Luminescent enamel substrate and its manufacture

Abstract

The object of the present invention is a luminous enamel substrate (and its manufacture) having a first glass sheet (1) comprising a discontinuous enamel scattering layer in vitreous binder and microcrystals.

Description

Technical Field

[0001] This invention relates to the field of enamel substrates for forming luminescent glass devices that are illuminated by a light source. Background Technology

[0002] Inorganic light-emitting diodes (LEDs) are used in the production of light-emitting glass units, particularly for vehicles. Light emitted by the diode is introduced into the glass unit, which forms the guide, via its edge surface. The light is then extracted from the glass unit through a scattering layer (defining the lamp surface). This scattering layer is typically a scattering enamel obtained by screen printing, containing dielectric scattering particles, such as alumina particles, dispersed in a glassy matrix. This can be, for example, a planar enamel or even a set of 300µm-wide screen-printed enamel spots, taking into account at least the screen printing resolution determined by the aperture size of the screen printing mesh.

[0003] The luminescent glass unit has a very blurry appearance in the scattering layer region. The enamel has a light transmittance of less than 40% and a haze of 90 to 100%. Summary of the Invention

[0004] Therefore, this invention seeks to develop an alternating scattering layer that further increases the transparency in the "off" state while maintaining the ability to extract light.

[0005] For this purpose, the first subject of the invention is an enamel substrate specifically for luminescent glass devices (particularly land, sea, rail or air vehicles or buildings or street facilities), comprising a first glass sheet (preferably clear or ultra-clear, particularly colorless, and preferably soda-lime-silica glass, particularly with a refractive index n0 of 1.4 to 1.6 at 550 nm, particularly with a thickness of up to 10 mm, and even up to 5 or 3 mm and preferably at least 0.1 mm, 0.3 mm or 0.7 mm).

[0006] The first glass sheet (directly or on a sublayer) includes a scattering layer on one (only one) first main surface (the opposite surface in the case of tin-faced or float glass), the scattering layer being made of a scattering enamel comprising a glassy matrix containing a glassy binder (preferably a glass-crystal binder in a glassy binder having crystals (microcrystals), generated in situ during firing with or without seed crystals). Specifically, the scattering layer comprises scattering particles and / or microcrystals of the glass-crystal glassy matrix.

[0007] The scattering layer includes at least one first scattering pattern having a width of at least 0.1 mm and even at least 0.5 mm or even 1 mm, particularly having a length of at least 0.6 or 1 mm and even 1 cm, and having a surface S0, particularly a surface S0 of at least 100 µm × 600 µm.

[0008] The first scattering pattern (and even one or more scattering patterns of the scattering layer) comprises a group of individual micropads of the scattering enamel, or even a group of non-intersecting micropads. Between the micropads (defining the mutual contact area), the first sheet is preferably transparent (without an enamel layer, e.g., extending more than 100µm), and the first main surface is preferably bare or has a sublayer.

[0009] Micropads (all or some) may have different shapes, irregular profiles (especially with a certain degree of roundness, as detailed later), and / or substrates distributed in an irregular or even random manner.

[0010] By defining an analytical surface area S1 smaller than S0 in the first scattering pattern, and S1 being at least 50µm × 50µm and at most 100µm × 600µm—for example, 500µm × 340µm—and a surface area S2, which is the sum of the surface areas of the micropads in the surface area S1.

[0011] - The first scattering pattern is defined by the equivalent average diameter Am of the micropads (the substrate of the micropads is circular) being less than 10µm or less than or equal to 5µm and at least 1µm.

[0012] - The first scattering pattern is defined by the average distance Bm between adjacent micropads, ranging from 0.3 to 2 or even up to 1.5 Bm / Am.

[0013] - Preferably, the first scattering pattern includes the coverage Tm of the micro pads, i.e., the surface area S2 divided by the surface area S1, where Tm is less than 50%, and even less than 45%, 40%, 35% or 30%, and preferably at least 5%, 8%, 10%, 11%, 15% or 20%.

[0014] Preferably, the arrangement of the micropads can be further defined by at least one of the following features:

[0015] - The average distance Bm is less than 5µm, 4µm or up to 3µm, and more preferably at least 1µm.

[0016] - In the analytical surface, the first scattering pattern is defined by an average perimeter Pm (preferably taken from the substrate) of at least 3µm or 4µm and preferably less than 10µm.

[0017] - In the analytical surface, the first scattering pattern is defined by an average circularity Cm (preferably taken from the substrate) of at least 0.7 or 0.75, 0.8 or 0.85, and less than 1 or 0.95, and

[0018] - At least for the first scattering pattern and preferably for the entire scattering layer (the first scattering pattern and one or more other scattering patterns), the micropads (all or some) have a thickness of up to 4.5µm, 4µm, or 3.5µm or 3µm, and at least 0.5µm or 1µm.

[0019] - At least in the analysis surface and preferably for the entire scattering layer (first scattering pattern and one or other scattering patterns), micropads with a width (taken from the substrate) greater than 1µm have a thickness of at least 0.5µm or 1µm.

[0020] - At least in the analyzed surface and preferably for the entire scattering layer (a first scattering pattern and one or other scattering patterns), the first scattering pattern comprises pads with a diameter of 1µm to 20µm or 10µm (referred to as primary pads) and pads with a diameter less than 1µm and at least 0.1µm (referred to as secondary pads, which are more numerous than the primary pads), particularly at least 70%, 80%, or 90% of the micropads (in number) have a diameter of at most 20µm, 15µm, 10µm, or 5µm.

[0021] - At least in the analysis surface and preferably for the entire scattering layer (first scattering pattern and one or other scattering patterns), the micro pads have curved surfaces, especially with an average contact angle of less than 160° or 120° and even greater than 60°.

[0022] This pad arrangement creates a substrate with one or more transparent patterns that does not significantly reduce light transmittance or haze compared to a solid continuous scattering layer. It is perfectly feasible for applications such as automotive glass units, side windows, rear windows, and glass roofs.

[0023] The first scattering pattern formed as a scattering layer, alone or together with one or more scattering patterns, can couple light from a light source to a first glass sheet forming a light guide to extract light.

[0024] In the case of multiple scattering patterns, by using enamels of various properties and / or thicknesses, different levels of transmission (translucent, semi-transparent) and / or various arrangements of spots (by adjusting process parameters and / or enamel paste) can be achieved, and the present invention makes it possible to obtain glass units that can emit light simultaneously or sequentially in different ways, especially having more or less transparency.

[0025] By using light sources of various properties (visible light and even ultraviolet UV light), or even light-emitting particles of various properties, this invention enables the production of glass units that can emit light simultaneously or sequentially in different ways or even in multiple colors.

[0026] In the most typical configuration, the enamel substrate is a single sheet, or part of a laminate and / or double-glazed unit, to maintain transparency (so that objects behind the scattering layer can be seen, or even the outside, such as the sky in the case of a car roof). However, it may be desirable for the enamel substrate with the scattering layer to be as invisible as possible when closed, and to be assembled with an additional opaque sheet or with an opaque layer behind the scattering layer.

[0027] The scattering layer may comprise a single first scattering pattern or a first scattering pattern together with one or more other scattering patterns, each scattering pattern having the same or similar micropad arrangement as described, while maintaining the parameters Am, Bm, Bm / Am, Cm and their quantities. Another scattering layer may coexist in the form of an enamel plane, preferably occupying less than 10% of the transparent area (clear glass area, etc.) of the first sheet.

[0028] The enamel scattering layer, for example, contacts the first main surface. A transparent liner (single or multiple layers), preferably of mineral, at least resistant to enamel firing, and even having a thickness of up to 1µm or 0.2µm, may be provided between the scattering layer and the first surface, provided that such thickness does not interfere with the guiding and / or extraction of light.

[0029] The glassy matrix is ​​preferably glass-crystalline, so the micropads contain microcrystals (generated during firing, rather than by adding particles to the liquid composition), particularly diffused in the glassy binder (together with the molten glass frit).

[0030] Microcrystals contain all or part of the elements of a vitreous binder, in an oxidized state. A microcrystal is a defined compound. Microcrystals are located within or on the surface of the vitreous binder, particularly in so-called primary pads of at least 1 µm—in dendritic or needle-like forms. Microcrystals exhibit a variety of unaligned, non-spherical, and rather elongated shapes.

[0031] These microcrystals have the advantage of diffused light and can replace all or part of the additional scattering elements added to the binder, such as metal oxide pigments (white, colored, distinguishable from black, etc.).

[0032] The vitreous adhesive may preferably be dense or slightly porous, including gas or vacuum pores, which may form part of the diffuse element together with microcrystals and / or added scattering particles (white or colored pigments).

[0033] The glassy matrix or even the glass-crystalline matrix can be a (transparent) matrix, preferably colorless, and in particular the volume fraction of the glassy binder is at least 80%, 85% or 90% of the enamel, and the remainder is microcrystals and / or other scattering particles.

[0034] Preferably, oxides of lead, cadmium, and mercury are avoided for vitreous adhesives. Oxides of transition metals other than zinc from groups 5 to 11 and even 12 of the periodic table are preferably avoided (or at a weight content of less than 1% of the total weight of the enamel). The total content of basic oxides (such as Li₂O and K₂O) other than Na₂O used in the vitreous adhesive is preferably at most 3% by weight of the vitreous adhesive (and even the enamel), especially 2% by weight and even 1% by weight or 0.5% by weight. In one case, the only basic oxide present is advantageously Na₂O. The weight content of the cumulative oxides of alkaline earth metals Mg, Ca, or even Mg, Ca, and Ba can be limited to 5% by weight, 2% by weight, 1% by weight, or 0.5% by weight of the vitreous adhesive (and even the enamel).

[0035] Furthermore, in the first implementation scheme, cumulatively:

[0036] - For glassy adhesives, silica (SiO2) has the highest weight content.

[0037] - The weight content of lead oxide (PbO) is at most 0.5% of the total weight of the vitreous binder (for enamel), and preferably zero, and the weight content of cadmium, mercury or chromium oxide is zero.

[0038] The glass binder and / or glass-crystalline matrix microcrystals may contain oxides of at least the following elements: Si, Bi, Na, Zn, Ti, Al, and B. The glass binder and / or glass-crystalline matrix microcrystals may be based on bismuth silicate and / or zinc, or bismuth borosilicate and / or zinc.

[0039] Preferably, regarding the composition of the scattering layer, one or more of the following alternative or cumulative properties are provided:

[0040] - The glassy adhesive comprises at least 80% or at least 90% of the total weight of the enamel.

[0041] - The impurities contained in the enamel shall not exceed 0.5% of the total weight of the enamel.

[0042] The total weight content of coloring elements (Fe2O3, CuO, CoO, Cr2O3, MnO2, Se, Ag, Cu, Au, Nd2O3, Er2O3) is at most 0.5% and even 0.1% of the total weight of the vitreous binder and even the vitreous matrix, and preferably zero (except for unavoidable impurities), so as to make the enamel colorless or as colorless as possible.

[0043] - The weight content of coloring additives, such as (metal oxide) pigments—black or white or even colored—is preferably at most 5% or 1% of the total weight of the enamel, especially 0.5% and even 0.1%, or even zero.

[0044] Enamel is preferably translucent, colorless or colored, whitish or of another color (not completely opaque).

[0045] It is preferable to greatly limit and better avoid coloring additives, such as metal oxide pigments (mixtures).

[0046] It can greatly limit and even avoid:

[0047] - One or more fillers, such as silica and quartz alumina, refractory oxide fillers, such as aluminoborosilicate, hydrated aluminosilicate, calcium silicate, sodium-calcium-aluminosilicate, wollastonite, feldspar,

[0048] - and / or other conventional additives, such as titanates of iron, silicon, zinc, etc.

[0049] Typically, the main faces of laminated glass units (cars or buildings) are numbered from 1 to 4:

[0050] - Surface F1 is the outer (exterior) surface of the exterior glass, which is preferably tinted in motor vehicles, and

[0051] -F2 is the inner surface of the outer glass (laminated interlayer side).

[0052] - The laminated interlayer is preferably PVB or EVA.

[0053] - Surface F3 is the inner surface (laminated laminate side) of the preferably colorless inner glass, and its thickness is typically less than or equal to the thickness of the outer glass.

[0054] -F4 is the inner side of the interior glass (crew compartment side).

[0055] Enamel can be translucent (especially when there is little or no pigment, it is whitish).

[0056] When the first surface is opposite the viewing surface of the scattered light pattern, the enamel can be almost opaque or even opaque, especially:

[0057] - The first face is face F1, and the observed face is face F2 (or the opposite if a visible pattern is required on the outside).

[0058] - Alternatively, if the first sheet is the inner glass of a laminated glass unit or is within a laminated glass unit (internal guide), then the viewing surface is surface F4.

[0059] Enamel is translucent (the first side is opposite to the side where the light pattern is observed, especially in the case of lamination, F2 or F4).

[0060] Microcrystals can occupy, for example, up to 60%, up to 50%, or 40% of the volume of a dimensionally variable micropad, particularly a so-called primary micropad with an equivalent diameter of at least 1 µm. The size (equivalent diameter) of the microcrystal is smaller than the size (thickness and / or equivalent diameter) of the micropad. Non-intersecting microcrystals may be present within the micropad (e.g., at least five), particularly a so-called primary micropad with an equivalent diameter of at least 1 µm. They may appear or remain within the micropad.

[0061] The microcrystals preferably have a diameter of at least 0.1µm, for example less than 2µm and even less than 1µm, such as an equivalent diameter (especially D50 or D90).

[0062] Microcrystals and / or other diffuse particles may occupy a volume fraction of the size-variable micropad within the micropad, particularly a so-called primary micropad having an equivalent diameter of at least 1 µm, for example, up to 60%, up to 50%, or 40%.

[0063] The scattering layer may optionally contain particles (inorganic, refractory, and especially oxide), particularly optionally crystalline scattering particles, which are additionally (e.g., added to the liquid composition) dispersed in a glassy matrix. These particles can be detected by X-ray diffraction, known as “XRD”.

[0064] When the glassy matrix is ​​glass-crystalline, these scattering particles (unlike possible growth germs) are not necessary or are present in reduced amounts to enhance diffusion.

[0065] The scattering particles preferably have a diameter of at least 0.1µm, for example less than 2µm and even less than 1µm (especially D50 or D90).

[0066] The scattering particles are, for example, solid and even optionally hollow particles, such as hollow silica. The scattering (non-luminescent) particles are selected from, for example, alumina, zircon, silica, titanium dioxide, calcium carbonate, barium sulfate, and in particular, they are (white) pigments.

[0067] The scattering layer (all or some of the micropads) may contain up to 10%, 5%, or 1% of the enamel volume of scattering porosity (in the first scattering pattern).

[0068] The scattering layer (all or some of the micropads) may contain scattering (additional particles, optionally added to the glass-crystallized glassy matrix in addition to seed crystals) at a weight of up to 10% or 5% or 1% of the total weight of the enamel, and even as low as 0%.

[0069] Apart from the microcrystals, the size (equivalent diameter) of the scattering particles is smaller than the size (thickness and / or equivalent diameter) of the micropads. Scattering particles may be present within the micropads (e.g., at least 5), especially so-called primary micropads with an equivalent diameter of at least 1 µm. They may appear or remain within the micropads.

[0070] The scattering layer may also optionally contain scattering particles individually or in combination with added scattering particles.

[0071] In one embodiment, the scattering layer contains up to 5% by weight of luminescent (inorganic) particles. The luminescent particles are dispersed in a vitreous binder of a glassy matrix, particularly a glass-crystalline glassy matrix.

[0072] When the scattering layer contains luminescent particles, it is preferable to add a light source, such as a light-emitting diode (LED), that emits light at a wavelength in the visible light region that excites the luminescent particles and causes them to re-emit light. This or these LEDs can be positioned as if they were LEDs emitting in visible light. The excitation wavelength is, for example, in UV, particularly UVA, and may be at 365, 400, or 390 nm. LEDs that emit in both this excitation wavelength and visible light can be considered.

[0073] By using various types of scattering particles and / or various types of light sources, or even various types of luminescent particles, the present invention enables the production of glass units capable of emitting light in multiple colors simultaneously or sequentially.

[0074] When it is necessary to maintain a clear window area that is as transparent as possible when closed, the scattering layer can cover less than 50% of the surface area of ​​the first glass sheet.

[0075] An outer light-emitting strip can be formed along the transverse or longitudinal, lower or upper edge of the first glass sheet.

[0076] The preferred brightness is at least 1 Cd / m 2 .

[0077] The scattering layer can be spaced at least 10 mm or even 40 mm from the light injection area (the wall, edge surface, or edge of the light redirecting element in the first sheet). Therefore, a transparent area with a width of up to 40 mm can be present between the injection area and the edge of the nearest scattering layer.

[0078] The first glass sheet having a scattering layer (preferably made of ultra-clear glass) preferably has:

[0079] - At least 70%, 75%, 80%, 85%, and preferably at least 90% light transmittance in the sense of EN 410:1998 standard.

[0080] - Up to 80%, and even up to 20%, 15%, or 5% (transmitted) haze.

[0081] - And preferably at least 80%, 90%, or 95% resolution.

[0082] In particular, the first glass sheet having the scattering layer (preferably made of ultra-clear glass) preferably has:

[0083] - At least 70% or 75% light transmittance, and at most 80% or 70% haze (transmission).

[0084] - At least 80% light transmittance and at most 55% haze (transmission).

[0085] - At least 85% light transmittance and at most 30% haze (transmission).

[0086] - At least 90% light transmittance and at most 6% haze (transmission).

[0087] Advantageously, the haze is at most 30%, the clarity is at least 90% or 95%, and the light transmittance is at least 88%.

[0088] In one embodiment, during haze measurement, the light spot at the surface of the scattering layer is on the order of centimeters, especially at most 5 cm, particularly about 2.6 cm, and the scattering layer (having a first scattering pattern) preferably occupies at least 30%, 50%, or 60% of the spot in the area illuminated by the spot.

[0089] The transmittance T can be calculated using the luminescent material D65. L For example, measurements can be taken using a spectrophotometer equipped with an integrating sphere, and then, where appropriate, the measured values ​​at a given thickness can be converted to a reference thickness of 4 mm according to standard EN 410:1998.

[0090] Haze and even clarity are preferably measured by a haze meter (e.g., BYK-Gardner Haze-Gard Plus), preferably according to standard ASTDM D1003 (uncompensated).

[0091] It is preferable to perform the measurement before possible lamination. For example, the luminescent body is placed opposite the first carrier surface of the scattering layer.

[0092] In addition, the scattering layer may include a gloss level of at least 60 or 80, and more preferably at least 100 (indicating a smooth surface), expressed in gloss units (ub).

[0093] The scattering layer is preferably a single layer (obtained by depositing a glass-based single layer).

[0094] In addition, the glass with a scattering layer (first pattern) may include a brightness L* of up to 60 and even up to 40 or 30.

[0095] Furthermore, the glass having a scattering layer (first pattern) may include an optical density of up to 0.4 and even up to 0.2.

[0096] The thickness (or maximum height) of the micropad can be determined by observing a cross-sectional view of the scattering layer using a scanning electron microscope at 250x magnification (e.g., at a voltage of 20kV).

[0097] The parameters Am, Bm, Tm, Cm, and Pm can be determined by processing and analyzing black-and-white SEM images of the surface at 250x magnification using a scanning electron microscope.

[0098] For SEM images, select CBS (Concentric Backscattered) mode. CBS is a backscattered electron detector that provides images under chemical contrast.

[0099] For example, software called ImageJ is used for processing and analyzing SEM images.

[0100] For each SEM image, SEM image thresholding is performed from 90 to 255; therefore, the threshold 90 is fixed, and any pixel with an intensity greater than or equal to the threshold 90 is assigned a value of 255, while the remaining pixels will be 0.

[0101] Within the first scattering pattern, the surface area S1 is chosen to be, for example, 500µm*340µm.

[0102] By default, all particle sizes and all roundness are considered.

[0103] Calculate the number of individual pads and measure parameters Am, Bm, Tm, Cm, and Pm.

[0104] The evaluation can be repeated in several regions of multiple scattering patterns, either in the first scattering pattern or even in order to calculate the parameters more representatively.

[0105] Preferably, the arrangement of the micropads can be further defined by at least one of the following features:

[0106] - The average distance Bm is less than 5µm, 4µm or up to 3µm, and even better, at least 1µm.

[0107] - In the analytical surface, the first scattering pattern is defined by an average perimeter Pm (preferably taken from the substrate) of at least 3µm or 4µm and preferably less than 10µm.

[0108] - In the analytical surface, the first scattering pattern is defined by an average circularity Cm (preferably taken from the substrate) of at least 0.7 or 0.75, 0.8 or 0.85 and less than 1 or 0.95.

[0109] The first glass sheet can have a rectangular, square, or even any other shape (circular, elliptical, polygonal) main surface. The glass sheet can have a diameter greater than 1.5m. 2 The size.

[0110] The glass of the first glass sheet (and even (one or more) other optional glass sheets) is preferably float glass. In this case, the scattering layer can be deposited equally well on both the "tin" side and the "atmosphere" side of the substrate.

[0111] Other features can be provided for the first glass sheet:

[0112] - The first glass sheet is curved or even tempered.

[0113] - The first glass sheet is specifically tempered by hot tempering (after firing in a rapid cooling tempering furnace, usually by a nozzle), and the firing in the tempering furnace enables the formation of an enamel layer from a liquid composition (paste) - optionally pre-dried - based on the glass frit.

[0114] For the roof (usually tinted), a non-zero transmittance TL is preferred, and even at least 0.5% or at least 2%, and at most 40% or even at most 8% transmittance TL.

[0115] For the rear glass unit (laminated or non-laminated, including the rear panel) or the rear window (preferably a laminated glass module), a non-zero transmittance TL is preferred, and even at least 10% or at least 20%, and especially at most 80% or at most 70% transmittance TL (especially for the rear glass unit or tinted window).

[0116] For the front glass unit (laminated or unlaminated, especially tinted), a non-zero transmittance TL is preferred, and even at least 50% or at least 70% transmittance TL.

[0117] For windshields (preferably laminated), a non-zero transmittance TL is preferred, and even at least 70% transmittance TL is preferred. These TL values ​​can be in areas with a scattering layer and / or adjacent to the scattering layer (and in areas of clear glass).

[0118] Desiredly, the scattering layer forms light markers, one or more light symbols. In this application, the term "symbol" should be understood as referring to icons and / or linguistic signifiers, i.e., using symbols (numbers, pictographs, signs, symbol colors, etc.) and / or letters or words.

[0119] In one implementation, the surface of the scattering layer can be a free surface (without (one or more) other elements on it).

[0120] This can be the surface F4 of a laminated glass unit, or the surface F1 or F2 of a single monolithic glass unit, or the outer or inner surface of a double-layered glass unit.

[0121] In one embodiment, the first glass sheet is monolithic, which optionally forms part of a double-layer glass unit, the scattering layer having a free surface or a surface covered by functional elements.

[0122] The functional components are optionally transparent, preferably having a thickness of up to 1.5 mm or sub-millimeter thickness, and in particular:

[0123] - Polymer film in adhesive contact with the scattering layer

[0124] - and / or functional (single or multiple) overlays.

[0125] It can be a film bonded to the first main surface with an optical adhesive, and in particular, the enamel substrate is a monolithic glass unit (not part of a laminate or multilayer glass unit).

[0126] The polymer film may be colored and / or may have a functional layer (conductive, low-emissivity, heating, etc.). Alternatively, a colored polymer film with a functional layer may be bonded to a second master surface.

[0127] The polymer film may have a thickness of 5µm to 1mm, preferably at least 50µm and at most 200µm. The polymer film may be selected from polyesters, especially polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), polyolefins such as polyethylene (PE), polypropylene (PP), polyurethane, polyamide, and polyimide.

[0128] PET is preferred due to its transparency, surface quality, mechanical strength, and availability in various sizes. The absorption rate of such transparent films, particularly PET transparent films, is preferably less than 0.5% or even at most 0.2%, and the haze is less than 1.5% or even at most 1%. Optically clear adhesives are preferred, particularly those based on polyester, acrylic, or silicone resins. It can be a pressure-sensitive adhesive (PSA).

[0129] In one embodiment, the first glass sheet forms part of a laminated glass unit (optionally curved), which includes:

[0130] -The first sheet, particularly colorless, is made of clear or ultra-clear glass.

[0131] -Laminated interlayers, especially colorless or even colored ones.

[0132] - and a second transparent colorless or colored transparent sheet, preferably clear or ultra-clear glass or even colored glass or plastic such as poly(methyl methacrylate) PMMA or polycarbonate PC.

[0133] Preferably, the first main surface is on the laminated interlayer side, and the scattering layer is in adhesive contact with the laminated interlayer or is covered (on it) by a functional element that is optionally in adhesive contact with the laminated interlayer.

[0134] Preferably, the laminated glass unit includes a light source, such as a light-emitting diode (LED). One or more LEDs may be in or near a (through) hole in the inner glass sheet for optical coupling through the wall defining the hole, or they may be facing the edge of the inner glass sheet.

[0135] Therefore, the enamel substrate may further include a light source, particularly a plurality of inorganic light-emitting diodes, optically coupled to a first glass sheet forming a light guide, specifically light incident from the light source.

[0136] -Through the edge surface of the first glass sheet

[0137] -or the wall of the hole in the first glass sheet

[0138] -Or via the first principal surface or the second principal surface opposite to the first principal surface, particularly by direct optical coupling or by means of optical devices, particularly light redirection elements, such as prism films, particularly reflective films, on the first or second principal surface and away from the scattering layer.

[0139] The first glass sheet may be a monolithic piece, which optionally forms part of a double-layer glass unit, the scattering layer having a free surface or a surface covered by functional elements including films and / or coatings (particularly functional elements in contact with the scattering layer and especially in the inter-pad region between micropads in contact with the first exposed surface or with the sublayer already described).

[0140] The first glass sheet may be part of a laminated glass unit, comprising:

[0141] - The first sheet is preferably made of clear or ultra-clear glass.

[0142] - A laminated interlayer, preferably made of PVB, optionally colored.

[0143] - and a second transparent glass or plastic sheet, preferably colored.

[0144] Preferably, the first main surface is the laminated interlayer side, and the scattering layer is in adhesive contact with the laminated interlayer or is covered by functional elements (especially functional elements in contact with the scattering layer, and particularly in the inter-pad region between micropads in contact with the first exposed surface or with the sublayer already described), preferably in adhesive contact with the laminated interlayer.

[0145] The first sheet is an internally assembled glass and preferably the first main surface is the inner surface referred to as surface F3, or the first sheet is between the second transparent sheet and the third glass sheet (forming an internal light guide within the laminated interlayer).

[0146] The laminated glass unit may include functional elements, particularly transparent functional elements, which are selected from one or more of the following elements:

[0147] - A silica layer, especially a porous silica layer, such as a sol-gel, forms an anti-reflective layer.

[0148] - A masking layer, optionally adjacent to a scattering layer, particularly on the periphery, especially an enamel layer.

[0149] - Conductive layers, especially electrodes, power supply or heating layers for (opto)electronic components, particularly transparent conductive oxide layers, especially within laminated glass units.

[0150] - Solar control (and / or low emissivity) layers, particularly coatings on the F4 surface, including functional layers of transparent conductive oxides or functional metallic layers within laminated glass units.

[0151] - Within the laminated glass unit (between surfaces F1 and F4), an electronically controlled device, particularly a variable scattering and / or hue, especially having a liquid crystal or electrochromic hue, or an optical valve (for an SPD in a suspended particle device) or a multi-pixel screen (liquid crystal, active-matrix OLED, etc.), such as as described in patent application WO2017 / 115036, or an additional lamp element, is positioned off-center from or facing the scattering layer.

[0152] - A low-refractive-index optical isolator element with a refractive index less than that of the first glass sheet, disposed between the first surface and the second glass sheet, particularly between the first surface and the colored laminate, wherein the coloring is particularly applied to the porous silica layer or fluorinated film on the first surface, especially selected from ethylene tetrafluoroethylene copolymer (ETFE) and fluorinated ethylene-propylene copolymer (FEP).

[0153] In applying for WO2008 / 059170, especially in Figure 11 In, or even in application WO2015 / 101745, a porous sol-gel silica layer with a refractive index of at most 1.3 or even at most 1.2 and a thickness of at least 200 nm or even at least 400 nm and preferably at most 1 µm is described.

[0154] In an external light configuration, the first glass sheet may be an externally mounted glass and preferably the first main surface is the inner surface referred to as surface F2.

[0155] In one configuration, the enamel substrate forms glass units for land, water, or air vehicles, or serves as glass panels for buildings, particularly:

[0156] - Curved laminated roof, the first glass sheet is either internally fitted glass or intermediate between a second glass sheet and a clear glass or polymer sheet.

[0157] - The rear window, especially the first glass pane, is an externally mounted glass, with a diffuser layer on the passenger compartment side.

[0158] - On the side, it is laminated or monolithic (window glass), and the first glass sheet is an inner or outer glass unit.

[0159] - Curved laminated windshield, the first glass sheet is either internally or externally assembled glass.

[0160] Preferably, the laminated interlayer with the lowest possible haze, i.e., at most 1.5% and even at most 1% (clear or colored), is selected.

[0161] These interlayer spacers can be based on polymers selected from polyvinyl butyral (PVB), polyvinyl chloride (PVC), polyurethane (PU), polyethylene terephthalate, or ethylene vinyl acetate (EVA). The interlayer preferably has a thickness of 100 µm to 2.1 mm, more preferably 0.3 to 1.1 mm. The laminated interlayer can be made of polyvinyl butyral (PVB), polyurethane (PU), or ethylene / vinyl acetate copolymer (EVA), formed from one or more films, for example, with a thickness of 0.2 mm to 1.1 mm. Conventional PVB can be selected, such as RC41 from Solutia or Eastman.

[0162] The laminated interlayer can optionally be composite in its thickness (PVB / plastic film such as polyester, PET, etc. / PVB).

[0163] The surface of the laminated interlayer can be smaller than the surface of the laminated glass unit, for example, leaving free grooves (as a frame or as a headband), so it is not laminated.

[0164] For laminated windshields, the laminated interlayer may have a wedge-shaped cross-section that gradually decreases from the top to the bottom of the laminated windshield, particularly to avoid ghosting when a head-up display (HUD) is attached. The laminated interlayer may be acoustic. Patent EP0844075 may be cited as an example of an acoustic sheet. Acoustic PVB described in patent applications WO2012 / 025685 and WO2013 / 175101 may also be cited, especially tinted PVB as in WO2015079159.

[0165] As examples of offset or non-offset glass units, in the case where the glass unit emits light from the edge, patent applications WO2010 / 049638, WO2013079832, and WO2013153303 may be mentioned.

[0166] The first glass sheet may include a masking layer, which is typically located on the periphery of the first or second surface, such as a black or dark opaque enamel layer forming a peripheral strip or even a peripheral frame.

[0167] The scattering layer can be more centered, away from the masking layer.

[0168] The first glass sheet may include, in particular, a masking layer, which is made of enamel and is adjacent to or offset from the scattering layer on the second surface, particularly along the periphery of the optical coupling edge surface coupled to the light source.

[0169] Preferably, at least in the guiding region, the width of the layer along the optical coupling edge surface (between the edge surface and the edge of the scattering layer) is eliminated or limited to less than 5 cm or even 3 cm.

[0170] More broadly,

[0171] - The inner glass unit (usually the first glass sheet) may have an outer inner masking layer (which may be a black or dark enamel layer, a paint layer or an opaque ink, preferably on surface F2 or a laminated interlayer, or even on an additional carrier film (PET, etc.).

[0172] - and / or the outer glass unit (sometimes the first glass sheet) may have an outer outer masking layer (respectively, the outer masking layer), which is a black or dark enamel layer, a lacquer layer or an opaque ink, preferably on surface F2 (respectively F3 or F4) or on the laminated interlayer, or even on an additional carrier film (PET, etc.).

[0173] Advantageously, the outer and inner shielding layers contain the same material, preferably enamel (especially black enamel), either on F2 and F4 or on F2 and F3.

[0174] The scattering layer can be on surface F3:

[0175] -In the resist of the inner masking layer on face F3 or face F4

[0176] - Outer shielding layer on face F2.

[0177] In an alternative implementation (colorless exterior glass, such as the rear window), the scattering layer can be on surface F2:

[0178] -In the resist layer of the outer shielding layer on surface F2

[0179] - and even the inner shielding layer on face F3 or F4.

[0180] The first glass sheet may include a transparent functional layer on the second main surface opposite to the first main surface having the enamel scattering layer and / or on the first surface adjacent to the scattering layer, provided that the layer does not significantly impede the light guiding function (through its absorption, etc.).

[0181] Several types of functional layers exist (on the first glass sheet or in the laminated glass unit), selected from at least one of the following layers:

[0182] - A masking layer, adjacent to the scattering layer, particularly on the periphery, especially the enamel layer, preferably has a width of less than 5 cm or 3 cm between the optical coupling edge and the nearest edge of the scattering layer.

[0183] - Conductive layers, especially electrodes (conductive layers connected to a power source), layers used to power (opto)electronic components (sensors, etc.) (forming circuits) – where possible, the components are as transparent and / or discrete as possible – especially transparent conductive oxide layers.

[0184] - Electromagnetic shielding layer

[0185] - Heating layer, also known as the electrically conductive layer (usually supplied by two current bands).

[0186] - A layer that reflects or absorbs solar radiation, referred to as a solar control layer (and / or a low emissivity layer), particularly a coating containing (at least) a transparent conductive oxide (TCO) functional layer or (at least) a metallic functional layer, may also be used as a heating layer. The solar control layer has an external current supply.

[0187] The conductive layer may contain transparent conductive oxides (TCOs), which are materials that are both good conductors and transparent in visible light, such as indium oxide (ITO) doped with tin, tin oxide (SnO2:F) doped with antimony or fluorine, or zinc oxide (ZnO:Al) doped with aluminum.

[0188] The conductive layer can also be a metallic layer, preferably a thin layer or a stack of thin layers, referred to as TCC (for "transparent conductive coating"), for example made of Ag, Al, Pd, Cu, Pt, In, Mo, Au, and typically with a thickness of 2 to 50 nm. Polymer films coated with the conductive layer can be used, such as the clear PET film called XIR from Eastman, co-extruded PET-PMMA films, such as the SRF type from 3M® (SRF is used for solar reflective films).

[0189] In the case of laminated glass units (skylights, etc.), the preferred embodiment is as follows:

[0190] - The first and / or second glass units are colored and / or the laminated interlayer is colored over its entire thickness.

[0191] - Surface F4 is coated with a transparent conductive oxide layer (referred to as TCO), especially a thin stack of TCO layers.

[0192] - and / or preferably, face F2 or F3 is coated with a thin layer stack having one or more silver layers.

[0193] As a low emissivity layer based on TCO, reference can be made to surface F4 in patent US2015 / 0146286, especially those described in embodiments 1 to 3.

[0194] The light source preferably includes multiple inorganic light-emitting diodes, although other types can be envisioned, such as light strips (OLEDs, etc.).

[0195] Another object of the present invention is to use the laminated glass unit obtained by the above manufacturing method as a glass unit for land, water or air vehicles, or as a glass panel in the construction industry, especially as a glass unit for motor vehicles, and most particularly for use on motor vehicle roofs.

[0196] The scattering layer containing a vitreous binder is preferably obtained by the following method, wherein:

[0197] - Mix glass frit with an organic medium to form a paste.

[0198] - The paste is deposited on the first glass sheet.

[0199] - Sinter the assembly.

[0200] Therefore, the present invention also relates to a method of manufacturing, particularly as described above, an enamel substrate comprising forming a scattering layer of a scattering enamel comprising a glassy matrix on a first main surface of a first glass sheet, (the scattering layer comprising a first scattering pattern having a width of at least 0.1 mm) sequentially relating to:

[0201] - A film of a liquid vitrifiable composition, referred to as enamel paste, comprising a mixture of an organic medium and an inorganic solid, wherein the inorganic solid comprises a glass frit having a given glass transition temperature Tg1, is deposited on a first glass sheet.

[0202] - It is preferable to dry at a temperature of up to 200°C (especially by infrared or even ultraviolet light).

[0203] - Firing at a temperature Tc higher than the glass transition temperature Tg1 of the glass material to form a glassy matrix.

[0204] The enamel paste contains an inorganic solid percentage of up to 40%, and even up to 30%, and even more preferably up to 20%, or up to 15% or 10%, or up to 5%, and especially at least 0.5% or 1%, and the first scattering pattern is discontinuous, formed by individual micropads of the scattering enamel.

[0205] Screen printing screens can be of varying fineness, such as 90T, 120T, 150T, and 180T, where T corresponds to the number of lines per centimeter.

[0206] The parameter that can affect the size of micropads and even the formation “threshold” of a layer (for a given paste composition) within a single micropad is the thickness of the liquid film.

[0207] The film thickness E0 depends on method parameters, such as deposition rate, screen printing squeegee pressure, etc.

[0208] In particular, the amount of inorganic solids per unit of printed surface area will affect the results.

[0209] The glass-crystal scattering layer is anti-stick or "non-adhesive". Glass sheets with a fired enamel layer can therefore be bent. Glass sheets with an enamel paste layer can be fired during bending.

[0210] Advantageous:

[0211] - Deposition is performed via screen printing.

[0212] - The glass frit is crystallizable, the enamel paste preferably contains seed crystals, firing specifically produces diffuse microcrystals, the matrix is ​​glass-crystalline and / or the enamel paste contains additional refractory particles, especially various scattering additives (e.g., black pigments).

[0213] The term "crystallizable glass frit" preferably refers to at least 30% by weight of oxides contained in the glass frit reacting during firing to form crystals. Suitable oxide glass frits include borosilicate glass frits, such as bismuth borosilicate glass frits and zinc borosilicate glass frits. For more details on glass frits, see patents US5153150, US6207285, and EP1888333.

[0214] The enamel paste may optionally contain up to 20% (by weight), for example, 0.1% to 20% or 2% to 10% (by weight) of growth seed crystals, such as bismuth silicate, zinc silicate, and bismuth titanate. Seed crystals may include, but are not limited to, one or more of Zn₂SiO₄, Bi₂SiO₂O, Bi₄(SiO₄)₃, Bi₂SiO₅, 2ZnO.₃TiO₂, Bi₂O₃.SiO₂, Bi₂O₃.₂TiO₂, 2Bi₂O₃.₃TiO₂, Bi₇Ti₄NbO₂¹, Bi₄Ti₃O₁², Bi₂Ti₂O₇, Bi₁²TiO₂₀, Bi₄Ti₃O₁², and Bi₂Ti₄O₁¹. Examples can be found in patents US6624104 and US5208191 or EP1888333.

[0215] Organic media may contain or even consist of one or more of the following organic compounds: alcohols, esters, diols, especially diol esters and terpineol. Terpinineols or terpinols are those with the empirical formula C0. 10 H 18 O-unsaturated monocyclic monoterpenoid alcohols (monoterpenoid alcohols).

[0216] The medium may contain or even consist of one or more of the following organic compounds: diethyl ether and diethylene glycol, butyl ether and diethylene glycol ether, vegetable oil, mineral oil, low molecular weight petroleum fraction, tridecanol, synthetic or natural resins (e.g., cellulose resins or acrylate resins), propylene glycol monomethyl ether (PM), dipropylene glycol monomethyl ether (DPM), tripropylene glycol monomethyl ether (TPM), propylene glycol monobutyl ether (PnB), dipropylene glycol monobutyl ether (DPnB), tripropylene glycol n-butyl ether (TPnB), propylene glycol n-propyl ether (PnP), dipropylene glycol n-propyl ether (DPnP), tripropylene glycol n-butyl ether (TPnB), propylene glycol monomethyl ether acetate (PMA), Dowanol DB (diethylene glycol monobutyl ether) sold by Dow Chemical Company, USA, or other ethylene glycol ethers or propylene glycol ethers.

[0217] Drying allows for the elimination of the vast majority (e.g., at least 80%) of the solvent by limiting the risk of dust contaminating the surface (which would affect the transparency of the scattering layer).

[0218] Specifically, the firing furnace can be used in an industrial bending (tempering) line. Tempering does not alter the optical properties of the scattering layer.

[0219] Bending occurs through gravitational sag, as described in patents WO2007138214 and WO2006072721, or through suction, as described in patent WO02 / 064519.

[0220] The glass frit is preferably in particle form with a D90 of up to 20µm, especially 5µm, or even 4µm. The particle size distribution can be determined using a laser particle size analyzer.

[0221] In the case of screen printing, it is preferable to use a screen made of textile or metal mesh, a cross-grinding tool, and a squeegee. The thickness is controlled by selecting the mesh size and tension of the screen, by selecting the distance between the first glass sheet and the screen, and by the moving pressure and speed of the squeegee.

[0222] The invention will be better understood by reading the examples of the vehicle luminous glass device according to the invention shown in the following figures, and other details and advantageous features of the invention will become apparent. Attached Figure Description

[0223] Figures 1 to 3 This is a schematic diagram of the luminescent enamel glass unit according to the present invention.

[0224] Figures 4 to 7 These are SEM (Scanning Electron Microscope) images of the surface of the enamel glass unit according to the present invention in Examples 1 to 4.

[0225] Figures 8 to 13 These are SEM images of the cross-sections of the enamel glass units according to the present invention in Examples 1, 2 and 4.

[0226] Figure 14 , 16 Images 1, 18, and 20 are SEM images of the surface of the enamel glass unit according to the present invention in embodiments 1, 2, 3, and 4.

[0227] Figure 15 , 17 Photos 19 and 21 are the photos after image processing.

[0228] Figure 22 This is an SEM image of the surface of the enamel glass unit in Comparative Example No. 6.

[0229] Figure 23 This is a graph showing the ratio of the light transmittance of the enamel glass unit according to the present invention (with six points for the above embodiments 1 to 6) to the light transmittance of the glass unit without enamel as a function of the inorganic content R% in the enamel paste.

[0230] Figure 24 This is a graph showing the change in the percentage (%) haze of the enamel glass unit according to the present invention (with six points for Examples 1 to 6 above) as a function of the inorganic content R% in the enamel paste.

[0231] Figure 25A schematic cross-sectional partial view of a light-emitting laminated glass unit for a motor vehicle in one embodiment of the invention is shown, comprising an enamel glass unit that emits light from its edge surfaces.

[0232] Figure 26 The use of a luminescent enamel glass unit according to the invention (e.g.) is shown. Figure 1 A schematic cross-sectional view of the illuminated roof of a car (the kind shown in the image).

[0233] Figure 27 A schematic cross-sectional view of a laminated luminescent glass unit according to one embodiment of the present invention is shown, which (for example) includes an enamel glass unit illuminated by the inner edge surface of the wall serving as a closed through-hole.

[0234] Figure 28 It shows Figure 27 A schematic front view of the illuminated enamel glass unit.

[0235] Figure 29 A schematic cross-section and partial view of a light-emitting laminated glass unit for a motor vehicle according to one embodiment of the present invention are shown, which includes an enamel glass unit panel illuminated by a light source facing light redirection elements on surfaces F4 and F3.

[0236] Figure 30 A schematic cross-sectional partial view of a light-emitting laminated glass unit for a motor vehicle according to one embodiment of the present invention is shown, which includes an enamel glass unit illuminated by its edge surfaces, the enamel glass unit being located between two glass sheets. Detailed Implementation

[0237] Other details and advantageous features of the invention will become apparent after reading the embodiments according to the invention illustrated in the following figures.

[0238] For clarity, it should be noted that the various elements of the objects shown are not necessarily reproduced to scale.

[0239] Figures 1 to 3 This is a schematic diagram of an enamel glass unit according to the present invention. Each unit includes an enamel layer with a plurality of transparent and translucent scattering patterns 20 (translucent micropads) on a first main surface 11, allowing visual observation through patterns that are as small and discrete as possible, and as invisible as possible. The pattern selection is as follows:

[0240] - Figure 1 A set of nine scattering rectangles (transparent and translucent) with increasing variable widths, for example from 2mm to 50mm, especially as they couple to the LED away from the light injection area, such as the edge face 10 of the glass.

[0241] - Figure 2A set of seven scattering circles (transparent and translucent), for example, on the order of centimeters.

[0242] - Figure 3 Two diffuse circles (e.g., 10cm x 10cm).

[0243] Figures 1 to 3 Each has a magnified view of its scattering characteristics at a microscale (observed via SEM), showing an independent group of enamel micropads with large pads 20 and smaller pads 21 randomly distributed.

[0244] The first glass sheet is preferably made of ultra-clear glass, such as 1.95mm OPTIWHITE. It can be curved, for example, and can be used as the side of a vehicle, especially a highway vehicle, or for retail counters, etc.

[0245] The first main surface 11 or the opposite surface may include a peripheral masking layer made of black enamel. The first main surface 11 may be covered by a functional film, such as a colored film bonded to the first main surface. To extract more light, a low refractive index layer, such as a porous silica layer on the first surface below the colored film, may be added to form a light isolator.

[0246] I. Embodiment of an Enameled Single-Layer Glass Unit

[0247] Six embodiments, numbered 1 to 6, were prepared on 1.95mm Optiwhite ultra-clear glass using enamel glass units with discontinuous scattering layers. The scattering layers comprised a first rectangular scattering pattern of 3cm / 1cm in size, created by screen printing from a crystallizable enamel paste containing an organic medium, a glass frit, and a seed crystal. Product DV778640 was used, which contains a bismuth silicate-based glass frit and a seed crystal (for growing crystals on itself) sold by PMI, and a carbohydrate / cellulose (derived)-based organic medium 808018 sold by Ferro.

[0248] Use 90T wire mesh.

[0249] In various embodiments, the ratio R of inorganic solids is simply changed by diluting it to different degrees with an organic medium.

[0250] The enamel paste is fired for 250 seconds above the glass transition temperature.

[0251] A preliminary step of evaporating the solvent can be carried out at, for example, 100°C to 200°C.

[0252] Enamel is a glassy crystalline material that contains a vitreous binder and seed crystals, the vitreous binder having microcrystals produced through firing. The enamel here is translucent (semi-transparent).

[0253] In Examples 1 to 5, the scattering layer is formed with a random distribution of large and small enamel micropad groups depending on the ratio R% of inorganic solids in the enamel paste.

[0254] In contrast, Example 6 corresponds to the enamel area with holes.

[0255] Table 1 below shows the ratio of organic media R0, ratio of inorganic solids R%, wet thickness of deposited film (continuous film), wet thickness after firing E0 or E1 (E1 is estimated by the SEM portion of Examples 1 to 5), haze H, transmittance TL, and clarity C for each embodiment.

[0256] [Table 1]

[0257] .

[0258] Haze and clarity are preferably measured using a haze meter (e.g., BYK-Gardner Haze-Gard Plus), preferably according to standard ASTDM D1003 (uncompensated). The haze of this 15µm thick glass-crystalline enamel continuous layer is 100°.

[0259] According to ISO 2813 standard, gloss was measured in gloss units (GU) using a gloss meter with a MICRO TRIGLOSS instrument (BYK-GARDNER) (measured at a 60° angle on the scattering layer side). The gloss range was 3 (Example 1 or 6) to 140 (Example 5). The gloss of the exposed glass was 159.

[0260] Measure the lightness. The lightness range is 3 (Example 1 or 6) to 140 (Example 5). The lightness of the continuous enamel is 159.

[0261] The optical density was measured in the range of 0.15 (Example 1) to 0.05 (Example 5). The optical density of the exposed glass was 0.03.

[0262] The glass-crystal scattering layer is anti-sticking. Glass sheets with a fired enamel layer can therefore be bent. Glass sheets with an enamel paste layer can be fired during bending.

[0263] Figures 4 to 7 The images are SEM photographs (magnification of 2500x) of the surface of the enamel glass unit according to the present invention, which are numbered 1 to 4 of the four embodiments. Each of them shows an independent enamel micro pad group with large pads 20 and smaller pads 21 randomly distributed depending on the percentage of inorganic solids in the enamel paste. Microcrystals 22 are seen in the large pads 20.

[0264] Figures 8 to 13These are SEM images of the cross-section of the enamel glass unit according to the present invention in Examples 1, 2 to 4, which include measurements of the thickness (maximum height) of the large pad 20.

[0265] Figure 14 , 16 Images 18 and 20 are SEM photographs (magnification of 250x) of the surface of the enamel glass unit according to the present invention in embodiments 1, 2, 3 and 4.

[0266] Figure 15 , 17 Images 19 and 21 are pre-processed photographs used to define the geometric parameters of the micropad group.

[0267] The parameters Am, Bm, Tm, Cm, and Pm can be determined by processing and analyzing the black-and-white SEM images of these four surfaces at 250x magnification using a scanning electron microscope.

[0268] For SEM images, select CBS mode to provide images with chemical contrast.

[0269] For each SEM image, apply an image threshold of 90 to 255.

[0270] For example, for image processing and analysis, software called Image J is used. Within the first scattering pattern, the surface area S1 is chosen to be 500µm * 340µm.

[0271] By default, all granularities and all roundness are considered.

[0272] Calculate the number of individual pads N and measure the parameters Am, Bm, Tm, Pm, and Cm (between 0 and 1).

[0273] The parameters are recorded in Table 2 below.

[0274] [Table 2]

[0275] .

[0276] When another analytical surface area was selected, such as 300µm×300µm, similar results were found.

[0277] Figure 22 This is an SEM image (magnification 1000x) of the surface of the enamel glass unit in Example 6.

[0278] The first scattering pattern comprises a continuous enamel region 2' having microcrystals 22 and independent (micrometer-scale) openings. The openings have irregular shapes and sizes and are irregularly distributed. Some enamel "particles" 20' may be present within the openings.

[0279] Figure 23 This is a graph showing the ratio of the light transmittance TL1 (with six points for Examples 1 to 6 above) of the enamel glass unit according to the present invention to the light transmittance TL0 of the glass unit without enamel as a function of the inorganic content R% in the enamel paste.

[0280] This ratio increases naturally with R and ranges from approximately 63.1% to approximately 100%.

[0281] Figure 24 This is a graph showing the change in the percentage (%) haze of the enamel glass unit according to the present invention (with six points for Examples 1 to 6 above) as a function of the inorganic content R% in the enamel paste.

[0282] The haze decreases naturally with R, ranging from approximately 63.1% to approximately 100%.

[0283] The substrate of Examples 1 to 6 may be part of a laminated glass unit.

[0284] II. Examples of Light-Emitting Laminated Glass Units

[0285] Figure 25 A schematic cross-sectional partial view of a light-emitting laminated glass unit for a motor vehicle according to one embodiment of the present invention is shown, which includes an enamel glass unit illuminated by edge surfaces.

[0286] Here, a laminated glass unit 100, which serves as the roof with an edge surface 10 and outer main surfaces referred to as surfaces F1 and F4, comprises:

[0287] - A first glass sheet, forming the interior assembly glass on the crew compartment side, for example, rectangular (e.g., having dimensions of 300 × 300 mm), made of mineral glass, having a main surface 12 corresponding to surface F3 and a first main surface 11 as surface F4 and an edge surface 10, preferably with rounded corners (to avoid detachment), here being the longitudinal edge surface (or, in a variant, the transverse edge surface), for example, a soda-lime-silica glass sheet, ultra-clear, for example, Diamant glass sold by Saint-Gobain Glass, with a thickness equal to, for example, 2.1 mm, and a refractive index n1 of about 1.51 at 550 nm, or 1.95 mm Optiwhite glass, optionally having an ITO stack 15 on surface F4 (crew compartment surface).

[0288] -Laminated interlayer 3, for example, clear or colored PVB with a thickness of 0.76 mm, preferably having a haze of up to 1.5%, having an edge face 30, here a longitudinal edge face, offset from the longitudinal edge face 10 towards the center of the glass, the refractive index n of the laminated interlayer. f Less than n1, equal to 1.48 at 550nm.

[0289] - A second glass sheet 1' having the same dimensions as the first glass sheet 1, forming an outer mounting glass, having a composition for coloring solar control functions (Venus VG10 or TSA4+ glass sold by Saint-Gobain Glass), for example, a thickness equal to, for example, 2.1 mm, and / or having clear glass covered with a solar control coating or coloring plastic film, having a main surface facing face 12 or F3 referred to as the inner or laminated surface 12' or F2, and another main surface 11' corresponding to face F1, and an edge surface 10' which is longitudinal here.

[0290] The laminated interlayer may include a transparent polymer sheet such as PET, particularly a cover surface, for example, covering at least 90%. This sheet may be coated with a transparent conductive coating, for example, for solar control and / or module supply. For example, it relates to PVB / sheet / PVB, and particularly PVB / PET / PVB assemblies.

[0291] The first glass sheet of this article includes a peripheral through-hole or notch along the longitudinal edge surface 10, the size of which is preferably smaller than that of the longitudinal edge surface.

[0292] Light-emitting diodes 4 extend along the periphery of the first glass sheet. These are side-emitting diodes housed within recesses. Therefore, these diodes 4 are arranged on the PCB 5 substrate, for example, as parallelepiped strips, preferably as opaque as possible, with their emitting surfaces parallel to the PCB substrate and facing the edge face 10 in the recessed edge portion. The PCB substrate is fixed to the edge of face F2 12', for example, by adhesive 7 (or double-sided adhesive), and a recess is provided between faces F2 and F3, which can be achieved by sufficiently removing the PVB from the edge face 30. An outer shielding strip 6 made of opaque enamel is added to face F2, which can shield the PCB carrier and even the emitted light from that area.

[0293] The distance between the diode and the edge surface 10 is minimized, for example, to 1 to 2 mm. The space between each wafer and the optically coupled edge surface 10 is protected from any contamination, such as water or chemicals, during the long-term manufacturing process of the light-emitting glass unit 100.

[0294] The luminescent glass unit features a polymer encapsulation, typically made of black polyurethane, particularly PU-RIM (molding reaction). This encapsulation is double-sided at the edges of the glass unit. This encapsulation ensures long-term sealing against water, cleaning products, etc. The encapsulation also provides good aesthetics and allows for the integration of other components or functions (reinforcing inserts, etc.).

[0295] As described in documents WO2011092419 or WO2013017790, polymer packages may have through-holes closed by removable covers to house or replace diodes.

[0296] The light-emitting glass unit 100 may have multiple light zones, wherein one or more light zones preferably occupy less than 50% of the surface of at least one face, especially in the case of a given geometry (rectangle, square, circle, etc.).

[0297] Light (after being refracted on edge surface 10) propagates in the first glass unit 1 forming the light guide through total internal reflection (at surface F3 and on surface F4).

[0298] For light extraction, an anti-adhesion enamel scattering layer 2 according to the invention is deposited on face F3 12 (or F4 11, as a variant). It comprises a glass-crystalline matrix incorporated with microcrystals and is in the form of non-intersecting pads.

[0299] Several series of diodes (one-edge, two-edge, three-edge) are available, with independent control across the entire perimeter and even different colors. White or colored LEDs can be selected for ambient lighting, reading, etc. Red light can be selected for signal transmission and can be alternated with green light.

[0300] The sintering of the scattering layer 2 can be carried out before or during bending.

[0301] The roof 100 can, for example, form a fixed illuminated panoramic roof 1000 for a motor vehicle such as a car, which is externally mounted to the body 8' via adhesive 61', as... Figure 26 As shown in the image.

[0302] The laminated luminescent glass unit 100 can alternatively form a front or rear bezel glass (optionally by removing the encapsulation). A scattering layer forms, for example, a turn signal indicator or sign. If so, it is on the first clear or ultra-clear glass unit, which is the outermost one, on face F1 or preferably on face F2 on the laminated side. Optionally, an opaque masking layer is located on the inner glass unit—colored or colorless—for example, on face F3.

[0303] This laminated luminescent glass unit can alternatively form the windshield (optionally by removing or adjusting the encapsulation). A scattering layer forms, for example, a collision avoidance signal for the driver and forms a strip, particularly along the lower longitudinal edge, on the innermost first clear or ultra-clear glass unit on face F4 or face F3. For example, the light illuminates (red) when a vehicle in front gets too close. The second glass unit is also clear or ultra-clear glass.

[0304] In one variant, the first glass sheet is recessed from the outer glass sheet.

[0305] Figure 27 A schematic cross-sectional view of a laminated luminescent glass unit 200 according to one embodiment of the present invention is shown, which (for example) includes an enamel glass unit illuminated by the inner edge surface of the wall serving as a closed through-hole.

[0306] As shown in Figure 2627, the laminated glass unit 200 includes a first glass sheet 1, which is adhesively bonded to a second glass sheet 1' via a laminating interlayer 3.

[0307] A through-hole 9 is drilled through the first glass sheet 1, forming an inner edge 17 in the first glass sheet 1 to accommodate the LED 4, with the emitting surface of the LED 4 facing the inner edge 17 (front emitting diode). A solar or heating control layer 16 is on surface F2 12'. The through-hole is sealed, for example, by a metal pad.

[0308] In one variant, this is a single-pane glass unit (window, side, etc.), optionally without through-holes.

[0309] In one variant, an optical module, such as a guiding element, is placed between diode 4 and wall 17, as described, for example, in patent WO2018178591.

[0310] Figure 28 It shows Figure 27 A schematic front view of the luminescent enamel glass unit. The scattering pattern is, for example, a star 2 formed by a set of translucent anti-stick enamel pads 20 and small pads 21.

[0311] Figure 29 A schematic cross-section and partial view of a light-emitting laminated glass unit of a motor vehicle 300 according to one embodiment of the present invention are shown. This unit includes an enamel glass unit illuminated via a light source 4, contrasting with the front laminated light-emitting glass unit 200. It includes a light source 4 facing surface F4 11 and a light redirection element 19, such as a prism film, particularly a reflective film, on surface F3 12 or on the prism film side F4 11, thus omitting holes in the sheet. The light source 4 remains an LED assembly. Layers 15 and / or 16 of the front glass unit may be retained.

[0312] Figure 30A schematic cross-section and partial view of a light-emitting laminated glass unit of a vehicle 400 according to one embodiment of the present invention are shown, comprising an enamel glass unit illuminated by its edge surfaces, the enamel glass unit being situated between two glass sheets (a colored outer sheet and a glass sheet 18 having a main surface 182 on the interlayer side and an opposing main surface 181) and more specifically, between two laminated interlayers 31, 32 (PVB, EVA, etc.). The light source 4 remains an LED group facing the edge surfaces of the sheets. Layer 15 is held on the innermost surface 181. For example, a scattering layer is situated on both surfaces of the sheet (two offset patterns).

[0313] certainly, Figure 25 Laminated glass units of 27, 29, or 30 mm, especially for road vehicle roofs (motor vehicles), may include other elements, such as:

[0314] - One or more functional layers within a laminate (on PET film, etc.)

[0315] -one or more sensors

[0316] - An electronically controlled device within the laminated glass unit, between surfaces F1 and F4, and even between surfaces F2 and F3, having variable scattering and / or hue, particularly with liquid crystal or electrochromic, or multi-pixel screens or additional lamp elements, offset or oriented towards the scattering layer.

[0317] - A low-refractive-index optical isolator element having a refractive index less than that of the first glass sheet, disposed between the first surface and surface F2, particularly colored between the first surface and the colored laminate interlayer, particularly a porous silica layer on the first surface or a fluorinated film (particularly ETFE or FEP).

[0318] The scattering layer can be of any shape and can even contain scattering particles as part or all of the microcrystals. It can contain luminescent particles and a dedicated light source, especially UV, coupled to the first glass sheet.

Claims

1. An enamel substrate comprising a first glass sheet (1), the first glass sheet (1) comprising a scattering layer (2) made of scattering enamel on a first main surface (11, 12), the scattering enamel comprising a vitreous matrix, the scattering layer (2) comprising at least a first scattering pattern having a width of at least 0.1 mm and a surface S0, the first scattering pattern comprising an independent micropad group of the scattering enamel. Its features are, By defining an analytical surface area S1 smaller than S0 and a defined surface area S2 within the first scattering pattern, S1 is at least 50µm × 50µm and at most 100µm × 600µm, and the surface area S2 is the sum of the surface areas of the micro pads in the surface area S1: - The first scattering pattern is defined by the equivalent average diameter Am of the micropads, which is less than 10µm and at least 1µm. - The first scattering pattern is defined by the average distance Bm between adjacent micropads, and Bm / Am is 0.3 to 2. The scattering layer comprises scattering particles and / or microcrystals of a glassy matrix, wherein the glassy matrix is ​​glass-crystalline.

2. The enamel substrate according to claim 1, characterized in that, The first glass sheet having the scattering layer has: - At least 70% light transmittance, - Up to 80% fog.

3. The enamel substrate according to any one of claims 1-2, characterized in that, The glassy matrix comprising a glassy binder, wherein the glassy binder and the microcrystals of the glass-crystalline matrix are based on bismuth silicate and / or zinc silicate or bismuth borosilicate and / or zinc borosilicate.

4. The enamel substrate according to any one of claims 1-2, characterized in that, The scattering layer contains coloring additives.

5. The enamel substrate according to any one of claims 1-2, characterized in that, The average distance Bm is less than 5µm.

6. The enamel substrate according to any one of claims 1-2, characterized in that: - The first scattering pattern includes the coverage Tm of the micro pads, which is the surface area S2 divided by the surface area S1, and Tm is less than 50%.

7. The enamel substrate according to any one of claims 1-2, characterized in that, The glassy matrix comprises the microcrystals in a glassy binder, and the scattering layer optionally comprises scattering particles separated from the microcrystals at a weight content of up to 10% of the total weight of the enamel.

8. The enamel substrate according to any one of claims 1-2, characterized in that, It also includes a light source that is optically coupled to the first glass sheet forming the light guide.

9. The enamel substrate according to claim 1, characterized in that, Bm / Am ranges from 0.3 to 1.

5.

10. The enamel substrate according to claim 4, characterized in that, The coloring additive is a pigment, and the weight content of the pigment is at most 5% of the total weight of the enamel.

11. The enamel substrate according to claim 4, characterized in that, The coloring additive is a pigment, and the weight content of the pigment is at most 1% of the total weight of the enamel.

12. The enamel substrate according to claim 6, characterized in that, The micropad has a curved surface.

13. The enamel substrate according to claim 6, characterized in that, The micropad has an average contact angle of less than 160°.

14. The enamel substrate according to claim 6, characterized in that, The micro pads have an average contact angle of less than 120°.

15. The enamel substrate according to claim 7, characterized in that, The scattering layer may optionally contain scattering particles separated from the microcrystals at a weight content of up to 5% of the total weight of the enamel.

16. The enamel substrate according to claim 7, characterized in that, The scattering layer optionally contains scattering particles separated from the microcrystals at a weight content of up to 1% of the total weight of the enamel.

17. A laminated glass unit comprising an enamel substrate according to any one of claims 1-16, characterized in that... The laminated glass unit includes: -The first glass sheet -Laminated interlayer (3), optionally colored, - and second transparent glass sheet or plastic sheet.

18. The laminated glass unit according to claim 17, characterized in that, The first glass sheet is an internally assembled glass and the first main surface is the inner surface of the internally assembled glass on the laminated interlayer side, or the first glass sheet is between the second transparent glass sheet or plastic sheet and the third glass sheet.

19. The laminated glass unit according to any one of claims 17 to 18, characterized in that, It includes functional elements, which are selected from one or more of the following elements: - A silicon dioxide layer, which forms an anti-reflective layer. - A masking layer, optionally adjacent to the scattering layer. -Conductive layer, -Solar control and / or low emissivity layer, - Within the laminated glass unit, an electronically controlled device, a multi-pixel screen, or an additional light-emitting element is included, the electronically controlled device being offset from or facing the scattering layer. - A low-refractive-index element forming an optical isolator, the refractive index of which is less than that of the first glass sheet, is disposed between the first glass sheet and the second transparent glass sheet or plastic sheet.

20. The laminated glass unit according to any one of claims 17-18, characterized in that, Laminated glass units are formed for use in land, water, or air transportation vehicles, or as glass units for use in the construction industry.

21. The laminated glass unit according to claim 20, characterized in that, Laminated glass units are formed for use in land, water, or air transportation vehicles, or as glass units for the construction industry, selected from: - Curved laminate roof -Rear window, -side, - Curved laminated windshield.

22. A method for manufacturing an enamel substrate, comprising forming an enamel scattering layer on a first main surface of a first glass sheet, the scattering layer comprising at least one first scattering pattern, wherein the method comprises, in sequence: - A liquid vitrifiable composition, referred to as enamel paste, is deposited on the first glass sheet to form a film. The enamel paste comprises a mixture of an organic medium and an inorganic solid, wherein the inorganic solid comprises a glass frit having a given glass transition temperature Tg1. - The glass material is fired at a temperature Tc higher than its glass transition temperature Tg1 to form a glassy matrix. Its features are, The enamel paste contains up to 30% inorganic solids by weight, and the first scattering pattern is discontinuous, formed by individual micropads of scattering enamel.

23. The method for manufacturing an enamel substrate according to claim 22, characterized in that, The deposition was performed by screen printing.

24. The method for manufacturing an enamel substrate according to any one of claims 22-23, characterized in that, The glass material is crystallizable.

25. The method for manufacturing an enamel substrate according to claim 22, characterized in that, The percentage of inorganic solids contained in the enamel paste is up to 20% by weight of the enamel paste.

26. The method for manufacturing an enamel substrate according to claim 22, characterized in that, The percentage of inorganic solids contained in the enamel paste is up to 15% by weight of the enamel paste.

27. The method for manufacturing an enamel substrate according to claim 24, characterized in that, The enamel paste contains seed crystals, the firing produces microcrystals, the glassy matrix is ​​glass-crystalline, and / or the enamel paste contains diffuse additional refractory particles.

28. The method for manufacturing an enamel substrate according to claim 27, characterized in that, The microcrystals are diffuse microcrystals.

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