaline earth metal oxides.

[0023] An embodiment (16) of the present disclosure relates to the decorated glass article according to any one of embodiments (1) to (15), wherein the decorative layer has a glass softening temperature of 650° C. or less.

[0024] An embodiment (17) of the present disclosure relates to a decorative glass article according to any one of embodiments (1) to (16), wherein the thickness of the glass substrate ranges from 2.0 mm to 6.0 mm.

[0025] An embodiment (18) of the present disclosure is a first glass substrate having a first main surface and a second main surface, -7%. The present invention relates to a glass substrate comprising: a first glass substrate formed from a borosilicate glass having a coefficient of thermal expansion ("CTE") of less than or equal to 10×10 / K; a second glass substrate having a third major surface and a fourth major surface; an intermediate layer in contact with the second major surface of the first glass substrate and the third major surface of the second glass substrate; and a first decorative layer adhered to at least a portion of the second major surface of the first glass substrate and in contact with the intermediate layer, the first decorative layer comprising a glass flux matrix, a plurality of low CTE additive component particles, and a plurality of pores, the first decorative layer comprising greater than 15% by weight of the low CTE additive component particles, each of the plurality of low CTE additive component particles being greater than 10×10 -7 / K or less, and the first decorative layer has a CTE of 15×10 of the CTE of the first glass substrate. -7 The glass laminate has a first decorative layer having a first CTE within 0.1 μm / K.

[0026] An embodiment (19) of the present disclosure relates to a glass laminate according to embodiment (18), wherein the second glass substrate is formed from glass having a second composition different from the first composition forming the first glass substrate.

[0027] An embodiment (20) of the present disclosure relates to a glass laminate according to any of embodiments (18)-(19), wherein the second composition comprises a soda-lime silicate composition, an aluminosilicate glass composition, an alkali aluminosilicate glass composition, an alkali-containing borosilicate glass composition, an alkali aluminophosphosilicate glass composition, or an alkali aluminoborosilicate glass composition.

[0028] An aspect (21) of the present disclosure relates to a glass laminate according to any of aspects (18) to (20), wherein the first glass substrate is not chemically strengthened by ion exchange, and the second glass substrate is strengthened by ion exchange.

[0029] An embodiment (22) of the present disclosure relates to a glass laminate according to any of embodiments (18) to (21), wherein the first glass substrate has a first thickness in the range of 2.0 mm to 6.0 mm, and the second glass substrate has a second thickness in the range of 0.1 mm to 1.6 mm.

[0030] The embodiment (23) of the present disclosure further includes a second decorative layer adhered to at least a portion of the third main surface of the second glass substrate and in contact with the intermediate layer, the second decorative layer having a CTE within 10×10 of the CTE of the second glass substrate. -7 The glass laminate according to any of embodiments (18) to (22), having a second CTE within a range of 0.1 to 1.0 μm / K.

[0031] An embodiment (24) of the present disclosure relates to a glass laminate according to any of embodiments (18)-(23), wherein the interlayer is disposed within at least one of the plurality of pores in the first decorative layer.

[0032] In an embodiment (25) of the present disclosure, the first CTE of the first decorative layer is 55×10 -7 / K or less according to any one of aspects (18) to (24).

[0033] An embodiment (26) of the present disclosure relates to a glass laminate according to any of embodiments (18)-(25), wherein each of the plurality of low-CTE additive component particles is made from a glass, a glass frit, a glass enamel, a ceramic enamel, a glass ceramic, or a ceramic material.

[0034] An embodiment (27) of the present disclosure relates to a glass laminate according to any of embodiments (18)-(26), wherein the first decorative layer comprises 20% or more and 40% or less by weight of low CTE additive component particles.

[0035] An embodiment (28) of the present disclosure relates to a glass laminate according to any one of embodiments (18) to (27), wherein the first decorative layer contains 5% or more and 30% or less by weight of a pigment.

[0036] An embodiment (29) of the present disclosure is a glass laminate having an L according to the CIELAB color coordinate system of less than 15.0 when illuminated from the first main surface with a D65 light source. * The glass laminate according to any one of embodiments (18) to (28), wherein the glass laminate exhibits a value.

[0037] An aspect (30) of the present disclosure relates to a glass laminate according to any one of aspects (18) to (29), wherein the glass laminate exhibits an integrated visible transmittance of 2.0% or less for light from 400 nm to 700 nm normally incident on the first main surface.

[0038] In an embodiment (31) of the present disclosure, the first glass substrate is formed from a borosilicate glass composition, and the borosilicate glass composition is preferably SiO 2 , B 2 O 3 , Al 2 O 3 , one or more alkali metal oxides, and one or more divalent cation oxides selected from the group consisting of MgO, CaO, SrO, BaO, and ZnO; 11 mol % or more and 16 mol % or less of B 2 O 3 , 2 mol% or more and 6 mol% or less of Al 2 O 3 and a total amount of Na of 7.0 mol% or more 2 OK 2 O, MgO and CaO, SiO 2 , B 2 O 3 , one or more alkali metal oxides, Al 2 O 3 and the concentration, on an oxide basis, of one or more alkaline earth metal oxides is expressed by the relationship: (R 2 O+R'O)≧Al 2 O 3 , 0.80<(1-[(2R 2 O+2R'O) / (SiO 2 +2Al 2 O 3 +2B 2 O 3 )])<0.93, wherein R 2 The glass laminate according to any one of the embodiments (18) to (30), wherein O is the sum of the concentrations of one or more alkali metal oxides and R'O is the sum of the concentrations of one or more alkaline earth metal oxides.

[0039] An embodiment (32) of the present disclosure is a method of preparing a glass article, comprising the steps of depositing a mixture containing a ceramic enamel and a low CTE additive component on a glass substrate to provide a decorative layer; and curing the decorative layer at a temperature above the glass softening temperature of the decorative layer to provide a glass article containing a plurality of pores and having a diameter of 55×10 -7 / K or less and a CTE of 10 of the glass substrate -7 providing a cured decorative layer having a coefficient of thermal expansion (CTE) within 0.5 / K.

[0040] An embodiment (33) of the present disclosure relates to a method according to embodiment (32), wherein the mixture comprises 40% to 85% by weight of the ceramic enamel and more than 15% by weight of the low-CTE additive component.

[0041] An embodiment (34) of the present disclosure relates to the method according to embodiment (33), wherein the mixture comprises 20% to 40% by weight of the low CTE additive component.

[0042] An embodiment (35) of the present disclosure is a method for producing a cured decorative layer having an L of 10.0 or less when the cured decorative layer is illuminated with a D65 light source. * The method according to any of the aspects (32) to (34), comprising 5% to 30% by weight of pigment, as indicated.

[0043] An embodiment (36) of the present disclosure relates to a method according to any of the embodiments (32)-(35), further comprising shaping the glass substrate such that the glass substrate includes a concave surface onto which the decorative layer is deposited.

[0044] An embodiment (37) of the present disclosure relates to a method according to embodiment (36), wherein curing of the glass substrate and the decorative layer is performed during shaping.

[0045] An embodiment (38) of the present disclosure is a decorative glass article comprising: a glass substrate having a first major surface and a second major surface disposed opposite the first major surface; and a decorative layer adhered to at least a portion of the second major surface, the decorative layer comprising a glass flux matrix and a plurality of pores, the decorative layer having a porosity of 25% or more and 30% or less, the glass substrate having a thickness of 2.1 mm or more, and the decorative layer having a porosity of at least 23×10 of the CTE of the glass substrate. -7 / K, and the decorated glass articles exhibit a B5 value of 55 MPa or greater when at least 10 pieces of the decorated glass articles are subjected to a ring-on-ring test in accordance with ASTM C-1499-03.

[0046] Aspect (39) of the present disclosure relates to a decorative glass article according to aspect (38), wherein the glass substrate is formed from a soda-lime-silicate glass composition.

[0047] An embodiment (40) of the present disclosure relates to a decorative glass article according to any of embodiments (38)-(39), wherein the glass substrate is not chemically strengthened.

[0048] The embodiment (41) of the present disclosure is characterized in that the difference between the CTE of the decorative layer and the CTE of the glass substrate is 15×10 -7 / K or more.

[0049] An embodiment (42) of the present disclosure relates to a decorated glass article according to any of embodiments (38)-(41), wherein the decorative layer comprises 20% or more and 40% or less by weight of low CTE additive component particles.

[0050] An embodiment (43) of the present disclosure relates to a decorative glass article according to embodiment (42), wherein each of the low CTE additive component particles is made from glass, glass frit, glass enamel, ceramic enamel, glass ceramic, or ceramic material.

[0051] An embodiment (44) of the present disclosure relates to a decorated glass article according to any of embodiments (38) to (43), wherein the decorative layer comprises 5% by weight or more of a pigment additive.

[0052] An embodiment (45) of the present disclosure relates to a decorative glass article according to embodiment (44), wherein the pigment additive comprises at least one of a CuCr-based pigment, a MgFe-based pigment, and a FeCrCoNi-based pigment.

[0053] An embodiment (46) of the present disclosure relates to a decorative glass article according to any of embodiments (42)-(45), wherein the low CTE additive component particles and pigment additive, if present, have an average particle size of 10 μm or less.

[0054] An embodiment (47) of the present disclosure relates to a decorative glass article according to any of embodiments (38)-(46), further comprising a second glass substrate and an intermediate layer disposed between the second glass substrate and the second major surface, wherein the polymeric material of the intermediate layer is present in the plurality of pores.

[0055] An embodiment (48) of the present disclosure is a glass article having an L of 10 or less in the area where the decorative layer is disposed thereon. * The decorative glass article according to embodiment (47) exhibits a value.

[0056] An embodiment (49) of the present disclosure relates to a decorated glass article according to any of embodiments (47)-(48), wherein when light from a D65 light source is reflected off of a glass substrate, the light exhibits a maximum ΔE value between two different positions on the glass article on which the decorative layer is disposed, calculated using the CIE76 equation, of 3.0 or less.

[0057] An embodiment (50) of the present disclosure relates to a decorated glass article according to any of embodiments (1)-(17) and (38)-(49), wherein the decorative layer covers 5% or more of the total surface area of ​​the second main face.

[0058] Additional features and advantages are set forth in the following detailed description, and in part will be readily apparent to those skilled in the art from that description, or may be learned by practicing the embodiments as described herein, including the following detailed description, the claims, and the accompanying drawings.

[0059] It is to be understood that both the foregoing general description and the following detailed description are merely exemplary and are intended to provide an overview or framework for understanding the nature and character of the claims. [Brief description of the drawings]

[0060] The accompanying drawings are included to provide a further understanding, and are incorporated in and constitute a part of this specification. The drawings illustrate one or more embodiment(s), and together with the description, serve to explain the principles and operation of the various embodiments. [Figure 1] FIG. 1 is an illustration of a vehicle including an automotive glazing according to one or more embodiments of the present disclosure. [Diagram 2] FIG. 2 is a cross-sectional view of an automotive glazing taken through line 2-2 of FIG. 1 in accordance with one or more embodiments of the present disclosure. [Diagram 3] 1 is a cross-sectional view of a curved laminate with a decorative layer according to one or more embodiments of the present disclosure. [Figure 4] 1 is a flow diagram of a method for manufacturing a decorative glass article and a laminate comprising the same, according to one or more embodiments of the present disclosure; [Diagram 5] 1 is a plot including a Weibull distribution for several example decorative glass articles according to one or more embodiments of the present disclosure. [Figure 6] 1 is a plot of surface elevation measurements used to determine the thickness of a decorative layer of an exemplary decorated glass article, according to one or more embodiments of the present disclosure; [Figure 7A] 1 is a scanning electron microscope image of an exemplary decorated glass article with a porous decorative layer according to one or more embodiments of the present disclosure. [Figure 7B] 1 is a scanning electron microscope image of an exemplary decorated glass article with a porous decorative layer according to one or more embodiments of the present disclosure. [Figure 7C] 1 is a scanning electron microscope image of an exemplary decorated glass article with a non-porous decorative layer according to one or more embodiments of the present disclosure. [Figure 8] 1 is a plot including a Weibull distribution for several example decorative glass articles according to one or more embodiments of the present disclosure. [Figure 9A] 1 is a scanning electron microscope image of a non-porous decorative layer disposed on a soda-lime-silicate glass substrate, according to one or more embodiments of the present disclosure. [Figure 9B] 1 is a scanning electron microscope image of a porous decorative layer disposed on a soda-lime-silicate glass substrate, according to one or more embodiments of the present disclosure. [Figure 9C] 1 is a plot including a Weibull distribution for a number of glass articles including soda-lime-silicate glass substrates, according to one or more embodiments of the present disclosure. [Figure 10A] 1 is a scanning electron microscope image of a porous decorative layer disposed on a borosilicate glass substrate according to one or more embodiments of the present disclosure. [Figure 10B] 1 is a scanning electron microscope image of a porous decorative layer disposed on a borosilicate glass substrate according to one or more embodiments of the present disclosure. [Figure 10C] 1 is a plot including a Weibull distribution for a number of glass articles including borosilicate glass substrates, according to one or more embodiments of the present disclosure. [Figure 11] 1 is a scanning electron microscope image of a porous decorative layer disposed on a borosilicate glass substrate according to one or more embodiments of the present disclosure. [Figure 12A] FIG. 14 is a schematic diagram of a plurality of scanning electron microscope images of glass articles having decorative layers disposed therein, the glass articles including various amounts of porosity, in accordance with one or more embodiments of the present disclosure. [Figure 12B] 12B is a plot of B5 values ​​for a number of glass articles shown in FIG. 12A as a function of porosity of the decorative layer, in accordance with one or more embodiments of the present disclosure. [Figure 13A] 1 is an image of a glass article with a porous decorative layer prior to lamination with a second glass substrate via a polymer interlayer, according to one or more embodiments of the present disclosure; [Figure 13B]13B is an image of the glass article shown in FIG. 13A after lamination with a second glass substrate via a polymer interlayer, according to one or more embodiments of the present disclosure. [Figure 14A] 1 is an image of a glass article formed from a porous decorative layer including porosity-inducing component particles having a d50 particle size of 1.0 μm, according to one or more embodiments of the present disclosure. [Figure 14B] 1 is an image of a glass article formed from a porous decorative layer including porosity-inducing component particles having a d50 particle size of 2.5 μm, according to one or more embodiments of the present disclosure. [Figure 14C] 1 is an image of a glass article formed from a porous decorative layer including porosity-inducing component particles having a d50 particle size of 5.0 μm, according to one or more embodiments of the present disclosure. [Figure 15A] Plots of Weibull B5 and scale values ​​as a function of particle size for the porosity-inducing components for the examples shown in Figures 14A-14C, in accordance with one or more embodiments of the present disclosure. [Figure 15B] 13 is a plot of Weibull B5 and scale values ​​as a function of particle size of the porosity-inducing component for another set of example glass articles, according to one or more embodiments of the present disclosure. [Figure 16] FIG. 15C is a plot showing the integrated light transmittance of samples constructed using the exemplary set of glass articles shown in FIG. 15C both before and after lamination, according to one or more embodiments of the present disclosure. It should be understood that numerous other modifications and examples may be devised by those skilled in the art that fall within the scope and spirit of the principles of the present disclosure. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0061] Referring generally to the drawings, a decorated glass article is described herein that includes a glass substrate and a decorative layer. The decorative layer is porous (e.g., has a porosity of 5% or more, 10% or more, 12% or more, 14% or more, 16% or more, 18% or more, 20% or more, 21% or more, 22% or more, 23% or more, 24% or more, 25% or more, and 30% or less). In an embodiment, the glass substrate has a porosity of 55×10 -7 / K or less (e.g., 50×10 -7 / K or less, 45×10 -7 / K or less, 40×10 -7 / K or less, 35×10 -7 / K or less, 32.5×10 -7 / K or less), a first major surface, and a second major surface disposed opposite the first major surface. A decorative layer may be disposed on the second major surface of the glass substrate and cover a suitable portion of the glass substrate. In embodiments, the decorative layer may occupy a surface area of ​​less than 60%, less than 50%, less than 40%, less than 30%, less than 20%, less than 10%, less than 5%, less than 1%, less than 0.1%, or less than 0.01% of the total surface area of ​​the second major surface. The decorative layer may be less than 23×10 of the CTE of the glass substrate such that the decorative layer does not reduce the mechanical strength of the glass substrate despite being in contact with the glass substrate. -7 / K. The decorative layer may be deposited on the second major surface of the glass substrate in a suitable pattern for decorative or concealing purposes. The relatively low CTE of the decorative layers described herein, as compared to certain existing commercially available enamels, enables the use of various borosilicate glasses in automotive glazing applications, such as components of automotive glazing (e.g., side windows, windshields).

[0062] The decorative layers described herein, when deposited on glass, such as automotive glass, can function as decorative enamels. The decorative enamels can serve an aesthetic purpose, a functional purpose, or both. In general, the decorative frits will have the dual function of providing an attractive appearance and acting as a shield to block visible and ultraviolet light.

[0063] In an embodiment, the decorative layer is formed from a suitable ceramic enamel and a low CTE additive component. Certain existing commercially available ceramic enamels are generally not compatible with low CTE glasses, such as borosilicate glasses, because such enamels have a relatively high CTE compared to such borosilicate glasses. Such a CTE difference can result in a decrease in the strength of the glass (such that the decorated glass article is weaker than the undecorated substrate). Thus, in an embodiment, the decorative layer includes at least 5% by weight (e.g., at least 10% by weight, at least 12% by weight, at least 14% by weight, at least 16% by weight, at least 18% by weight, at least 20% by weight, at least 22% by weight, at least 24% by weight, at least 26% by weight, at least 28% by weight, at least 30% by weight) of the low CTE additive component, thereby matching the CTE of the glass substrate (CTE ガラス ) and the CTE of the decorative layer (CTE d ) is 15×10 -7 / K or less (e.g., 10×10 -7 / K or less, 8×10 -7 / K or less, 8×10 -7 / K or less, 7×10 -7 / K or less, 6×10 -7 / K or less, 5×10 -7 / K or less, 4×10 -7 / K or less, 3×10 -7 / K or less, 2×10 -7 / K or less, 1×10 -7 / K or less, 0.5×10 -7 / K or less, 0.1×10 -7 / K or less, or any other range described herein. Such a CTE match can help prevent defects from forming in the decorative layer during manufacture of the glass article and can enable the decorated glass article to exhibit favorable mechanical strength properties.

[0064] It has been found that the addition of low CTE additive components to ceramic enamels can make the decorative layer porous after the ceramic enamel is fired. The porosity prevents the decorative layer from reducing the strength of the glass substrate and, in some cases, has even been found to increase the strength of the glass substrate. The porosity is introduced during the curing process of the enamel. In embodiments, for example, the addition of low CTE additive components (e.g., in particulate form) and a suitable vehicle to commercially available ceramic enamels results in improved enamels that can be applied to glass substrates by suitable application techniques and then cured to form a porous structure.

[0065] In an aspect, the improved enamels including any of the low CTE additive components described herein may have various properties suitable for automotive glass production. For example, in an embodiment, the improved enamels are compatible with the temperature requirements for bending and laminating a decorative glass article with another glass article in a process to form a laminate. In an embodiment, the uncured improved enamels may be cured before or during the heating step associated with bending a glass substrate into a shape suitable for a glazing application. For example, in an embodiment, the improved enamels may be cured during the heating cycle of the bending process to improve process efficiency. Thus, in an embodiment, the improved enamels have a glass softening temperature that is equal to or lower than the sagging temperature of the glass substrate. In an embodiment, the glass softening temperature of the improved enamels may be equal to or lower than 750° C. (e.g., 725° C. or lower, 700° C. or lower, 675° C. or lower, 650° C. or lower, 625° C. or lower, 600° C. or lower, 575° C. or lower, 550° C. or lower) to facilitate such simultaneous bending and hardening operations.

[0066] After firing and cooling the ceramic enamel on the glass substrate, the decorative layer may have a thickness of 30 μm or less (e.g., 25 μm or less, 1.0 μm or more and 25.0 μm or less, 5.0 μm or more and 25.0 μm or less, 5.0 μm or more and 20.0 μm or less, 5.0 μm or more and 10.0 μm or less). As a result of including low CTE additive components, the decorative layer may also include a porous structure. It has been found that the porosity prevents the decorative layer from reducing the mechanical strength of the glass substrate. Without intending to be bound by theory, it is believed that the porosity reduces the size of the continuous contact area between the glass substrate and the decorative enamel, which reduces the buildup of CTE-induced stresses that occur during the manufacture of the decorated glass article, thereby preventing the formation and propagation of flaws. In embodiments, the porosity of the decorative layers described herein ranges from 5% to 40% (e.g., 15% to 40%, 20% to 40%, 20% to 30%, 25% to 30%). The porosity may also aid in the decorative layer having a desired color appearance when incorporated into a laminate. For example, in embodiments, an interlayer used to attach a decorated glass substrate to another glass substrate may at least partially fill some of the pores in the decorative layer, which may result in a darker appearance of the decorative enamel.

[0067] The decorative enamel may also have optical properties that are favorable for decorative automotive applications. For example, in embodiments, the decorative enamel may have a relatively high blackness (e.g., an L value according to the CIELAB color coordinate system of 20 or less, 15 or less, 5 or less, 2.5 or less) at a thickness of 30 μm or less as described herein. * In embodiments, the decorative layer exhibits an integrated visible transmittance of 2.0% or less (e.g., 1.8% or less, 1.6% or less, 1.4% or less, 1.2% or less, 1.0% or less, 0.8% or less, 0.6% or less, 0.4% or less, 0.2% or less, 0.1% or less) for light from 400 nm to 700 nm normally incident on the glass article. Such low light transmittance helps the decorative layer perform a variety of concealing and decorative functions in automotive applications.

[0068] As used herein, the terms "light transmittance," "percent transmittance," and "transmittance" are used interchangeably and refer to the percentage of light transmitted through an article over the wavelength range of interest. The "integral visible transmittance" for light within a particular wavelength range is calculated according to the following formula:

[0069]

number

[0070] where T(λ) represents the transmission spectrum over the wavelength range and Φ(λ) is equal to the transmittance of the light source used to measure the transmittance.

[0071] As used herein, the term "coefficient of thermal expansion" or CTE means, unless otherwise specified, the value obtained by measuring the expansion of the referenced material between temperatures of 25°C and 300°C.

[0072] Embodiments of decorative glass articles are described herein with respect to a vehicle 100 shown in FIG. 1. The vehicle 100 includes a body 110 defining an interior and at least one opening 120 communicating with the interior. The vehicle 100 further includes an automotive glazing 130, i.e., a window, disposed within the opening 120. The automotive glazing 130 includes at least one ply made from one of the decorative glass articles described herein. The automotive glazing 130 may form a side window, a windshield, a rear window, a window, and a sunroof in the vehicle 100. In some embodiments, the automotive glazing 130 may form an interior partition (not shown) in the interior of the vehicle 100, or may be disposed on the exterior of the vehicle 100, forming, for example, an engine block cover, a headlight cover, a taillight cover, a door panel cover, or a pillar cover. As used herein, vehicle 100 includes automobiles (an example of which is shown in FIG. 1), rolling stock, locomotives, boats, ships, aircraft, helicopters, drones, spacecraft, etc. Additionally, although this disclosure is configured with respect to vehicles, the decorative glass articles described herein may be used in other contexts, such as architectural glazing or bulletproof glazing applications.

[0073] FIG. 2 is a schematic diagram illustrating a cross-sectional view of an automotive glazing 130 taken through line 2-2 shown in FIG. 1 in accordance with one or more embodiments of the present disclosure. As can be seen, the automotive glazing 130 includes a first glass ply 200, a second glass ply 220, and an interlayer 230 disposed between the first and second glass plies 200 and 220. As used herein, the term "glass ply" is used interchangeably with the term "glass substrate." The first glass ply 200 has a first major surface 202, a second major surface 204, and a thickness 206 extending between the first and second major surfaces 202 and 204. The second glass ply 220 has a first major surface 222, a second major surface 224, and a thickness 226 extending between the first and second major surfaces 222 and 224. The interlayer 230 has a thickness 236 and serves to bond the first major surface 222 to the second major surface 204. In an embodiment, the first major surface 202 of the first glass ply 200 forms an exterior surface of the automotive glazing 130 (facing the exterior of the vehicle 100) and the second major surface 224 of the second glass ply 220 forms an interior surface of the automotive glazing 130 (facing the interior of the vehicle 100).

[0074] In an embodiment, the first ply of glass 200 comprises, consists of, or consists essentially of a borosilicate glass composition. As a result, the first ply of glass 200 has a thickness of 55×10 -7 / K or less (e.g., 52.5×10 -7 / K or less, 50×10 -7 / K or less, 47.5×10 -7 / K or less, 45×10 -7 / K or less, 42.5×10 -7 / K or less, 40×10 -7 / K or less, 37.5×10 -7 / K or less, 35×10 -7 / K or less, 32.5×10 -7 / K or less, 32×10 -7 / K or less. Such a CTE range may make the first ply of glass 200 incompatible with existing commercially available enamel decorations.

[0075] In an embodiment, the first ply of glass 200 is made of 60 mol % to 90 mol % SiO 2 , about 1 mol % to about 20 mol % Al 2 O 3 , 7 mol% to 16 mol% B 2 O 3 , 2 mol % to 20 mol % of R 2 O, where R 2 O is Na 2 O, Li 2 O, and K 2 O. For example, in an embodiment, the borosilicate glass composition has about 83.60 mol % SiO 2 , about 1.20 mol% Al 2 O 3 , about 11.60 mol% B 2 O 3 , about 3.00 mol% Na 2 O, and about 0.70 mol % K 2 O, approximately 32 × 10 -7 / K. Such borosilicate glass would be particularly beneficial when the first glass ply 200 constitutes an exterior ply of the automotive glazing 130 (e.g., such that the first major surface 202 is the exterior surface of the automotive glazing 130) because the borosilicate glass may be more thermal shock resistant and more resistant to crack formation from an impact event with road debris (e.g., stones, etc.) than the soda-lime silicate glasses currently used as exterior plies in automotive glazings. Borosilicate glass is known to exhibit unusual cracking behavior and is less prone to forming cracks that propagate radially from the point of impact of debris, which is particularly beneficial for the durability of the automotive glazing.

[0076] In an embodiment, the first glass ply 200 may be formed from any of the glass compositions described in U.S. Provisional Patent Application No. 63 / 123863, filed December 10, 2020, entitled "Fusion Formable Borosilicate Glass Composition and Articles Formed Therefrom," U.S. Provisional Patent Application No. 63 / 183271, filed May 3, 2021, entitled "Fusion Formable Borosilicate Glass Composition and Articles Formed Therefrom," U.S. Provisional Patent Application No. 63 / 183292, filed May 3, 2021, entitled "Glass with Unique Fracture Behavior for Vehicle Windshield," U.S. Provisional Patent Application No. 17 / 363266, filed June 30, 2021, entitled "Glass with Unique Fracture Behavior for Vehicle Windshield," and U.S. Provisional Patent Application No. 17 / 363266, filed June 30, 2021, entitled "Glass with Unique Fracture Behavior for Vehicle Windshield," each of which is incorporated herein by reference in its entirety. It is particularly advantageous for the glass to be made from one of the fusion-formable borosilicate glass compositions described in International Patent Application No. US2021 / 061966, filed December 6, 2021, entitled "Polymer-Based Behavior for Vehicle Windshields." In an embodiment, such a borosilicate glass composition may be made from, in terms of constituent oxides, SiO 2 , B 2 O 3 , Al 2 O 3 , one or more alkali metal oxides, and one or more divalent cation oxides selected from the group consisting of MgO, CaO, SrO, BaO, and ZnO. In an embodiment, the borosilicate glass composition may, for example, contain 11 mol % or more and 16 mol % or less of B. 2 O 3 , 2 mol% or more and 6 mol% or less of Al 2 O 3 and a total amount of Na of 7.0 mol% or more 2 OK 2O, MgO and CaO. SiO 2 , B 2 O 3 , one or more alkali metal oxides, Al 2 O 3 and the concentration, on an oxide basis, of one or more alkaline earth metal oxides is expressed by the relationship: (R 2 O+R'O)≧Al 2 O 3 , and 0.80<(1-[(2R 2 O+2R'O) / (SiO 2 +2Al 2 O 3 +2B 2 O 3 )])<0.93, wherein R 2 where O is the sum of the concentrations of one or more alkali metal oxides and R'O is the sum of the concentrations of one or more alkaline earth metal oxides. Such glasses have been found to exhibit favorable ring cracking behavior that prevents radial propagation of cracks from the impact point.

[0077] In an embodiment, the first ply of glass 200 is made of 74 mol % to 80 mol % SiO 2 , 2.5 mol% to 6 mol% Al 2 O 3 , 11.5 mol% to 14.5 mol% B 2 O 3 , 4.5 mol% to 8 mol% Na 2 O, 0.5 mol% to 3 mol% K 2 O, 0.5 mol % to 2.5 mol % MgO, and 0 mol % to 4 mol % CaO (e.g., such that the total amount of CaO and MgO is less than 5 mol %), -7 / K or higher and 56 x 10 -7 / K or less (e.g., 40×10 -7 / K or more and 50 x 10 -7 / K or less, 42×10 -7 / K or higher and 48 x 10 -7 / K or less, 43×10 -7 / K or higher and 47 x 10 -7The present invention is made from a fusion formable borosilicate glass composition having a CTE of 0.1 to 0.5 μm / K or less. Such a fusion formable glass composition may be made from a fusion formable borosilicate glass composition having a concentration of SiO 2 ≧72 mol%, e.g., SiO 2 ≧72.0, e.g., SiO 2 ≧73.0, e.g., SiO 2 ≥ 74.0, and / or SiO 2 ≦92, e.g., SiO 2 ≦90; (Relationship 2) B 2 O 3 ≧10 mol%, for example, B 2 O 3 ≧10.0, e.g., B 2 O 3 ≥ 10.5, and / or B 2 O 3 ≦20, e.g., B 2 O 3 ≦18; (Relationship 3) (R 2 O+R'O)≧Al 2 O 3 , for example, (R 2 O+R'O)≧(Al 2 O 3 +1), (R 2 O+R'O)≧(Al 2 O 3 +2); and / or (Equation 4) 0.80 ≤ (1-[(2R 2 O+2R'O) / (SiO 2 +2Al 2 O 3 +2B 2 O 3 )])≦0.93(wherein, R 2 SiO in mole percent concentration on an oxide basis that satisfies some (e.g., one or more combinations) or all of the following: O is the sum of the concentrations of one or more alkali metal oxides, and R'O is the sum of the concentrations of one or more divalent cation oxides, if included in the borosilicate glass composition. 2 , B 2 O 3 , one or more alkali metal oxides (R 2 O), Al 2 O 3, and one or more divalent cation oxides R'O. 2 O is, for example, Li 2 O, Na 2 OK 2 O, Rb 2 O, Cs 2 R'O may be the sum of MgO, CaO, SrO, BaO, ZnO, for example. Compositions satisfying relations 1-4 described in this paragraph may exhibit unique fracture behavior in which a ring crack forms around the contact area between the glass and the impact body, tending to prevent radial crack propagation. Such fusion-formed glasses may also exhibit chemical durability, scratch resistance, mechanical strength, and optical performance (e.g., in terms of both light transmission and optical distortion) superior to other borosilicate glasses. Examples of such glass compositions are provided herein.

[0078] Still referring to FIG. 2 , in embodiments, the second ply of glass 220 comprises, consists of, or consists essentially of a second glass composition that is different from the composition of glass used to form the first ply of glass 200. In embodiments, the second glass composition comprises a soda-lime silicate composition, an aluminosilicate glass composition, an alkali aluminosilicate glass composition, an alkali-containing borosilicate glass composition, an alkali aluminophosphosilicate glass composition, or an alkali aluminoborosilicate glass composition. In embodiments, the second ply of glass 220 is made from one of the boroaluminosilicate glass compositions described in U.S. Provisional Patent Application No. 63 / 318,221, filed March 9, 2022, entitled “Boroaluminosilicate Glass Composition having High Fusion Flow Rate and Advantaged Pair Shaping Temperature.” In an embodiment, the second ply of glass 220 is formed from one of the glass compositions described in U.S. Patent Application No. 16 / 002,276, filed June 7, 2018, entitled "Automotive Glass Compositions, Articles, and Hybrid Laminates," or U.S. Patent No. 10,125,044, filed November 14, 2014, entitled "Ion Exchangeable High Damage Resistance Glasses," the contents of each of which are incorporated herein by reference in their entirety.

[0079] Regardless of the particular compositions used to form the first and second plies of glass 200 and 220, embodiments are contemplated in which neither the first ply of glass 210 nor the second ply of glass 220 is strengthened (e.g., chemically, thermally, or mechanically). Embodiments are also contemplated in which at least one of the first and second plies of glass 210 and 220 is strengthened (e.g., chemically, thermally, or mechanically). In embodiments, for example, the second ply of glass 220 is chemically strengthened (e.g., when made from a suitable alkali aluminosilicate glass composition) and the first ply of glass 200 is not strengthened (but may be annealed, if desired) and exhibits a surface compressive stress of less than about 3 MPa, about 2.5 MPa or less, 2 MPa or less, 1.5 MPa or less, 1 MPa or less, or about 0.5 MPa or less. Such embodiments can help reduce the mass of automotive glazing while still providing favorable mechanical strength and meeting various regulatory requirements associated with automotive applications. Embodiments are contemplated in which both the first ply of glass 200 and the second ply of glass 220 are reinforced.

[0080] Turning now to the thickness of the components of the automotive glazing 130, in embodiments, the first thickness 206 is at least 0.5 mm, at least 1 mm, at least 2 mm, at least 3 mm, at least 3.3 mm, or at least 3.8 mm.In one or more embodiments, the first thickness is from about 0.1 mm to about 6 mm, 0.2 mm to about 6 mm, 0.3 mm to about 6 mm, 0.4 mm to about 6 mm, 0.5 mm to about 6 mm, 0.6 mm to about 6 mm, 0.7 mm to about 6 mm, 0.8 mm to about 6 mm, 0.9 mm to about 6 mm, 1 mm to about 6 mm, 1.1 mm to about 6 mm, 1.2 mm to about 6 mm, 1.3 mm to about 6 mm, 1.4 mm to about 6 mm, 1.5 mm to about 6 mm, 1.6 mm to about 6 mm, about 1.8 mm to about 6 mm, about 2 mm to about 6 mm, about 2.2 mm to about 6 mm. , about 2.4mm to about 6mm, about 2.6mm to about 6mm, about 2.8mm to about 6mm, about 3mm to about 6mm, about 3.1mm to about 6mm, about 3.2mm to about 6mm, about 3.3mm to about 6mm, about 3.4mm to about 6mm, about 3.5mm to about 6mm, about 3.6mm to about 6mm, about 3.7mm to about 6mm, about 3.8mm to about 6mm, about 3.9mm to about 6mm, about 4mm to about 6mm, about 4.2mm to about 6mm, about 4.4mm to about 6mm, about 4.5mm to about 6mm, about 4.6mm to about 6mm, about 4.8mm to about 6mm, about 5mm to about 6mm, about 6mm to about 6mm, about 7mm to about 6mm, about 8mm to about 6mm, about 9mm to about 6mm, about 10mm to about 6mm, about 11mm to about 6mm, about 12mm to about 6mm, about 13mm to about 6mm, about 14mm to about 6mm, about 15mm to about 6mm, about 16mm to about 6mm, about 17mm to about 6mm, about 18mm to about 6mm, about 19mm to about 6mm, about 20mm to about 6mm, about 21mm to about 6mm, about 22mm to about 6mm, about 23mm to about 6mm, about 24mm to about 6mm, about 25mm to about 6mm, about 26mm to about 6mm, about 27mm to about 6mm, about 28mm to about 6mm, about 29mm to about 6mm, about 30mm to about 6mm, about 31 from about 6 mm, from about 5.2 mm to about 6 mm, from about 5.4 mm to about 6 mm, from about 5.5 mm to about 6 mm, from about 5.6 mm to about 6 mm, from about 5.8 mm to about 6 mm, from about 1.6 mm to about 5.8 mm, from about 1.6 mm to about 5.6 mm, from about 1.6 mm to about 5.5 mm, from about 1.6 mm to about 5.4 mm, from about 1.6 mm to about 5.2 mm, from about 1.6 mm to about 5 mm, from about 1.6 mm to about 4.8 mm, from about 1.6 mm to about 4.6 mm, from about 1.6 mm to about 4.4 mm, from about 1.6 mm to about 4.2 mm, from about 1.6 mm to about 4 mm, from about 1.6 mm to about 3.9 mm, from about 1.6 mm to about 3.8 mm, from about 1.6 mm to about 3.7 mm, from about 1.6 mm to about 3.6 mm, from about 1.6 mm to about 3.5 mm, from about 1.6 mm to about 3.4 mm, from about 1.6 mm to about 3.3 mm, from about 1.6 mm to about 3.2 mm, from about 1.6 mm to about 3.1 mm, from about 1.6 mm to about 3 mm, from about 1.6 mm to about 2.8 mm, from about 1.6 mm to about 2.6 mm, from about 1.6 mm to about 2.4 mm, from about 1.6 mm to about 2.2 mm, from about 1.6 mm to about 2 mm, from about 1.6 mm to about 1.8 mm, from about 3 mm to about 5 mm, or from about 3 mm to about 4 mm.

[0081] In an embodiment, the thickness 226 of the second ply of glass 220 is less than the thickness 206. In an embodiment, the thickness is 2.0 mm or less (e.g., 0.1 mm to 2.0 mm, 0.1 mm to 1.8 mm, 0.1 mm to 1.6 mm, 0.5 mm to 1.5 mm, 0.7 mm to 1.4 mm, 0.7 mm to 1.2 mm, 0.7 mm to 1.1 mm). In an embodiment, the total glass thickness (i.e., thickness 226 plus thickness 206) is 8 mm or less, 7 mm or less, 6.5 mm or less, 6 mm or less, 5.5 mm or less, or 5 mm or less. In an embodiment, the lower limit of the total glass thickness is about 2 mm.

[0082] The interlayer 230 bonds the second major surface 204 of the first glass ply 200 to the first major surface 222 of the second glass ply 220. In embodiments, the interlayer 230 is made from a polymer such as polyvinyl butyral (PVB), acoustic PVB (APVB), ionomer, ethylene vinyl acetate (EVA), and at least one of thermoplastic polyurethane (TPU), polyester (PE), polyethylene terephthalate (PET), and the like. The thickness 236 of the interlayer 230 may range from about 0.5 mm to about 2.5 mm, particularly about 0.7 mm to about 1.5 mm. In other embodiments, the thickness 236 may be less than 0.5 mm or greater than 2.5 mm. Additionally, in embodiments, the interlayer 230 may include multiple polymer layers or films that provide various functionalities. For example, in embodiments, interlayer 230 may incorporate at least one of a display, solar insulation, sound deadening, antenna, anti-glare treatment, or anti-reflective treatment, among others. In particular embodiments, interlayer 230 is modified to provide ultraviolet (UV) absorption, infrared (IR) absorption, IR reflection, acoustic control / attenuation, adhesion promotion, and color tint. Interlayer 230 can be modified with suitable additives, such as dyes, pigments, dopants, etc., to impart desired properties.

[0083] In embodiments, at least one of the first and second plies of glass 200 and 220 may be provided with a functional or decorative coating in addition to the interlayer 230. Such functional or decorative coating may be deposited on any of the first major surface 202, the second major surface 204, the first major surface 222, and the second major surface 224. In embodiments, the coating is at least one of an infrared reflective (IRR) coating, a frit, an anti-reflective coating, or a pigmented coating. In an exemplary embodiment of an IRR, the second major surface 204 of the first ply of glass 200 or the first major surface 222 of the second ply of glass 220 is coated with an infrared reflective film and, optionally, one or more layers of a transparent dielectric film. In embodiments, the infrared reflective film is made of a highly conductive metal, such as silver, gold, or copper, which reduces the transfer of heat through the automotive glazing. In embodiments, an optional dielectric film can be used to prevent reflection of the infrared reflective film and to control other properties and characteristics of the coating, such as color and durability. In embodiments, the dielectric film is made from one or more oxides of zinc, tin, indium, bismuth, and titanium, among others. In an exemplary embodiment, the IRR coating includes one or two silver layers, each sandwiched between two layers of transparent dielectric film. In embodiments, the IRR coating is applied, for example, using physical or chemical vapor deposition methods, or by lamination.

[0084] In embodiments, at least one of the first ply of glass 200 and the second ply of glass 220 includes a decorative layer disposed thereon. In the illustrated embodiment, for example, the first decorative layer 240 is disposed on the first major surface 222 of the second ply of glass 220, and the second decorative layer 250 is disposed on the second major surface 204 of the first ply of glass 200. Such a decorative layer may serve to protect an adhesive used to attach the automotive glazing 130 to the aperture 120 from degradation due to exposure to ultraviolet light. Providing the first and second decorative layers 240 and 250 on the inner surface of the laminate may be beneficial in that they may serve to protect, for example, the IRR coating from mechanical degradation and / or oxidation. Additionally, disposing first and second decorative layers 240 and 250 on second major surface 204 and first major surface 222 may also help hide any IRR film or other components (e.g., conductive elements associated with a defogging system) embedded between first ply of glass 200 and second ply of glass 220. Multiple decorative bands are particularly beneficial in providing a desired aesthetic appearance when first ply of glass 200 and second ply of glass 220 are fabricated from glass of different compositions and / or thicknesses.

[0085] As described herein, embodiments are contemplated in which the first ply of glass 200 and the second ply of glass 220 are formed from different compositions. For example, in an embodiment, the first ply of glass 200 is 55×10 -7 / K or less (e.g., 52.5×10 -7 / K or less, 50×10 -7 / K or less, 47.5×10 -7 / K or less, 45×10 -7 / K or less, 42.5×10 -7 / K or less, 40×10 -7 / K or less, 37.5×10 -7 / K or less, 35×10 -7 / K or less, 32.5×10 -7 / K or less, 32×10 -7 / K or less). In such embodiments, the second ply of glass 220 is made of a borosilicate glass composition having a CTE greater than the CTE of the borosilicate glass composition (e.g., 60×10 -7 / K or higher, 60×10 -7 / K or higher and 120 x 10 -7 / K or less, 70×10 -7 / K or higher and 120 x 10 -7 / K or less, 80×10 -7 / K or higher and 120 x 10 -7 1. The first and second plies of glass 200 and 220 may be made of a soda-lime silicate glass or a chemically strengthenable alkali aluminosilicate glass composition having a CTE of at least 5×10 -7 / K (e.g., at least 5 × 10 -7 / K, at least 10 × 10 -7 / K, at least 20 × 10 -7 / K, at least 25 × 10 -7 / K, at least 30 × 10 -7 / K, at least 35 × 10 -7 / K, at least 40 × 10 -7 / K, at least 40 × 10 -7 / K, at least 45 × 10 -7 / K, at least 50 × 10 -7 For example, the first ply of glass 200 may differ from the first ply of glass 200 by approximately 32×10 -7 2. The second ply of glass 220 is made of glass having a first CTE of about 90×10 -7 Consider an example in which the first ply of glass 200 is made of glass having a second CTE of about 45×10 -7 2. The second ply of glass 220 is made of glass having a first CTE of about 90×10 -7 Another example may be made from a glass having a second CTE of 0.15 / K.

[0086] In an embodiment, the first and second decorative layers 240 and 250 are 10×10 of the CTE of the glass plies to which they are laminated.-7 Preferably, the first decorative layer 240 is made from a material having a CTE within 10×10 / K of the CTE of the second ply of glass 220. -7 / K, and the second decorative layer 250 has a first CTE within 10×10 of the CTE of the first glass ply 200. -7 / K。 As described herein, the first and second plies of glass 200 and 220 may be formed from glasses having substantially different CTEs, and the first and second decorative layers 240 and 250 may be made from different materials.

[0087] In an embodiment, the first decorative layer 240 is formed from a commercially available ceramic enamel or glass frit. In an embodiment, the first decorative layer 240 is formed from a frit designed to be ion-exchangeable. That is, the frit can be applied to the ion-exchangeable glass before it undergoes the ion-exchange process. Such frits are made to allow for the exchange of ions between the glass and the process bath. In an embodiment, the frit is Bi-Si-B alkaline, Zn-based Bi-based, Bi-Zn-based, Bi-based, Bi-free or low Bi-based Si-Zn-B-Ti-based, Si-Bi-Zn-B-alkali-based, and / or Si-Bi-Ti-B-Zn-alkali-based, among others. One example of an ion-exchangeable frit with colorants is 45.11 mol % Bi 2 O 3 , 20.61 mol% SiO 2 , 13.56 mol% Cr 2 O 3 , 5.11 mol% CuO, 3.48 mol% MnO, 3.07 mol% ZnO, 2.35 mol% B 2 O 3 , 1.68 mol% TiO 2 , 1.60 mol% Na 2 O, 1.50 mol% Li 2 O, 0.91 mol% K 2 O, 0.51 mol% Al 2 O 3 , 0.15 mol% P 2 O5 , 0.079 mol% SO 3 , 0.076 mol% BaO, 0.062 mol% ZrO 2 , 0.060 mol% Fe 2 O 3 , 0.044 mol% MoO 3 , 0.048 mol% CaO, 0.018 mol% Nb 2 O 5 , 0.006 mol % Cl, and 0.012 mol % SrO. Other examples of ion-exchangeable frits are disclosed in International Patent Application US2020 / 28176, filed April 15, 2022, U.S. Patent No. 9,346,708 B2 (Application No. 13 / 464,493, filed May 4, 2012), and U.S. Patent Application Publication No. 2016 / 0002104 A1 (Application No. 14 / 768,832, filed August 19, 2015), entitled "Filled Pore Decorative Layer for Ion Exchangeable and Automotive Glass," each of which is incorporated herein by reference in its entirety.

[0088] In embodiments, the first decorative layer 240 may include a colorant coating including an ink, such as an organic ink, (e.g., instead of or in addition to the enamel / frit-based components described in the previous paragraph). In embodiments particularly suited to such a colorant coating, the colorant coating may be applied to the first major surface 222 or the second major surface 224. Advantageously, such a colorant coating may be applied to the second ply of glass 220 while the second ply of glass 220 is in a planar configuration, and the second ply of glass 220 may then be cold-formed into a curved configuration without destroying the colorant coating, e.g., the organic ink coating. In an embodiment, the colorant coating includes at least one pigment, at least one inorganic filler, and a binder including an alkoxysilane-functionalized isocyanurate or an alkoxysilane-functionalized biuret. Examples of such colorant coatings are described in EP 2 617 690 B1, which is incorporated herein by reference in its entirety. Other suitable colorant coatings and methods of applying the colorant coatings are described in U.S. Patent Application Publication No. 2020 / 0171800A1 (Application No. 16 / 613010, filed November 12, 2019), and U.S. Patent No. 9,724,727 (Application No. 14 / 618398, filed February 10, 2015), both of which are hereby incorporated by reference in their entirety.

[0089] 2, given the relatively low CTE of the first ply of glass 200, certain existing commercially available enamels are not suitable for depositing and curing thereon as the second decorative layer 250. Certain existing decorative enamels have a viscosity of approximately 80×10 -7 / K, or a CTE that is substantially different than the CTE of the first ply of glass 200 according to some embodiments described herein. Applicant has found that such existing decorative enamels, when deposited and cured on the borosilicate glass described herein, exhibit cracking due to the CTE mismatch, thereby reducing the appearance and mechanical strength of the automotive glazing 130.

[0090] In view of the above, the second decorative layer 250 is made of an enamel that has been modified by the addition of one or more low CTE additive components. As a result of the addition of one or more low CTE additive components, the second decorative layer 250 has a CTE that is greater than or equal to the CTE of the first ply of glass 200 (CTE g ) 10×10 -7 / K CTE (CTE d In some embodiments, 0≦|CTE g -CTE d |≦10, 0≦| CTE g -CTE d |≦9, 0≦| CTE g -CTE d |≦8, 0≦| CTE g -CTE d |≦7, 0≦| CTE g -CTE d |≦6, 0≦| CTE g -CTE d |≦5, 0≦| CTE g -CTE d |≦4, 0≦| CTE g -CTE d |≦3, 0≦| CTE g -CTE d |≦2, 0≦| CTE g -CTE d |≦1, 0≦| CTE g -CTE d |≦0.5, 0≦| CTE g -CTE d |≦0.25, 0≦|CTE g -CTE d |≦0.20, 0≦|CTE g -CTE d |≦0.15, 0≦|CTE g -CTE d |≦0.1, 0≦| CTE g -CTE d |≦0.05. In an embodiment, CTE d ≦55×10 -7 / K (e.g., 20×10 -7 / K≦CTE d ≦55×10 -7 / K, 20×10-7 / K≦CTE d ≦50×10 -7 / K, 20×10 -7 / K≦CTE d ≦45×10 -7 / K, 20×10 -7 / K≦CTE d ≦40×10 -7 / K, 20×10 -7 / K≦CTE d ≦35×10 -7 / K, 20×10 -7 / K≦CTE d ≦32.5×10 -7 / K, 35×10 -7 / K≦CTE d ≦50×10 -7 / K, 40×10 -7 / K≦CTE d ≦50×10 -7 / K, and any intervening ranges). As discussed herein, configuring the second decorative layer 250 to have a CTE close to that of the first ply of glass 200 prevents cracks from forming in the second decorative layer 250 during manufacture of the automotive glazing 130, and also prevents the incorporation of the second decorative layer 250 from reducing the mechanical strength of the first ply of glass 200.

[0091] In embodiments, the second decorative layer 250 is formed by modifying a commercially available enamel with any of the low CTE additive components described herein. In embodiments, the commercially available enamel includes a glass or ceramic enamel with a glass frit component, a stain component, and, optionally, an additive component. The glass frit component determines various characteristics of the second decorative layer 250, including mechanical strength and required firing conditions. In embodiments, the glass frit includes one or more of Bi, B, Zn, or Si oxides. The glass frit can be characterized by the presence of Bi, B, Zn, or Si oxide as a major component. In some embodiments, the glass frit has 1 wt%, 5 wt%, or 10 wt% or more of Bi, B, Zn, or Si oxide. In some embodiments, the glass frit has less than 1 mol% Na 2 O, less than 10 mol% Fe 2 O 3 or less than 25 mol % P 2 O 5 In some embodiments, the glass frit comprises Na 2 O, Fe 2 O 3 , or P 2 O 5In embodiments, the dye component is included in the glass frit and includes one or more of Cu, Co, Fe, Ni, Mn, or Cr oxides. In some embodiments, the dye component includes non-Fe oxides or does not include Fe oxides. Examples of suitable ceramic enamels are available from Ferro Corporation (Mayfield Heights, Ohio), including Product No. 14316 (matte black, bismuth-based frit system with a wide firing range of 570-640°C in 6 minutes and a relatively high melting point) and Product No. VPS4100 (a black enamel that can be fired at 630-650°C). The enamel can be black, white, or any color, such as red, deep blue, blue, green, brown, orange, purple, yellow. Commercially available enamels can be dispersed in a suitable medium to form a paste that is applied to the first ply of glass 200. In embodiments, the medium is made of an oil or organic resin suitable for drying by evaporating the solvent.

[0092] In an embodiment, the low CTE additive component is added to the commercially available enamel as loose particles of a suitable low CTE material. The addition of the low CTE additive component serves not only to lower the CTE of the enamel but also to impart porosity to the resulting second decorative layer 250 after hardening. In an embodiment, the second decorative layer 250 comprises, after hardening, 15% to 50% by weight (e.g., 15% to 45%, 20% to 45%, 20% to 40%, 25% to 45%, 25% to 40%) of the low CTE additive component, and thus the second decorative layer 250 comprises 40% to about 85% by weight (e.g., 50% to 85%, 50% to 80%, 50% to 75%, 50% to 70%) of the enamel. The enamel can be about 40% by weight, about 45% by weight, about 50% by weight, about 55% by weight, about 60% by weight, about 65% by weight, about 70% by weight, about 75% by weight, about 80% by weight, or about 85% by weight of the second decorative layer 250.

[0093] The second decorative layer 250 may include a mixture of ceramic enamel and low CTE additive particles prior to curing. In an embodiment, the low CTE additive particles have an average particle size of 100 μm or less (e.g., 50 μm or less, 40 μm or less, 30 μm or less, 20 μm or less). It has been found that the size of the additive particles affects the porosity of the second decorative layer 250 after curing. The low CTE additive particles prevent densification of the enamel around them during sintering, resulting in a porous structure.

[0094] In embodiments, the low CTE additive component is present as filler particles in the second decorative layer 250. The materials forming the low CTE additive component may have a higher melting point or softening temperature than those associated with the frit component in the enamel.

[0095] A variety of suitable materials for the low CTE additive component particles are contemplated within the scope of the present disclosure. In an embodiment, the low CTE additive component is a 10×10 -7 / K or less (e.g., 5×10 -7 / K or less, 0×10 -7 / K or less, -5×10 -7 / K or less, -10×10 -7 / K or less, -50×10 -7 / K or less, -100×10 -7 / K or less. It has been found that the CTE of the second decorative layer 250 after curing is approximately a weighted average of all of the components. Thus, the CTE of the particular low CTE additive component selected will determine the mass percentage required to achieve the desired CTE. In embodiments, the refractive index of the low CTE additive component is greater than or equal to 1.5 and less than or equal to 1.6. In embodiments, the refractive index of the low CTE additive component is greater than 1.6. A higher refractive index would be preferred to maintain a higher opacity of the decorative layer.

[0096] In embodiments, the low CTE additive component comprises a ceramic or glass-ceramic material having a CTE within any of the ranges described herein. An example of a ceramic has a CTE of approximately -10×10 -7Another example of a ceramic is the beta-eucryptite ceramic 118VTC developed by Corning® Incorporated, which has a CTE equal to -10×10 / K. -7 / K. Suitable glass-ceramic materials include aluminum titanate ceramics with CTEs of approximately 0×10 -7 and KeraBlack® Plus ceramics sold by EuroKera SNC, which have a CTE of 0.15 to 0.5 μm / K. In embodiments, the low CTE additive component has a negative CTE. Such negative CTE materials may include Bi-Ni-Fe-oxide, Zr-W-oxide, and other suitable materials.

[0097] In addition to the CTE, the low CTE additive component may be selected so that the resulting second decorative layer 250 has a desired opacity. The low CTE additive component may be selected, for example, to absorb light in the visible spectrum (on average) (e.g., at least 50% of the light, at least 60% of the light, at least 70% of the light, at least 80% of the light, at least 90% of the light). In embodiments, the low CTE additive component may be selected so that the second decorative layer 250 exhibits a high blackness (e.g., an L of 20 or less, 18 or less, 16 or less, 14 or less, 13 or less, 12 or less, 10 or less, 8 or less, 6 or less, 5 or less) when illuminated by a D65 light source at an illumination angle of 0°. * The L described herein is selected to have a value. * Values ​​assume a 2° standard observer.

[0098] In embodiments, the enamel may exhibit a blackness outside this range if it is only modified by the addition of the low CTE additive component. For example, the 118VTC ceramic described above tends to exhibit a white color and a low refractive index. In such cases, suitable pigment particles can be further added to the enamel to give the desired appearance. In embodiments, the pigment particles are added in an amount equal to or less than the amount of the low CTE additive component. The pigment may also be included in the base ceramic enamel (e.g., as a dye component). In embodiments, the pigment, if included, is added such that the pigment is present in an amount of 0% to 50% by weight of the second decorative layer 250 when cured (e.g., 0% to 40% by weight, 0% to 30% by weight, 5% to 30% by weight, 5% to 20% by weight). Examples of suitable pigments include B1G pigment, 30C965 (CuCr-based pigment), and 20F944 (MgFe-based pigment) from Shepherd (Cincinnati, OH), and V7709 (CuCr-based pigment) and 240137 (FeCrCoNi-based pigment) from Ferro Corporation (Mayfield Heights, OH). The pigments can be black, blue, green, brown, orange, purple, yellow, or metallic variations thereof. In various embodiments, the pigment is the same or a similar color as the enamel (e.g., the pigment and enamel differ from each other by less than 5 a when illuminated by a D65 light source at an illumination angle of 0°). * and b * value).

[0099] In embodiments, pigments having the following main components are selected to obtain the desired colors, for example: black (CuCrFe, CrFe, manganese ferrite spinel, FeCrCoNi), blue (cobalt aluminate, cobalt chromite spinel, CoZnCrAl), green (cobalt titanate green spinel), brown (manganese antimony titanium bufftil, zinc iron chromite brown spinel, iron titanium brown spinel), orange (zinc tin rutile), purple (cobalt phosphate), yellow (nickel antimony titanium yellow rutile, niobium sulfur tin zinc oxide), and metallic aspects (titanate, titanate and tin oxide, or mica flakes covered with iron oxide).

[0100] Applicants have found that the introduction of the low CTE additive and pigment (if present) into the enamel introduces a level of porosity into the second decorative layer 250 after curing. The level of porosity is affected by the frit composition, particle size, the amount of low CTE additive and pigment added, and the firing temperature. Without intending to be bound by theory, it is believed that a greater amount of low CTE additive or a lower firing temperature will result in increased porosity. As described herein, at least some porosity in the second decorative layer 250 is desirable, particularly when the CTE of the second decorative layer 250 is at least 5×10 -7 / K is different from that of the first glass ply 200 (5≦|CTE g -CTE d |≦10), has been found to help increase the mechanical strength of the automotive glazing 130. It is believed that porosity beneficially helps reduce thermally induced stresses caused by CTE mismatch, thereby reducing the likelihood of cracking and improving adhesion and mechanical durability. Porosity can be measured, for example, using a scanning electron microscope (SEM) and comparing the percentage of surface occupied by pores to the total surface. In various embodiments, the porous inorganic layer can have a porosity of at least about 15%, 20%, 40%, 50%, 60%, or more (e.g., 25% to 30%).

[0101] A relatively high level of porosity in the second decorative layer 250 may tend to reduce the cohesion of the second decorative layer 250 to the first glass ply 200, which may reduce scratch resistance and color strength. For example, it has been observed that if the second decorative layer 250 is porous, the second decorative layer 250 may exhibit a gray appearance after firing, even if the enamel is initially black. It has been found that this grayness is reduced after lamination due to interaction with the material of the interlayer 230 (e.g., the polymeric material may flow at least to some extent into some of the pores during lamination, resulting in the automotive glazing 130 having a desired appearance).

[0102] While the embodiment depicted in Figure 2 depicts the automotive glazing 130 as a flat structure (e.g., where the first and second glass plies 200 and 220 are planar in shape), it should be understood that embodiments in which the automotive glazing 130 has a curved shape are also contemplated and within the scope of the present disclosure. In embodiments, the automotive glazing 130 exhibits at least one curvature along at least a first axis having a radius of curvature in the range of 300 mm to about 10 m. In embodiments, the automotive glazing 130 exhibits at least one curvature along a second axis transverse to, and in particular perpendicular to, the first axis having a radius of curvature in the range of 300 mm to about 10 m.

[0103] In embodiments, the curvature is introduced into at least one of the first ply of glass 200 and the second ply of glass 220 by a thermal process. The thermal process may include a drooping process, using gravity to shape the first ply of glass 200 or the first and second plies of glass 200 and 220 when heated. In a drooping process, a ply of glass, such as the first ply of glass 200, is placed on a mold having an open interior, heated in a furnace (e.g., a box furnace, or a glass annealing furnace), and allowed to gradually droop under the influence of gravity into the open interior of the mold. In one or more embodiments, the thermal process may include a pressing process, using a mold to shape the first ply of glass 200 or the first and second plies of glass 200 and 220 when or while heated. In some embodiments, two plies of glass, such as the first and second plies of glass 200 and 220, are formed together in a "pair forming" process. In such a process, one ply of glass is placed over another ply of glass to form a laminate (which may also include an intervening release layer), which is placed into a mold. In embodiments, to facilitate the co-molding process, the second ply of glass 220, which in some embodiments is used as the inner and / or thinner ply of glass, has a higher co-molding temperature (10° C.) than that of the first ply of glass 200. 11 (temperature in poise).

[0104] In one or more embodiments, the mold used during sagging may have an open interior for use in the sagging process. Both the laminate and the mold are heated by placing them in a furnace, and the laminate is gradually heated to the bending or sagging temperature of the glass plies. During this process, the plies are formed together into a curved shape. 11 Beneficially, the viscosity curves of at least some of the borosilicate glass compositions made herein with poise viscosities are similar to those of the glasses used for the second ply of glass 220, allowing existing equipment and technology to be utilized.

[0105] According to an exemplary embodiment, the time and temperature of heating is selected to obtain the desired degree of curvature and final shape. The one or two glass plies are then removed from the oven and cooled. For paired formed glass plies, the two glass plies are separated and reassembled with an interlayer, such as interlayer 230, disposed between the glass plies, and heated, e.g., under vacuum, to seal the glass plies and interlayer together into a laminate.

[0106] In embodiments, only one of the glass plies (e.g., the first glass ply 200) is curved using heat (e.g., by a sagging or pressing process) and the other glass ply (e.g., the second glass ply 220) is curved using a cold-forming process by pressing the glass ply at a temperature below the softening temperature of the glass composition (specifically, at a temperature below 200° C., below 100° C., below 50° C., or at room temperature) to curve it to match the already curved glass ply. The pressure to cold-form the glass ply to the other glass ply may be applied, for example, by a vacuum, a mechanical press, or one or more clamps. The cold-formed glass ply may be held in conformity with the curved glass ply by an interlayer and / or by being mechanically fastened or otherwise bonded thereto.

[0107] In an embodiment, an improved enamel that is cured into the second decorative layer 250 as described herein is deposited on the first ply of glass 200 before the first ply of glass 200 is bent. As described herein, the enamel used to form the second decorative layer 250 may have a softening temperature of about 700° C. or less, about 650° C. or less, about 600° C. or less, about 570° C. or less, about 550° C. or less, about 525° C. or less, about 500° C. or less, about 475° C. or less, or about 450° C. Typical bending temperatures (e.g., 10° C. or less) used for the first ply of glass 200 may be about 100° C. or less. 11The temperature in poise) may be at or above the softening temperature associated with the enamel in the second decorative layer 250. Therefore, the enamel may be baked and fused to the second major surface 204 during the bending process to form the second decorative layer 250, thereby providing process efficiency.

[0108] FIG. 3 illustrates an exemplary embodiment of a curved glass laminate 300. The curved glass laminate 300 is similar in construction to the automotive glazing 130 described herein with respect to FIGS. 1-2, which are indicated by the incorporation of like reference numerals. As can be seen in FIG. 3, the second major surface 204 of the first glass ply 200 has a first depth of curvature 310, defined as the maximum depth from the plane of the second major surface 204 (dashed line). In embodiments in which the second glass ply 220 is curved, the second major surface 224 of the second glass ply 220 has a second depth of curvature 320, defined as the maximum depth from the plane of the second major surface 224 (dashed line).

[0109] In an embodiment, one or both of the first depth of curvature 310 and the second depth of curvature 320 is about 2 mm or more. The depth of curvature may be defined as the maximum distance that a surface is perpendicularly away from a plane defined by points on the circumference of the surface. For example, one or both of the first depth of curvature 310 and the second depth of curvature 320 may range from about 2 mm to about 30 mm. In an embodiment, the first depth of curvature 310 and the second depth of curvature 320 are substantially equal to each other. In one or more embodiments, the first depth of curvature 310 is within 10% of the second depth of curvature 320, and in particular, within 5% of the second depth of curvature 320. For illustration, in an example where the second depth of curvature 320 is about 15 mm, the first depth of curvature 310 would range from about 13.5 mm to about 16.5 mm (or within 10% of the second depth of curvature 320).

[0110] In an embodiment, the first depth of curvature 310 is induced in the first ply of glass 200 by hot forming (e.g., the first ply of glass 200 is bent under gravity sag) and the second depth of curvature 320 is induced in the second ply of glass 220 by cold forming. In an embodiment, the first and second depths of curvature 310 and 320 are induced by hot bending the first and second plies of glass 200 and 220 (e.g., in a co-bending process or a process in which the plies are bent independently of one another).

[0111] Referring now to Figure 4, a flow diagram of a method 400 for manufacturing a glass laminate is shown, according to an exemplary embodiment of the present disclosure. For example, the method 400 may be used to manufacture the curved glass laminate 300 described herein with respect to Figure 3. Accordingly, the various components shown in Figures 2-3 will be referenced to aid in describing the method. It should be understood that alternative methods may be used to form the curved glass laminate 300. Additionally, the method 400 may be used to form laminates other than the curved glass laminate 300.

[0112] At block 402, a first glass substrate is provided. The first glass substrate may be in the form of a first ply of glass 200, as described herein with respect to FIG. 2. For example, the first glass substrate as initially provided may be in the form of a planar glass sheet made from one of the borosilicate glass compositions described herein. The first glass substrate may be manufactured or purchased commercially. Any suitable glass forming technique may be used to manufacture the first glass substrate. The glass forming technique used will depend on the borosilicate glass composition, as some compositions may not be compatible with certain glass forming techniques. However, embodiments are contemplated in which the first glass substrate is formed by a suitable downdraw or float process. The first glass substrate may be formed to have a thickness within any of the ranges described herein with respect to the first ply of glass 200.

[0113] At block 404, a mixture is formulated for depositing the second decorative layer 250 directly onto the second major surface 204. The mixture may include an enamel (e.g., ceramic enamel) including a glass or ceramic frit, a dye component, and optional additives dispersed in a suitable medium. The enamel may have a formulation as described herein for the second decorative layer 250. The enamel (before it is cured) may be improved by the addition of any of the low CTE additive components described herein in combination with additional media. Any of the glass-ceramics or ceramics described herein may be mixed with the uncured enamel in appropriate proportions such that the second decorative layer 250 has a CTE within the ranges described herein that substantially matches the CTE of the first glass substrate after the enamel is cured. Pigments may be added to the enamel if the low CTE additive components introduce undesirable color.

[0114] When the low CTE additive component is added to the mixture, a dispersing device with a toothed blade rotating at an initial speed (e.g., between 1000 rpm and 2000 rpm) may be used to mix the enamel. After the low CTE additive component is added to the enamel, additional media may be added to the mixture to adjust the viscosity. The additional media may be the same media as that contained in the original enamel and may be added to the formulation in an equivalent amount to the low CTE additive component and any pigments to keep the total solids in the formulation close to the original enamel. After the addition of the media, the toothed blade may be rotated at an increased speed (e.g., at least 8000 rpm) for at least 10 minutes to obtain a proper dispersion of the additional component. The bath temperature should be maintained below 40° C. to avoid evaporation of the solvent and degradation of the media. After dispersion, the fineness of grind is controlled using a Hegman gauge and may be equal to or less than the target value given to the original enamel. The final viscosity of the improved enamel is 5s using a flow meter. -1 Measured at shear rate, it can range from 500 mPa·s to 50,000 mPa·s (e.g., about 10,000 mPa·s).

[0115] At block 406, the improved enamel is deposited on the second major surface 204 of the first ply of glass 200. Deposition may use any suitable technique (e.g., screen printing, spraying, brushing, banding), with the understanding that viscosity adjustments may be required (e.g., by the addition of water or additional media) depending on the deposition technique selected. At block 408, the improved enamel is cured onto the first ply of glass 200 by heating to an appropriate firing temperature (e.g., at least the softening temperature associated with the enamel) to melt the solvent and solidify the glass frit into a glass fuse matrix surrounding the low CTE additive components. At block 410, the first ply of glass 200 is shaped. In embodiments, blocks 408 and 410 are performed simultaneously because the improved enamels described herein are advantageously suited for hot bending techniques and will be hardened as the first ply of glass 200 is heated to a forming temperature in a furnace with appropriate shaping equipment (e.g., a bending ring or mold).

[0116] At block 412, the second glass substrate is laminated to the first glass substrate via the interlayer. For example, in an embodiment, a second ply of glass 220 having any of the compositions described herein can be provided having a planar shape. The second ply of glass 220 can be pressed against the first glass substrate 200 with the interlayer 230 therebetween, and while pressure is applied, the laminate can be heated to a glass transition temperature associated with the material of the interlayer 230, and then cooled to solidify the interlayer 230 and attach the first ply of glass 200 to the second ply of glass 220, such that the second ply of glass 220 is maintained in a curved shape that matches the curved shape of the first ply of glass 200. In this example, the second ply of glass 220 can have the first decorative layer 240 already formed thereon prior to lamination to the first ply of glass 200. In an embodiment, for example, the first decorative layer 240 may be formed from a commercially available enamel that is applied to the second ply of glass 220 when it is flat. In another example, both the first and second plies of glass 200 and 220 may be hot formed (e.g., co-draped simultaneously or curved separately). Embodiments in which one or more of the first and second decorative layers 240 and 250 are deposited on a curved surface (e.g., after the first and second plies of glass 200 and 220 have been shaped) are also contemplated.

[0117] 2, various exemplary compositions of borosilicate glass included in first ply of glass 200 will now be described. Examples 1-6 are described with respect to composition and various properties in Table 1 below.

[0118] [Table 1]

[0119] As shown in Table 1, each of the glass compositions exhibits a low temperature coefficient of thermal expansion (LTCTE), obtained by measuring the expansion of the glass between 0°C and 300°C, of ​​5.6 ppm / °C or less, particularly 5.3 ppm / °C or less, and especially 5.1 ppm / °C or less.

[0120] Additional exemplary borosilicate glass compositions are set forth in Table 2 below.

[0121] [Table 2]

[0122] As shown in Table 2, Examples 12 to 14 are B 2 O 3 The above example shows that increasing the amount of Na can have a density reducing effect. 2 O+K 2 O and a total of at least 7.0 mol % Na 2 O+K 2 From the examples in Tables 1 and 2, the embodiment of the present disclosure contains Na 2 O+K 2 When the total amount of O+MgO+CaO is at least 7.0 mol%, in particular at least 5.5 mol% Na 2 O+K 2 T for fusion molding when O and at least 1.5 mol% MgO+CaO are present 200P Moreover, embodiments of the present disclosure are believed to exhibit a liquidus viscosity of about 100% by weight, regardless of the amount of MgO and CaO. 2 O+K 2 When O is at least 8 mol %, the T required for fusion molding is 200P and liquidus viscosity.

[0123] Iron may also be added to the borosilicate glass composition to provide desired light transmission performance for automotive glazing applications. Examples containing various amounts of iron are shown in Table 3 below. In various embodiments, the first ply of glass 200 may use any of the examples described in any of the following patent applications: U.S. Provisional Patent Application No. 63 / 123863, filed December 10, 2020, entitled "Fusion Formable Borosilicate Glass Composition and Articles Formed Therefrom," U.S. Provisional Patent Application No. 63 / 183271, filed May 3, 2021, entitled "Fusion Formable Borosilicate Glass Composition and Articles Formed Therefrom," U.S. Provisional Patent Application No. 63 / 183292, filed May 3, 2021, entitled "Glass with Unique Fracture Behavior for Vehicle Windshield," U.S. Provisional Patent Application No. 17 / 363266, filed June 30, 2021, entitled "Glass with Unique Fracture Behavior for Vehicle Windshield," and U.S. Provisional Patent Application No. 17 / 363266, filed June 30, 2021, entitled "Glass with Unique Fracture Behavior for Vehicle Windshield." International Patent Application No. US2021 / 061966, filed December 6, 2021, entitled "Fracture Behavior for Vehicle Windshield."

[0124] [Table 3]

[0125] As illustrated in the previous examples, in embodiments, the borosilicate glass composition forming the first ply of glass 200 has an amount of SiO 2 ranging from 72 mol % to 80 mol % (e.g., 74 mol % to 80 mol %). 2 , 10 mol% to 20 mol% (e.g., 11 mol% to 20 mol%, 11 mol% to 16 mol%) 2 O3 , Al in an amount ranging from 2 mol% to 6 mol% (e.g., 2.5 mol% to 5 mol%, 3 mol% to 5 mol%) 2 O 3 , Na in an amount ranging from 3 mol% to 8 mol% (e.g., 4 mol% to 8 mol%, 4.5 mol% to 6.5 mol%) 2 O, Na 2 Amount of K less than the amount of O 2 O (e.g., K 2 O vs Na 2 % MgO, such that the ratio of NaO ranges from 0.1 to 0.75, or from about 0.1 to about 0.45, and up to 5 mol % MgO, as currently corrected. 2 The amount of O is at least 1.0 mol % (e.g., at least 1.25 mol % or at least 1.5 mol %) of Al 2 O 3 This combination of amounts of compositions can be useful for a first ply of glass 200 that is formed by a fusion molding technique (thus obtaining the optical distortion performance benefits and scratch resistance associated with that molding technique), while being stable during molding and having desirable chemical and mechanical durability characteristics. EXAMPLES

[0126] The embodiments of the present disclosure will be further understood in light of the following examples.

[0127] In the following examples, commercially available enamels from Ferro Corporation were modified by including low CTE additive components. The starting materials in the following examples are set forth in Table 4 below.

[0128] [Table 4]

[0129] Five examples (Examples 23-38 and 31) were formulated as set forth in Table 5 below. The examples were flat glass substrates onto which a decorative layer of the indicated composition was deposited according to method 400 described herein with respect to FIG. 4. The borosilicate glass compositions used in the following examples were approximately 45×10 -7 / K (25 to 300° C.). Each of Examples 23 to 28 exhibited a porosity of 25% to 30%.

[0130] [Table 5]

[0131] For each of the examples listed in Table 5, mechanical performance was measured by ring-on-ring (ROR) testing with a diameter of 32 mm and a glass thickness of 3.8 mm. The ROR test was performed according to the ASTM C-1499-03 standard for "Monotonic Equibiaxial Flexural Strength of Advanced Ceramics at Ambient Temperatures". For each of the samples, a Weibull distribution was calculated. The Weibull distribution for some of the examples is shown in FIG. 5. As can be seen from the figure, Examples 23 and 26 unexpectedly exhibited better mechanical performance than an uncovered glass substrate (having the same composition but without a decorative layer disposed thereon). As can be seen from the figure, the Weibull slope for each of Examples 23 and 26 was smaller than that of the uncovered glass substrate. Furthermore, as can be seen from Table 5 above, each of Examples 23-27 and 31 exhibited a B10 value (mechanical load at which there is a 10% probability of failure) of 60 MPa or more, while the uncovered glass substrate exhibited a B10 value of about 47 MPa. Glass substrates decorated with the enamels of the present disclosure have unexpectedly exhibited higher mechanical strength (as indicated by higher B10 values) as well as superior reliability (as indicated by smaller Weibull slope parameters) than uncoated substrates. In embodiments, when the glass substrates of the glass articles described herein have a thickness of 2.1 mm or greater, the decorated glass articles exhibit B10 values ​​of 60 MPa or greater (e.g., 65 MPa or greater, 70 MPa or greater, 75 MPa or greater, 80 MPa or greater, 85 MPa or greater).

[0132] As shown in FIG. 5, counter example CE1 exhibited inferior mechanical performance to Examples 23-27 and the uncovered glass substrate. The CTE of counter example CE1 was relatively low, 10×10 that of the glass substrate. -7 / K, but the relatively low mechanical strength was believed to be due to the lack of porosity within the decorative layer. It is believed that the decorative layer of counter example CE1 was observed to be almost non-porous due to the relatively small amount of low CTE additive added (the decorative layer only contained 15% by weight of the low CTE additive). Thus, in an embodiment, the decorative layer of the glass article described herein may contain more than 15% by weight (e.g., 16% by weight or more, 17% by weight or more, 18% by weight or more, 19% by weight or more, 20% by weight or more, 21% by weight or more, 22% by weight or more, 23% by weight or more, 24% by weight or more, 25% by weight or more, 20% by weight or more and 50% by weight or less, 20% by weight or more and 45% by weight or less, 25% by weight or more and 45% by weight or less, 30% by weight or more and 40% by weight or less, and any intermediate range). This amount of low CTE additive component provides a decorative layer in the desired CTE range, while still rendering the decorative layer porous for superior mechanical strength attributes.

[0133] Referring to Table 5, the CTE of the enamel was measured on sintered pellets of the modified enamel. To measure the CTE, a thin layer of enamel was placed on a glass-ceramic sample and placed in an oven (120°C) for several hours to remove the solvent. After complete evaporation of the solvent, the enamel became a dry powder. The powder was then crushed in an agate bowl to obtain a fine powder. The powder was compressed into small pellets using a pelletizer and sintered at 625°C for 7 minutes. The CTE was measured on the sintered pellets using TMA. This measurement was performed using a TAM Q400 EM from TA Instruments. As shown in Table 5, each of Examples 23-27 had a 50×10 -7 The CTE of each decorative layer in the embodiment was 34×10 -7 / K to 50 x 10 -7 / K. Examples 23 and 24 had CTE values ​​closest to that of the glass substrate. Example 23 showed the highest B10 value, while Example 24 showed the lowest Weibull slope.

[0134] The color of each of Examples 23, 26, and 27 was measured by illuminating the samples with a D65 light source at an observer angle of 10°. The integrated visible transmittance across the visible spectrum was also measured for each of these examples. As can be seen, for each of these examples, the L * The values ​​were less than 15, in some cases less than 10, and even less than 5. The integral visible transmittance before lamination was 2.0% or less, in some cases 1.5% or less, and in some cases 1.0% or less. After lamination, the integral visible transmittance was slightly less than before lamination as a result of the PVB interlayer filling at least some of the pores in the decorative layer. The laminate was a 0.7 mm thick inner ply of aluminosilicate glass, a 0.76 mm thick PVB interlayer, and a 3.8 mm thick outer glass ply of the borosilicate glass composition described herein. The decorative layer was disposed on the outer ply adjacent to the interlayer.

[0135] The thickness of the decorative layer of each of the examples was measured using a 2 mm confocal sensor on an Altisurf™ 100. Profiles were created using MountainsMap® software with the following measurement filters: a polynomial order of 3 was used to remove geometric defects and a Gaussian robust filter was used to remove measurement artifacts. An exemplary thickness profile of the counter example CE2 is shown in Figure 6. This resulted in a thickness measurement of 12.24 μm. As can be seen, the surface height deviates from the obtained average value as a result of the porosity of the decorative layer.

[0136] 7A, 7B, and 7C show scanning electron microscope images for Example 23, Example 26, and Counter Example CE1. FIG. 7A is an image 700 of Example 23. FIG. 7B is an image of Example 26. FIG. 7C is an image of Counter Example CE1. As can be seen, each of Examples 23 and 26 exhibits porosity, and each contains pores with a maximum diameter of more than 1.0 μm. Both Examples 23 and 26 exhibit pores with a maximum pore diameter of more than 2.0 μm. As shown in FIG. 7A, Example 23 includes a pore 701 with a maximum diameter 703 of about 4.0 μm. As shown in FIG. 7B, Example 26 includes a pore 705 with a maximum diameter 707 of about 5.0 μm. As used herein, "maximum diameter" refers to the longest straight line length included in the volume of the pore without intersecting the pore boundary. Such maximum diameter ends may occur at the surface of the glass substrate.

[0137] As shown in Figures 7A-7B, each of Examples 23 and 26 exhibits pores (e.g., voids devoid of decorative layer material) at the interface between the glass substrate and the decorative layer (Example 23 includes interfacial pore 710, and Example 26 includes interfacial pore 712). That is, in these examples, the interface between the glass substrate and the decorative layer does not include a continuous contact area between the glass and the hardened enamel, but rather includes discontinuous areas of contact. Breaking the contact area between the glass substrate and the decorative layer would help provide superior mechanical strength performance to the decorated glass article.

[0138] 7C, counter example C1 included a non-porous decorative layer 720 without any pores with a maximum diameter of more than 1.0 μm. As a result, the interface between the glass substrate and the non-porous decorative layer 720 was a continuous contact area between the glass and the material of the decorative layer. Such continuous contact is believed to increase the possibility of crack formation in the decorative layer and reduce the mechanical strength of the glass substrate by introducing more defects.

[0139] To investigate the relationship between the decorative layer and the porosity, additional exemplary decorative layers were formed on soda-lime silicate glass substrates. The glass substrates in these examples were approximately 90×10-7 The polymer had a CTE of 0.15 to 0.5 μm / K. Three examples were formulated, the details of which are given in Table 6 below.

[0140] [Table 6]

[0141] As shown in Table 6, Example 28 consisted of an uncoated glass substrate, Example 29 included a glass substrate decorated with a commercial enamel to provide a non-porous decorative layer, and Example 30 included a glass substrate with an improved decorative enamel with pigment additive to provide a porous decorative layer. Each sample was subjected to ROR testing, the results of which are shown in FIG. 8. As can be seen, the porous enamel exhibits higher B10 values ​​than the non-porous examples. Furthermore, the slope of the Weibull distribution appears to be higher upon deposition of the enamel, indicating improved reliability. Example 30 performs better than Example 29 in terms of B10 values, indicating the desirability of a porous decorative layer.

[0142] Embodiments of the present disclosure may be further understood in light of the following information.

[0143] The decorative layers described herein generally comprise a base enamel (e.g., including any one or more of the glass frit components, dye components, and additive components described herein) and a low CTE additive component described herein (e.g., LiAlSiO 4The decorative layer may include one or more porosity-inducing components such as either β-eucryptite phase of CrN, other fillers such as alumina, zeolite, and / or pigment additives that promote the development of porosity in the decorative layer after curing. In embodiments, the decorative layer preferably develops a porosity of 5% or more (e.g., 10% or more, 15% or more, 20% or more, 25% or more, 30% or more) after curing. Porosity can be determined by SEM image analysis, averaging four images at different non-overlapping positions from the same sample. When measuring the porosity of the examples described herein, each image in the SEM measurement captured a length of about 55 μm of the decorative layer. Decorative layers exhibiting such porosity have a difference in CTE (ΔCTE) of about 23×10 -7 It has been found that glass articles described herein that include a porous decorative layer can be printed on glass substrates up to 1000 nm / K and still provide acceptable mechanical strength results. In embodiments, the glass articles described herein that include a porous decorative layer can achieve B5 values ​​of 45 MPa or greater (e.g., 50 MPa or greater, 55 MPa or greater, 60 MPa or greater, 65 MPa or greater, 70 MPa or greater, or even 75 MPa or greater) when incorporated into various laminate structures, provided the foregoing porosity and ΔCTE requirements are met.

[0144] It has been found that even when such porosity is present in the decorative layers described herein, the glass articles described herein exhibit a desired opaque appearance. In embodiments, after lamination, the glass articles described herein have a CIELAB L of 12 or less (e.g., 11 or less, 10 or less, 9 or less, 8 or less, 7 or less) in areas where the interlayer material (e.g., a polymeric interlayer such as PVB) fills at least some of the pores in the decorative layer as a result of lamination. *The glass articles described herein may also exhibit a minimum ΔE value of 3.0 or less (e.g., 2.5 or less, 2.0 or less, 1.5 or less, 1.0 or less) calculated using the CIE76 formula between two different locations of the article where the decorative layer is disposed and fills the pores at least to some extent. In embodiments, the glass article exhibits an integrated visible transmission (either before or after lamination) of 2.0% or less (e.g., 1.8% or less, 1.6% or less, 1.4% or less, 1.2% or less, 1.0% or less, 0.8% or less, 0.6% or less, 0.4% or less, 0.2% or less, 0.1% or less) for light from 400 nm to 700 nm normally incident on the glass article (in the area where the decorative layer is disposed). Thus, after lamination, the decorative layer provides a desirable, uniform appearance of opaqueness that helps hide various components that may be disposed behind the glass article (such as in automotive obscuration).

[0145] In embodiments, the decorative layer described herein may include one or more regions in which the pores in the decorative layer are not filled with the polymeric material of the interlayer (e.g., the glass article may not be a laminate, or the material of the interlayer may not flow into the pores during lamination). Such regions may have an L of 30 or less. * It is possible to provide a wide variety of appearances that may exhibit value and that may be desirable for a particular application.

[0146] In embodiments, the glass articles described herein pass standard automotive industry weathering tests, such as bake tests, boil tests, and UV resistance, as specified by ANSI Z26. To facilitate passing such tests, the outer edges of the porous decorative layer may be encapsulated within the polymeric material of the interlayer when the decorative glass article is incorporated into a laminate.

[0147] To further understand the performance attributes of the decorative layers described herein, additional examples were constructed and analyzed for various mechanical and optical performance properties. A first set of examples was constructed on a sheet of 2.1 mm thick soda-lime glass. FIG. 9A shows an example glass article having a non-porous decorative layer (e.g., having the same composition as the decorative layer described above with respect to Example 29). In the example shown in FIG. 9A, the non-porous decorative layer has a thickness of about 10×10 relative to the glass. -7 9B shows an example glass article having a porous decorative layer (having the same composition as the decorative layer described above with respect to Example 30). In the example shown in FIG. 9B, the porous decorative layer has a ΔCTE of about 5×10 -7 / K (porosity was less than 20% but greater than 5%).

[0148] The examples shown in Figures 9A and 9B, as well as the uncovered soda lime glass substrate, were subjected to a 32 mm diameter ROR test according to ASTM C-1499-03. The results are shown in Figure 9C. As can be seen, consistent with the results previously described for Examples 28, 29, and 30, the examples with the porous decorative layer showed superior mechanical strength to those with the non-porous decorative layer. Indeed, the uncovered substrate showed a B5 value of 65 MPa, the examples with the non-porous decorative layer showed a B5 value of 41 MPa, and the examples with the porous decorative layer showed a B5 value of 62 MPa. These results indicate that the porous decorative layer unexpectedly did not significantly impede the mechanical strength of the glass substrate. Indeed, the examples with the porous decorative layer showed a B5 value of 45 MPa or more, indicating that the decorative layer described herein provides superior mechanical performance compared to certain existing decorative materials. The porosity in the decorative layer resulted in less than 10% decrease in mechanical strength compared to the uncovered undecorated substrate, and even improved the mechanical strength results. Such results suggest that the porous decorative layer may find use even when used to decorate glass substrates that are not chemically strengthened, such as soda-lime silicate glass compositions in automotive glazing (e.g., soda-lime glass may be used as an outer and / or inner ply in a glazing and decorated with one of the decorative layers described herein).

[0149] An additional set of exemplary decorative layers was prepared using Example 22 (approximately 45.2×10 -7 The first porous decorative layer was formed on a 3.8 mm thick glass substrate formed from the borosilicate glass composition described herein for a 3.8 mm thick glass substrate having a CTE of 100 nm / K. FIG. 10A shows a first porous decorative layer on the borosilicate glass. This first porous decorative layer had the same composition as the decorative layer of Example 31 herein. The first porous decorative layer had a density of about 3×10 -7The second porous decorative layer had a ΔCTE relative to the glass substrate of 0.05 μm / K. FIG. 10B shows the second porous decorative layer on the borosilicate glass. This second porous decorative layer contained a base enamel of Ferro 13316 and 25 wt. % zeolite as a porosity-inducing component. This second porous decorative layer had a ΔCTE of approximately 23×10 -7 / K. Both examples exhibited porosity between 25% and 30%.

[0150] The examples shown in Figures 10A and 10B were subjected to ROR testing in the same manner as described above with respect to Figures 9A and 9B. An uncovered substrate of borosilicate glass was also tested. A glass substrate decorated with a non-porous decorative layer (made from a base enamel of Ferro 14316 containing 15% by weight of 118VTC particles) was also tested. The results of the example shown in Figure 10A, the uncovered substrate and the non-porous decorative layer are shown in Figure 10C. As can be seen, the example with the porous decorative layer showed a mechanical strength superior to that of the example with the non-porous decorative layer. Indeed, the uncovered substrate showed a B5 value of 68 MPa, the example with the non-porous decorative layer showed a B5 value of 26 MPa and the example with the porous decorative layer showed a B5 value of 71 MPa. The example shown in Figure 10B was also tested and showed a B5 value of 85 MPa. Unexpectedly, the decorative layer with zeolite additive showed a B5 value of 23 x 10 -7 Despite the relatively high ΔCTE of the porous decorative layer against the glass substrate of 0.15 mm / K, the porous decorative layer showed excellent mechanical strength results. Such results unexpectedly indicated that a porous decorative layer having a ΔCTE of 10.0 or more (e.g., 11.0 or more, 12.0 or more, 13.0 or more, 14.0 or more, 14.0 or more, 15.0 or more, 16.0 or more, 17.0 or more, 18.0 or more, 19.0 or more, 20.0 or more, 21.0 or more, 22.0 or more, 23.0 or more) against the glass substrate can be used while still exhibiting acceptable mechanical strength.

[0151] A further porous decorative layer made of Ferro 14316 as base enamel modified with 35% by weight of alumina particles as porosity-inducing component was constructed on a borosilicate glass (3.8 mm thick) according to Example 22, an example of which is shown in Figure 11. The porous decorative layer had a porosity of about 30% and a particle size of about 30 x 10 -7 11 shows a ΔCTE for a glass substrate of 1000 nm / K. ROR strength testing was performed in a manner consistent with the other examples, and the example shown in FIG. 11 was determined to exhibit a B5 value of about 24 MPa, which was similar to the example having a non-porous decorative layer. These results indicate that the porosity is 30×10 -7 This indicates that this may be insufficient to overcome the relatively high ΔCTE above 1 / K.

[0152] To determine the desired amount of porosity for the decorative layer described herein, several samples were constructed on the borosilicate glass composition described herein with respect to Example 22. The samples had a porous decorative layer formed using various amounts of zeolite ZSM-5 as the porosity-inducing component. The zeolite particles had a particle size (d50) between 2.5 μm and 3.0 μm. Each of these samples is shown in FIG. 12A. As can be seen, the porosity in the decorative layer tends to increase in proportion to the amount of zeolite added. These samples were subjected to ROR testing using a method consistent with the other examples. The B5 value of each of the samples was determined and plotted as a function of the porosity of each of the samples. The results are shown in FIG. 12B. As can be seen, the decorative layers with porosities between 6.7% and 18.5% exhibited relatively low B5 values ​​of less than 25 Mpa. When the porosity was greater than 18.5%, the B5 value increased sub-linearly as a function of the porosity. Therefore, for these particular examples, it was determined that a decorative layer exhibiting at least 25% porosity was likely to exhibit a target B5 value of at least 55 MPa. This is because the examples including 25% by weight zeolite in the decorative layer exhibited a porosity of approximately 23×10 -7 / K. It is believed that the porous filler zeolite (the zeolite particles themselves contain pores ranging in size from 1 nm to 10 nm) may contribute to these favorable results.

[0153] FIG. 13A shows an example of a porous decorative layer on a borosilicate glass substrate before lamination. As can be seen, this example has a gray appearance (approximately 30 L) when viewed from the glass side. * 13B shows the same example after lamination with another glass substrate via a PVB interlayer. In these examples, the borosilicate glass was 3.8 mm and the interlayer material was a PVB layer with a thickness of 0.76 mm. The interlayer material was applied between a decorated borosilicate glass substrate and an aluminosilicate glass substrate with a thickness of 0.7 mm. The laminate was degassed at 118° C. at a pressure of 0.95 bar (95 kPa) and subsequently heated to 140° C. at 13 bar (1.3 MPa) in an autoclave. As can be seen, during lamination the interlayer material flows into the pores of the decorative layer, darkening the appearance of the article. After lamination, the article has an L of less than 8 when viewed from the same glass side as in FIG. 13A. * values, which are desirable for automotive applications. This example shows how the porous decorative layers described herein can achieve a pleasing appearance despite the porosity therein.

[0154] In embodiments, the porous decorative layer described herein may cover at least 5% (e.g., at least 6%, at least 7%, at least 8%, at least 9%, at least 10%, at least 15%, at least 20%, at least 25%, or 10% or more and 30% or less) of the total surface area (of the major surface on which it is disposed) of the glass article. For example, in automotive applications, the glass article may cover at least 0.25 m 2 (e.g. at least 0.5m 2 , at least 0.75m 2 , at least 1.0m 2 , at least 1.5m 2 , at least 2.0m 2 , at least 2.5m2 ) surface area (e.g., as measured on the outer surface). Thus, the porous decorative layer may have a surface area (e.g., as measured on the outer surface) of at least 0.00125 m 2 In an embodiment, the glass article may cover a surface area of ​​2.0 m 2 or more, and the porous decorative layer has a surface area of ​​at least 0.1 m 2 Or at least 0.2m 2 The surface area covered by the decorative layer may extend to the periphery of the glass article (e.g., forming a decorative border of the glass article on a major surface from the vicinity or outer edge of the glass article inward). Despite the porous decorative layer covering such a large area, the glass article can exhibit the mechanical strength attributes described herein.

[0155] Further samples were constructed to determine the effect of particle size of the porosity-inducing component. A first set of samples was formed using a decorative layer having the composition described herein with respect to Example 31, and varying the d50 particle size of the 118 VTC additive. The first example included 118 VTC that was wet milled and dried to provide a d50 particle size of 1 μm. This is shown in FIG. 14A. The second example included 118 VTC that was jet milled to provide a d50 particle size of 2.5 μm. This is shown in FIG. 14B. The third example included 118 VTC that was jet milled to provide a d50 particle size of 5 μm. This is shown in FIG. 14C. The porosity of the first example was about 26.8%. The porosity of the second example was about 27.3%. The porosity of the third example was about 26.4%. As can be seen, decreasing the particle size of the porosity-inducing component (or in this case, the low CTE additive component) decreases the average pore size while keeping the overall porosity relatively constant.

[0156] These decorative layers deposited on 3.8 mm thick borosilicate glass articles were subjected to ROR testing in a manner consistent with the other examples. The B5 values ​​as well as the Weibull scale values ​​are plotted as a function of d50 grain size in FIG. 15A. As can be seen, both the B5 values ​​and the Weibull scale values ​​appear to decrease as the additive grain size increases. A similar test was performed on a second set of examples with decorative layers having the compositions described herein with respect to Example 23. The grain size for the 118 VTC additive was varied in a similar manner as in the first set of examples shown in FIGS. 13A-13C (d50 grain size of 1 μm, 2.5 μm, and 5 μm, respectively). The second set of examples were subjected to ROR testing, and the B5 values ​​and the Weibull scale values ​​are plotted as a function of grain size in FIG. 15B. As can be seen, the B5 values ​​and the Weibull scale values ​​of the second set of examples also tended to decrease with increasing additive grain size. Based on these results, it would be preferred for the porosity-inducing additive to have a d50 particle size of 10 μm or less (e.g., 0.01 μm to 10 μm, more preferably 5 μm or less) to avoid adverse effects on mechanical performance. In embodiments, the porosity-inducing additive may have a particle size of 0.01 μm to 10 μm (e.g., 0.1 μm to 10 μm, 0.5 μm to 10 μm, 1.0 μm to 10 μm, 0.01 μm to 5 μm, 0.1 μm to 5 μm, 0.5 μm to 5 μm, 1.0 μm to 5 μm, 0.01 μm to 2.5 μm, 0.1 μm to 2.5 μm, 0.5 μm to 2.5 μm, 1.0 μm to 2.5 μm). In embodiments, the d50 particle size of the porosity-inducing component is 1.0 μm or more and 5 μm or less. Maintaining the particle size within these ranges can beneficially prevent the decorative layers described herein from adversely affecting the mechanical performance of the glass articles described herein (e.g., the decorative layers may not reduce the B5 or B10 values ​​of the uncovered glass substrate by more than 10%).

[0157] To evaluate the effect of the particle size of the porosity-inducing component on the optical performance, the integrated visible transmittance was measured for a second set of examples both before and after lamination of the aluminosilicate glass to another glass ply via a PVB interlayer. Light from a D65 light source was transmitted through the samples to measure the light transmission performance. The results are shown in FIG. 16. As can be seen, the integrated visible transmittance increases with increasing particle size of the porosity-inducing component both before and after lamination. Notably, samples with d50 particle size less than 5 μm exhibited a light transmittance of less than 0.5% relative to the product. Each of the samples also exhibited an increase in the integrated visible transmittance due to lamination. As shown in FIG. 16, the difference before and after lamination is smallest at the smallest particle size. In other words, lamination minimized the difference in light transmittance when the particle size of the porosity-inducing component was smallest. This indicates that a smaller particle size (e.g., d50 particle size less than 5 μm, less than 3 μm, or less than 2 μm) would be beneficial from the standpoint of both mechanical and optical performance.

[0158] In embodiments, the porous decorative layer described herein can be characterized in that it comprises at least 15 volume percent of a porosity-inducing component (e.g., a low CTE additive, a pigment, or other filler such as alumina or zeolite). In embodiments, the porous decorative layer described herein can comprise an amount of porosity-inducing component particles (e.g., one or more of a low CTE additive, a pigment additive, or any other suitable material described herein) that constitutes 15 volume percent to 40 volume percent of the porous decorative layer. Such an amount can ensure adequate porosity to provide the desired mechanical strength attributes described herein. The term "porous decorative layer" is used interchangeably with "porous inorganic layer" herein.

[0159] This disclosure contemplates the production of porous decorative layers by a variety of different techniques. The porosity-inducing components described herein (e.g., low CTE additive components, alumina, pigment additives, or other suitable materials) are generally added to the enamel (uncured) in an amount sufficient to induce porosity after firing (e.g., for pigments, above the critical pigment volume concentration, and similar amounts for other porosity-inducing components). The amount of porosity-inducing component required to induce porosity in the decorative layer will vary depending on the composition of the enamel (e.g., the composition of the glass frit component and / or the amount of pigment and other fillers already present in the enamel). In embodiments, rather than introducing porosity-inducing component particles into the enamel, porosity can be induced by introducing an organic pore-forming material that will produce porosity after pyrolysis during firing. The organic material can, for example, be burned off during firing, leaving voids in the decorative layer in any of the amounts described herein. Examples formed using such techniques may be free of porosity-inducing component particles in the cured decorative layer to the same extent as other examples that rely solely on porosity-inducing component particles to induce porosity. Any suitable method for producing porosity in a frit-based decorative layer may be used.

[0160] As used herein, the term "disposing" includes coating, depositing, and / or forming a material on a surface using any method known in the art. The disposed material may constitute a layer, as defined herein. The phrase "disposed on" includes instances where a material is formed on a surface such that the material is in direct contact with the surface, and also includes instances where a material is formed on a surface with one or more intervening materials between the disposed material and the surface, which intervening materials may constitute a layer, as defined herein.

[0161] Ranges may be expressed herein as from "about" one particular value, and / or to "about" another particular value. When such a range is expressed, another embodiment includes from the one particular value and / or to the other particular value (i.e., the range includes the expressly stated endpoints). Similarly, when values ​​are expressed as approximations, by use of the antecedent "about," it will be understood that the particular value forms another embodiment. For example, the range "from about 1 to about 2" expressly includes the range "from 1 to 2." Similarly, the range "about 1 to about 2" expressly includes the range "from 1 to 2." It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint.

[0162] As used herein, directional terms - e.g., up, down, right, left, front, back, top, bottom - are used only in relation to the drawings depicted and are not intended to imply absolute orientations.

[0163] Unless otherwise expressly stated, it is in no way intended that any method described herein be construed as requiring that its steps be performed in a particular order or as requiring a particular orientation for any apparatus. Thus, where a method claim does not actually recite an order in which its steps are to be followed, or an apparatus claim does not actually recite an order or orientation with respect to individual components, or where the claims or description do not recite the steps to be limited to a particular order or a particular order or orientation with respect to the apparatus components, no order or orientation is intended to be implied in any respect. This applies to any possible non-expressive criteria of interpretation, including sequence of steps, operational flow, order of components, or orientation of components; obvious meanings derived from grammatical construction or punctuation; and logical matters regarding the number or type of embodiments described in the specification.

[0164] As used herein, nouns include plural referents unless the context clearly indicates otherwise. Thus, for example, reference to an element includes aspects having two or more of such elements unless the context clearly indicates otherwise.

[0165] The configurations and arrangements of compositions, assemblies, and structures as shown in the various exemplary embodiments are merely exemplary. Although only a few embodiments are described in detail in this disclosure, many modifications are possible (e.g., variations in size, dimensions, structure, shape, and proportions of various elements, parameter values, mounting arrangements, material use, color, orientation) without substantially departing from the novel teachings and advantages of the subject matter described herein. Materials such as glass sheets disclosed herein can be used for glass sheets in architectural applications (e.g., windows, partitions) or for other applications such as packaging (e.g., containers). The order or sequence of any process, logic algorithm, or method steps may be modified or resequenced according to alternative embodiments. Also, other substitutions, modifications, changes, and omissions may be made in the design, operating conditions, and arrangements of the various exemplary embodiments without departing from the scope of the technology of the present invention.

[0166] Preferred embodiments of the present invention will be described below in detail.

[0167] EMBODIMENT 1 a glass substrate having a first major surface and a second major surface disposed opposite the first major surface; and a decorative layer adhered to at least a portion of the second major surface, a glass flux substrate, and Multiple pores, A decorative layer including A decorative glass article comprising: The glass substrate has a thickness of 2.1 mm or more, The decorative layer has a coefficient of thermal expansion ("CTE") of 23×10 of the glass substrate. -7 / K or less CTE, The decorative glass article exhibits a B5 value of 45 MPa or greater when at least 10 of the decorative glass articles are subjected to a ring-on-ring test in accordance with ASTM C-1499-03.

[0168] EMBODIMENT 2 2. The decorative glass article of claim 1, wherein the porosity is 5% or greater.

[0169] EMBODIMENT 3 3. Decorative glass article according to claim 1 or 2, wherein the B5 value is 55 MPa or more.

[0170] EMBODIMENT 4 4. The decorated glass article of any one of claims 1 to 3, wherein the decorative layer comprises at least 15 volume percent of porosity-inducing component particles.

[0171] EMBODIMENT 5 5. The decorative glass article of embodiment 4, wherein the porosity-inducing component particles comprise a plurality of particles of at least one of beta-eucryptite ceramic, alumina, pigment additive, and zeolite.

[0172] EMBODIMENT 6 6. The decorative glass article of claim 5, wherein the plurality of particles has a d50 particle size of 1 μm or more and 5 μm or less.

[0173] EMBODIMENT 7 7. The decorated glass article of any one of claims 1 to 6, wherein the decorative layer covers 5% or more of the total surface area of ​​the second major surface.

[0174] EMBODIMENT 8 The glass substrate is not chemically strengthened; and the glass substrate is formed from a soda-lime-silicate glass composition; 8. The decorative glass article according to any one of claims 1 to 7, wherein at least one of the following is true:

[0175] EMBODIMENT 9 9. The decorated glass article of any one of the preceding claims, wherein the decorative layer is encapsulated within a polymeric material.

[0176] EMBODIMENT 10 The difference between the CTE of the decorative layer and the CTE of the glass substrate is 15×10 -7 10. The decorative glass article of any one of claims 1 to 9, wherein the .lambda. / K is greater than or equal to .

[0177] EMBODIMENT 11 The decorative layer comprises 20% by weight or more and 40% by weight or less of low CTE additive particles, and at least some of the low CTE additive particles have a molecular weight of 10×10 -7 11. The decorative glass article of any one of the preceding claims, having a CTE of no more than 1 / K.

[0178] EMBODIMENT 12 12. The decorative glass article of claim 11, wherein each of the low CTE additive component particles is made from glass, glass frit, glass enamel, ceramic enamel, glass ceramic, or ceramic material.

[0179] EMBODIMENT 13 13. Decorative glass article according to any one of the preceding claims, wherein the decorative layer comprises 5% by weight or more of a pigment additive.

[0180] EMBODIMENT 14 14. The decorative glass article of embodiment 13, wherein the pigment additive comprises at least one of a CuCr-based pigment, a MgFe-based pigment, and a FeCrCoNi-based pigment.

[0181] EMBODIMENT 15 15. The decorative glass article of any one of claims 11 to 14, wherein the low CTE additive component particles and the pigment additive, if present, have an average particle size of 10 μm or less.

[0182] EMBODIMENT 16 16. The decorative glass article of any one of the preceding claims, further comprising a second glass substrate and an intermediate layer disposed between the second glass substrate and the second major surface, wherein a polymeric material of the intermediate layer is present in the plurality of pores.

[0183] EMBODIMENT 17 The glass article has an L of 30 or less in the area where the decorative layer is disposed. * 17. The decorative glass article of embodiment 16, exhibiting a value.

[0184] EMBODIMENT 18 The glass article has an L of 10 or less in an area where the polymeric material is present in the plurality of pores. * 18. The decorative glass article of embodiment 17, exhibiting a value.

[0185] EMBODIMENT 19 19. The decorative glass article of claim 17 or 18, wherein when light from a D65 light source is reflected off the glass substrate, the light exhibits a maximum ΔE value between two different positions on the glass article on which the decorative layer is disposed, calculated using the CIE76 formula, of 3.0 or less.

[0186] EMBODIMENT 20 55×10 -7 a glass substrate having a coefficient of thermal expansion ("CTE") of less than or equal to 1 / K, a first major surface, and a second major surface disposed opposite the first major surface; a decorative layer adhered to at least a portion of the second major surface, Glass flux substrate, A plurality of low CTE additive component particles, and Multiple pores, Including, The decorative layer comprises more than 15% by weight of the low CTE additive component particles, Each of the plurality of low CTE additive component particles has a particle size of 10×10 -7 / K or less CTE, The decorative layer has a CTE of 15×10 of the glass substrate. -7 A decorative layer having a CTE within 0.1 mm / K; A decorative glass article comprising:

[0187] EMBODIMENT 21 21. The decorated glass article of claim 20, wherein the decorated glass article has a probability of failure of less than 10% when subjected to a ring-on-ring test at a load of 60 MPa with a ring diameter of 32 mm.

[0188] EMBODIMENT 22 The CTE of the decorative layer is 55×10 -7 22. The decorative glass article of claim 20 or 21, wherein the viscosity is less than or equal to 1 / K.

[0189] EMBODIMENT 23 23. The decorative glass article of any one of claims 20 to 22, wherein each of the plurality of low CTE additive component particles is made from glass, glass frit, glass enamel, ceramic enamel, glass ceramic, or ceramic material.

[0190] EMBODIMENT 24 24. The decorated glass article of any one of claims 20 to 23, wherein the decorative layer comprises 20% by weight or more and 40% by weight or less of the low CTE additive component particles.

[0191] EMBODIMENT 25 25. The decorated glass article of any one of claims 20 to 24, wherein the decorative layer comprises 5% by weight or more and 30% by weight or less of a pigment.

[0192] EMBODIMENT 26 When the decorative glass article is illuminated from the first major surface with a D65 light source, the L according to the CIELAB color coordinate system is less than 15.0. * 26. The decorative glass article of any one of claims 20 to 25, exhibiting a value.

[0193] EMBODIMENT 27 27. The decorative glass article of any one of claims 20 to 26, wherein the decorative glass article exhibits an integrated visible transmittance of 2.0% or less for light from 400 nm to 700 nm normally incident on the first major surface in the area where the decorative layer covers the second major surface.

[0194] EMBODIMENT 28 28. Decorative glass article according to any one of claims 20 to 27, wherein the decorative layer has an average thickness of 20 μm or less.

[0195] EMBODIMENT 29 29. The decorative glass article of any one of claims 20 to 28, wherein at least one of the plurality of pores has a maximum diameter greater than 1.0 μm.

[0196] EMBODIMENT 30 30. The decorated glass article of any one of claims 20 to 29, wherein the decorative layer has a porosity of at least 15%. [Explanation of symbols]

[0197] 100 vehicles 110 Body 120 aperture 130 Automotive glass 200 1st glass ply 202 First main surface of first glass ply 204 Second main surface of first glass ply 220 Second Glass Ply 222 first main surface of second glass ply 224 Second main surface of second glass ply 230 Middle Class 240 First decorative layer 250 Second decorative layer 300 curved glass laminate 310 First Curvature Depth 320 Second Curvature Depth

Claims

1. a glass substrate having a first major surface and a second major surface disposed opposite the first major surface; and a decorative layer adhered to at least a portion of the second major surface, a glass flux substrate, and Multiple pores, A decorative layer including A decorative glass article comprising: The glass substrate has a thickness of 2.1 mm or more, The decorative layer has a coefficient of thermal expansion ("CTE") of 23×10 of the glass substrate. －７ / K or less, The decorative glass article exhibits a B5 value of 45 MPa or more when at least 10 pieces of the decorative glass article are subjected to a ring-on-ring test in accordance with ASTM C-1499-03, and the porosity is 5% or more.

2. The decorated glass article of claim 1 , wherein the decorative layer comprises at least 15 volume percent of the porosity-inducing component particles.

3. The decorative glass article of claim 2 , wherein the porosity-inducing component particles comprise a plurality of particles of at least one of beta-eucryptite ceramic, alumina, pigment additive, and zeolite.

4. 4. The decorative glass article of claim 3, wherein the plurality of particles have a d50 particle size of 1 μm or more and 5 μm or less.

5. 5. The decorated glass article of claim 1, wherein the decorative layer covers 5% or more of the total surface area of ​​the second major surface.

6. 5. The decorative glass article of claim 1, wherein the decorative layer is encapsulated in a polymeric material.

7. The difference between the CTE of the decorative layer and the CTE of the glass substrate is 15×10 －７ 5. The decorative glass article according to claim 1, wherein the glass composition is a glass matrix having a refractive index of 1 / K or more.

8. The decorative layer comprises 20% by weight or more and 40% by weight or less of low CTE additive component particles, and at least some of the low CTE additive component particles have a thickness of 10×10 －７ 5. The decorative glass article of claim 1, wherein the decorative layer has a CTE of 0.1 to 0.5 K or less, each of the low CTE additive component particles is made of glass, glass frit, glass enamel, ceramic enamel, glass ceramic or ceramic material, the decorative layer comprises 5% by weight or more of a pigment additive, the pigment additive comprises at least one of a CuCr-based pigment, an MgFe-based pigment, and an FeCrCoNi-based pigment, and the low CTE additive component particles and the pigment additive have an average particle size of 10 μm or less.

9. The glass article further comprises a second glass substrate and an intermediate layer disposed between the second glass substrate and the second main surface, wherein a polymeric material of the intermediate layer is present in the plurality of pores, and the glass article has an L of 30 or less in an area where the decorative layer is disposed. ＊ and wherein the glass article exhibits an L value of 10 or less in an area where the polymeric material is present in the plurality of pores. ＊ 5. The decorative glass article of claim 1, wherein the decorative glass article exhibits a value.

10. 10. The decorative glass article of claim 9, wherein light from a D65 light source, when reflected off of the glass substrate, exhibits a maximum ΔE value between two different locations of the glass article having the decorative layer disposed thereon, calculated using the CIE 76 formula, of 3.0 or less.

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