Decorative laminated glazing

Abstract

The present invention relates to a laminated glazing (10) comprising a first glass sheet (11) and a second glass sheet (12) adhesively connected to each other by a lamination interlayer (14) comprising a polymer sheet, called a carrier sheet (140), coated with a decorative coating (16) comprising a plurality of superimposed organic ink layers (161, 162, 163) including a first ink layer (161) which is the ink layer closest to the first glass sheet (11) and a second ink layer (162) which is the ink layer closest to the second glass sheet (12).

Description

[0001] This invention relates to the field of laminated glazing, particularly but not exclusively for use in motor vehicles. It especially relates to decorative glazing.

[0002] Today, there is a growing demand for personalized interior and exterior appearances of motor vehicles, particularly through alterations to the look of their fitted glass, without compromising occupant safety and comfort, especially thermal or acoustic comfort. However, extensive customization presents a challenge, as it is often difficult to match with industrial tools designed for mass production, which can also lead to a significant increase in production costs.

[0003] The object of this invention is to provide a decorative glass assembly and a method for manufacturing such glass assembly, which satisfies these different and contradictory requirements.

[0004] Therefore, the present invention relates to a laminated assembled glass comprising a first glass sheet and a second glass sheet bonded together by a laminating interlayer, the laminating interlayer comprising a polymer sheet, referred to as a carrier sheet, the carrier sheet being coated with a decorative coating comprising a plurality of stacked organic ink layers, the plurality of stacked organic ink layers including a first ink layer (which is the ink layer closest to the first glass sheet) and a second ink layer (which is the ink layer closest to the second glass sheet).

[0005] The present invention also relates to a laminated intermediate layer comprising a polymer sheet, referred to as a carrier sheet, coated with a decorative coating comprising a plurality of stacked organic ink layers.

[0006] The present invention also relates to a method for obtaining laminated assembled glass according to the invention, comprising printing a decorative coating (the decorative coating comprising a plurality of stacked organic ink layers) on a polymer sheet, and laminating a first glass sheet and a second glass sheet through a lamination interlayer comprising the polymer sheet.

[0007] The assembled glass according to the invention is a laminated assembled glass, i.e., it comprises two glass sheets bonded together by a laminated interlayer. This assembled glass enhances the safety, anti-theft, and sound insulation properties of vehicles. Although this document focuses on the application of assembled glass for vehicles, the assembled glass according to the invention can also be used in other applications, such as in buildings or household appliances. Therefore, any reference to vehicles can also be understood as a reference to buildings or appliances.

[0008] The glass sheets are typically made of soda-lime glass (also known as soda-lime silicate glass), but can also be made of other types of glass, such as borosilicate glass or aluminosilicate glass. Preferably, the first and second glass sheets are made of soda-lime glass. Alternatively, the assembling glass can be a mixture, meaning that the glass sheets are two different types in some sense. For example, the first sheet can be made of borosilicate glass and the second sheet of soda-lime glass, or the first sheet can be made of soda-lime glass and the second sheet of aluminosilicate glass.

[0009] The thickness of the glass sheet is preferably between 0.5 and 6.0 mm, particularly between 1.0 and 4.0 mm, or even between 1.1 and 3.0 mm. At least one dimension of the assembled glass is preferably at least 1 m.

[0010] Each glass pane can be independently transparent or colored, such as green, gray, or blue. To achieve this, the glass composition includes a colorant, particularly iron oxide, in a total weight percentage (expressed as Fe2O3) ranging from 0.05% to 1.5%, particularly from 0.1% to 1.2%. Other colorants include selenium and oxides of cobalt, chromium, copper, or rare earth elements. Preferably, the outer pane of the mounting glass (i.e., the pane intended to be located on the exterior of the vehicle) is colored. This is the case, for example, if the mounting glass is to appear black or at least dark when viewed from the exterior of the vehicle. The inner pane of the mounting glass is preferably transparent (or ultra-transparent) so that the decorative coating can be clearly seen when intended to be viewed from inside the vehicle.

[0011] At least one glass sheet may be coated with a functional thin layer or a stack of thin layers (containing at least one functional layer). A thin layer refers to a layer whose physical thickness is preferably between 1 nm and 10 µm, particularly between 2 nm and 1 µm. These may particularly include functional layers with infrared radiation reflective properties, especially low-emissivity coatings, designed to provide daylight control and / or thermal insulation properties for the assembled glass. By way of example, a stack of thin layers containing at least one (particularly two, three, or four) silver layers may be deposited on face 2 or face 3 of the laminated assembled glass, i.e., the face in contact with the interlayer of the laminate. In the art, the faces of the glass sheet are generally numbered starting from the face of the assembled glass facing the exterior of the vehicle, hence face 1. Optionally or cumulatively, a stack of thin films containing at least one transparent conductive oxide (TCO) layer (e.g., indium tin oxide (ITO) or aluminum-doped or gallium-doped zinc oxide, or fluorine-doped or antimony-doped tin oxide) may be deposited on face 4 of the laminated assembled glass. In this stack, the functional layer is preferably surrounded by a dielectric layer, particularly an oxide, nitride, or oxynitride-based dielectric layer. The stacking of these layers is preferably deposited by cathode sputtering, particularly magnetic field-assisted sputtering (known as the "magnetron" method). Other deposition methods such as chemical vapor deposition (CVD) or sol-gel methods are also possible.

[0012] At least one glass sheet may be coated with an enamel layer on a portion of its surface, particularly an opaque black enamel in stripe form around the perimeter of the mounting glass, intended to protect and conceal the joint that secures the mounting glass to the vehicle body opening. This enamel layer is preferably present on surface 2 or 3 of the mounting glass, or even on surface 4. The luminance L* of the enamel layer, measured by reflectance on the glass side, should preferably be less than 5. Therefore, the method of the invention may include the step of depositing such an enamel layer on the first and / or second glass sheets, particularly by screen printing or digital printing a fluid enamel composition. This enamel composition specifically comprises glass frit, pigments, and organic media. This enamel can advantageously be replaced by a silicate coating. Alternatively, a black peripheral stripe with the same function can be obtained by printing black ink onto at least one polymer sheet of a laminated interlayer.

[0013] The decorative coating may cover all or part of the surface of the assembled glass. In one embodiment, it occupies the entire surface of the assembled glass, or at least its entire effective surface. "Effective surface" refers to the surface of the assembled glass in which the glass panes are transparent. This area is also called the "transparent area," and specifically excludes areas with opaque enamel. According to another embodiment, the decorative coating occupies only a portion of the surface of the assembled glass, for example, between 10% and 80%, or between 20% and 60%.

[0014] The glass used for mounting is preferably opaque (at least in areas where a decorative coating is present). Its light transmittance is preferably less than 1%, even less than 0.1%. In this document, light transmittance is calculated considering a light source of D65 and a CIE-1964 standard observer. Its optical density should preferably be at least 2, or even at least 3. Even when the glass becomes opaque through this decoration, it remains of interest, particularly for its reflective appearance, which distinguishes it from metal.

[0015] The laminated interlayer comprises at least one polymer sheet. Preferably, it comprises at least two, and even at least three, particularly between two and five, or even three or four.

[0016] The carrier sheet is coated with a decorative coating consisting of multiple stacked layers of organic ink. Using decoration printed on the interlayer of the laminate instead of one of the glass sheets (e.g., through enamel or mineral coatings) makes the method more flexible and allows for greater customization of the decoration without significantly impacting production costs. This also means that more complex decorations can be created without adversely affecting the mechanical strength of the assembled glass.

[0017] The decorative coating comprises at least two stacked organic ink layers: a first ink layer (which is the ink layer closest to the first glass plate) and a second ink layer (which is the ink layer closest to the second glass plate). These two ink layers have different properties. The presence of the two stacked ink layers allows for the creation of two distinct finishes, one visible from the exterior of the vehicle and the other from the interior.

[0018] In one embodiment, the decorative coating consists of two stacked organic ink layers. Alternatively, and according to a preferred embodiment, the decorative coating comprises more than two stacked organic ink layers; in particular, it consists of three stacked organic ink layers.

[0019] Preferably, the second organic ink layer is a decorative, multi-colored, or monochromatic layer, while the first organic ink layer is a monochromatic layer, particularly black. In this case, if the first glass pane is intended as an outer pane, the assembled glass will appear monochromatic, particularly black, when viewed from the outside of the vehicle. Colors other than black can also be chosen, for example, to match the color of the assembled glass to the body color, or to choose a different color that might be used on other parts of the vehicle, such as rearview mirrors. On the other side, in this case, from the inside of the vehicle, the monochromatic or multi-colored trim is visible. This trim can be anything, such as based on a photograph. It could, for example, depict a landscape. In this case, it is preferable that the glass pane and polymer sheet located between the vehicle interior and the trim are transparent (particularly uncolored and with high light transmittance, particularly at least 80%, or even at least 85% or 90%) to allow for a good view of the trim. The resolution of the trim should preferably be at least 360 dpi (dots per inch).

[0020] According to one variation, the two organic ink layers can be decorative, monochrome, or multicolored. Preferably, each layer will represent a different decoration.

[0021] Preferably, the decorative coating includes a third organic ink layer disposed between the first ink layer and the second ink layer. This third ink layer is advantageously opaque, particularly white. White ink has the advantage of high opacity (particularly a light transmittance of less than 1%, or even less than 0.1%, and / or a light density of at least 2, or even at least 3). This allows for complete separation of the decoration on each ink layer, avoiding any decorative overlap that would adversely affect the aesthetics of the assembled glass.

[0022] The decorative coating preferably comprises no more than three ink layers to avoid unnecessarily complicating the printing process.

[0023] Preferably, the decorative coating is printed using inkjet printing technology, particularly using inks that are polymerizable or crosslinkable under ultraviolet radiation. This technology offers advantages in speed and productivity due to the near-instantaneous drying of the ink, and produces durable, scratch-resistant decorations with excellent print quality.

[0024] Preferably, multiple stacked organic ink layers are printed simultaneously in a single pass. UV inkjet printing technology allows for the simultaneous printing of several stacked layers, which is a major advantage in terms of productivity.

[0025] The ink preferably comprises one or more pigments and a binder. It advantageously contains a photoinitiator, particularly selected from benzophenones, phosphine oxide derivatives, acetophenones, and isopropylthioxanthone. "Organic ink" refers to an ink where the binder is organic, as opposed to mineral enamels or coatings where the binder is inorganic (e.g., based on mineral glass or silicates). On the other hand, the pigment can be organic or inorganic. For example, white ink may contain titanium dioxide. The binder is, for example, of the acrylate, epoxy, or polyester type. The binder may particularly include monomers and / or oligomers of the (meth)acrylate, polyether-acrylate, polyester-acrylate, polyurethane-acrylate, epoxy-acrylate, or silicone-acrylate type. The ink may also contain additives, such as viscosity or surface tension modifiers, stabilizers, etc.

[0026] The laminated interlayer preferably comprises at least two polymer sheets, wherein a first polymer sheet is closest to a first glass sheet and a second polymer sheet is closest to a second glass sheet, and a decorative coating is disposed between the first and second polymer sheets. In this case, the second polymer sheet is preferably transparent to allow good visibility of the trim when it is to be viewed from inside the vehicle. The first polymer sheet is preferably tinted, particularly when the fitted glass appears black or at least dark from the outside of the vehicle (this is the configuration of the first glass sheet as the outer sheet of the fitted glass).

[0027] The first and second polymer sheets are preferably made of polymers selected from polyvinyl butyral (PVB), ethylene-vinyl acetate copolymer, and thermoplastic polyurethane. This ensures good adhesion to the glass sheet, thereby meeting regulatory requirements regarding the safety of laminated glass.

[0028] According to the first embodiment, the carrier sheet is a first polymer sheet or a second polymer sheet. Preferably, the decorative coating is located on the surface of the polymer sheet (first or second) facing another polymer sheet of the laminating interlayer. This prevents the decorative coating from contacting the glass and from being damaged during lamination.

[0029] According to the second embodiment, the laminated interlayer further includes a third polymer sheet located between the first and second polymer sheets, and the carrier sheet is this third polymer sheet. In this case, the third polymer sheet is preferably made of polyethylene terephthalate (also known as PET). This material has the advantage of being optically transparent and compatible with plasticizers commonly used in polyvinyl butyral.

[0030] At least one polymer sheet in the laminated interlayer can have infrared radiation reflective properties, thereby contributing to daylight control and / or heat insulation of the assembled glass. This function can be achieved, in particular, by dispersing infrared reflective particles, especially metal or metal oxide particles, in the polymer sheet, or by coating the polymer sheet with an infrared reflective coating.

[0031] A laminated interlayer can be obtained, in particular, by stacking the polymer sheets that make up it (e.g., a PET sheet between two PVB sheets) and then locally welding these PVB sheets at the edges of the interlayer. Alternatively, two polymer sheets can be pre-assembled to form a bilayer. For example, a carrier sheet, particularly made of PET, can be thermally bonded to a PVB sheet and then joined to another PVB sheet.

[0032] The glass is preferably used on the roof of a motor vehicle. Other applications are also possible, particularly in transportation, construction, and household appliances, as mentioned above.

[0033] The mounting glass, particularly the roof of a motor vehicle, is preferably curved, with a first glass sheet being the outer sheet and a second glass sheet being the inner sheet. The term "outer sheet" refers to the sheet intended for use on the exterior of the vehicle, which will be located on the convex side of the mounting glass, while the term "inner sheet" refers to the sheet intended for use on the interior of the vehicle, which will be located on the concave side.

[0034] Therefore, the method preferably includes a bending step before the lamination step. Preferably, the two glass sheets are bent together, with the second sheet on top of the first. The glass can be bent, particularly by gravity (the glass deforms under its own weight) or by pressing, typically at temperatures of 550 to 720°C. Rapid cooling can be performed after the pressing process to achieve surface strengthening (tempering or hardening). During the bending process, the glass sheets can be kept apart by placing an intermediate layer powder between them to ensure a gap of tens of micrometers, typically 20 to 50 µm. This intermediate layer powder is, for example, based on calcium carbonate and / or magnesium carbonate.

[0035] The lamination step can be carried out, particularly by treatment in an autoclave, for example at a temperature of 110 to 160°C and a pressure of 10 to 15 bar. Prior to autoclave treatment, trapped air between the glass sheet and the interlayer can be eliminated by calendering or by applying negative pressure.

[0036] Figures 1 to 3 The invention is shown in a non-limiting manner.

[0037] [ Figure 1 [This is an exploded view of the assembled glass according to one embodiment of the present invention.] Figure 2 [This is an exploded view of the assembled glass according to another embodiment of the present invention.] Figure 3 [ ] is an exploded view of the assembled glass according to another embodiment of the present invention.

[0038] Figures 1 to 3 These are schematic and exploded views of the assembled glass according to the invention. These views are exploded so that the various elements deposited on which sheets (glass or polymer) are visible. These views are obviously not to scale; the thickness of some elements is greatly exaggerated to facilitate their observation. For simplicity, these assembled glasses are shown in a flat form, but in most automotive applications they will be curved. Faces 1 to 4 of the glass sheets are shown in the figures, designated F1, F2, F3, and F4, respectively. In these examples, the first glass sheet is therefore the outer sheet of the assembled glass, i.e., the one intended to be located on the exterior of the vehicle. These assembled glasses will be described here in conjunction with applications such as the roof of a motor vehicle, but other applications are certainly possible, in the transportation sector as well as in the building industry (facades, partitions, etc.) or in household appliances.

[0039] exist[ Figure 1 In the embodiment shown, the mounting glass 10 comprises a first glass sheet 11 and a second glass sheet 12, which are connected to each other by a laminated interlayer 14. As previously mentioned, the first glass sheet 11 is preferably tinted. The second glass sheet 12 is preferably transparent so that the trim can be easily seen. The laminated interlayer 14 consists of two polymer sheets, a first sheet 141 and a second sheet 142. These two sheets are made, in particular, of polymers selected from polyvinyl butyral (PVB), ethylene-vinyl acetate copolymer (EVA), and thermoplastic polyurethane (TPU). Like the glass sheets, the second polymer sheet 142 is preferably transparent so that the trim can be easily seen from the vehicle interior. The first polymer sheet 141 may be tinted. The first glass sheet 11 here has a peripheral black enamel strip 17 coated on surface 2 (referred to as F2), which is designed to protect and conceal the fixed joint of the mounting glass in the body opening. This optional enamel layer may alternatively be deposited on surface 3 or surface 4.

[0040] In this example, decorative coating 16 is preferably disposed between the two polymer sheets 141 and 142 to avoid damage to it during lamination. Decorative coating 16 is printed on carrier sheet 140, which is the second polymer sheet 142, but it can also be printed on the first polymer sheet 141. Then the ink layer deposition order would be reversed, with the first ink layer 161 in contact with the carrier sheet.

[0041] In this example, the decorative coating 16 consists of three stacked organic ink layers: a first layer 161 closest to the first glass sheet 11, a second layer 162 closest to the second glass sheet 12, and a third layer 163 located between the first and second layers. In the example shown, the first layer 161 is a black ink layer, the second layer 162 is a multi-colored decorative layer, and the third layer 163 is a white opaque layer. The result is an opaque vehicle roof, which appears black from the outside, while the appearance from the inside is determined by the selected trim. The optional third layer 163 provides good opacity and separates the trim seen from the trim seen from the inside. Other configurations are also possible. For example, the first layer 161 can be a multi-colored trim, or it can be a single color other than black, for example, to match the color of the body or other vehicle components.

[0042] The organic ink layers are preferably deposited on the carrier sheet 140 by ultraviolet inkjet printing. They are preferably deposited simultaneously in a single pass.

[0043] [ Figure 2 The assembled glass 20 shares many elements with the assembled glass 10 described above: the first glass sheet 21 is coated with a peripheral enamel layer 27 on its surface 2 and is connected to the second glass sheet 22 via a laminated interlayer 24 comprising a first polymer sheet 241 and a second polymer sheet 242. A decorative coating 26 comprising three stacked ink layers 261, 262, and 263 is printed on the polymer carrier sheet 240. The descriptions of the corresponding elements already detailed in conjunction with the assembled glass 10 also apply here.

[0044] The main difference from the assembled glass 10 is that the laminated interlayer 24 also includes a third polymer sheet 243 disposed between the first polymer sheet 241 and the second polymer sheet 242, and the carrier sheet 240 is this third polymer sheet 243. This third polymer sheet 243 is preferably made of polyethylene terephthalate (PET). Therefore, the laminated interlayer 24 consists, for example, of a PET sheet surrounded by two PVB sheets. Such an assembly can be achieved, for example, by stacking these three polymer sheets and welding them together at the edges of the interlayer.

[0045] [ Figure 3The assembled glass 30 shown is similar to assembled glass 20: it contains a first glass sheet 31 coated with a peripheral enamel layer 37 on its surface 2, and connected to a second glass sheet 32 ​​via a laminated interlayer 34 comprising a first polymer sheet 341, a second polymer sheet 342, and a third polymer sheet 343, the third polymer sheet being a carrier sheet 340 for a decorative coating 36 comprising three stacked ink layers 361, 362, and 363. The descriptions of the corresponding elements already detailed in conjunction with assembled glasses 10 and 20 also apply here.

[0046] The main difference between this and the assembly glass 20 is that the decorative coating 36 contacts the first polymer sheet 341, while in the case of assembly glass 20 it contacts the second polymer sheet 242. Therefore, the order of the ink layers is reversed: in the case of assembly glass 20, the ink layer closest to the carrier sheet is the first layer 261, while in the case of assembly glass 30 it is the second layer 362. This configuration may be more advantageous when the first polymer sheet 341 is colored, in order to avoid possible interactions between the decorative ink and the pigments of the colored polymer sheet. In this respect, the PET sheet is a good barrier against the migration of ink components during decoration.

Claims

1. A laminated assembled glass (10, 20, 30) comprising a first glass sheet (11, 21, 31) and a second glass sheet (12, 22, 32) bonded together by a laminated interlayer (14, 24, 34), the laminated interlayer (14, 24, 34) comprising a polymer sheet, referred to as a carrier sheet (140, 240, 340), the carrier sheet being coated with a decorative coating (16, 26, 36), the decorative coating comprising a plurality of stacked organic ink layers (161, 162, 163, 261, 262, 263, 361, 362, 363), the organic ink layer comprising a first ink layer (161, 261, 361) closest to the first glass sheet (11, 21, 31) and an ink layer (12, 22, 32) closest to the second glass sheet (12, 21, 31). The second ink layer (162, 262, 362) of the ink layer 22, 32).

2. The laminated assembled glass (10, 20, 30) according to claim 1, wherein, The second organic ink layer (162, 262, 362) is a decorative, multi-colored or monochromatic layer, while the first organic ink layer (161, 261, 361) is a monochromatic layer, particularly black.

3. The laminated glass (10, 20, 30) according to any one of the preceding claims, wherein the decorative coating (16, 26, 36) includes a third organic ink layer (163, 263, 363) disposed between a first ink layer and a second ink layer, the third ink layer (163, 263, 363) being opaque, particularly white.

4. The laminated glass (10, 20, 30) according to any one of the preceding claims is opaque in the areas where the decorative coating (16, 26, 36) is present.

5. The laminated assembled glass (10, 20, 30) according to any one of the preceding claims, wherein the laminated interlayer (14, 24, 34) comprises at least two polymer sheets, the polymer sheets comprising a first polymer sheet (141, 241, 341) closest to the first glass sheet (11, 21, 31) and a second polymer sheet (142, 242, 342) closest to the second glass sheet (12, 22, 32), and the decorative coating (16, 26, 36) is disposed between the first polymer sheet (141, 241, 341) and the second polymer sheet (142, 242, 342).

6. The laminated assembled glass (10, 20, 30) according to the preceding claim, wherein the first polymer sheet (141, 241, 341) and the second polymer sheet (142, 242, 342) are made of polymers selected from polyvinyl butyral, ethylene-vinyl acetate copolymer and thermoplastic polyurethane.

7. The laminated assembled glass (10, 20, 30) according to any one of claims 5 or 6, wherein the carrier sheet (140, 240, 340) is a first polymer sheet (141, 241, 341) or a second polymer sheet (142, 242, 342).

8. The laminated assembled glass (20, 30) according to any one of claims 5 or 6, wherein the laminated interlayer (24, 34) further comprises a third polymer sheet (243, 343) located between the first polymer sheet (241, 341) and the second polymer sheet (242, 342), and the carrier sheet (240, 340) is the third polymer sheet (243, 343).

9. The laminated assembled glass (20, 30) according to the preceding claim, wherein the third polymer sheet (243, 343) is made of polyethylene terephthalate.

10. The laminated assembly glass (10, 20, 30) according to any one of the preceding claims, which is a vehicle roof, the assembly glass being curved, the first glass sheet (11, 21, 31) being the outer sheet of the assembly glass, and the second glass sheet (12, 22, 32) being the inner sheet of the assembly glass.

11. The laminated glass (10, 20, 30) according to the preceding claim, wherein the two stacked ink layers (161, 162, 163, 261, 262, 263, 361, 362, 363) establish two different finishes, one visible from the exterior of the vehicle and the other visible from the interior of the vehicle.

12. A laminated interlayer (14, 24, 34) comprising a polymer sheet, referred to as a carrier sheet (140, 240, 340), said carrier sheet being coated with a decorative coating (16, 26, 36) comprising a plurality of stacked organic ink layers (161, 261, 262, 162, 262, 363, 361, 362, 363).

13. A method for obtaining laminated assembled glass (10, 20, 30) according to any one of claims 1 to 11, comprising printing a decorative coating (16, 26, 36) comprising a plurality of stacked organic ink layers (161, 162, 163, 261, 262, 263, 361, 362, 363) on a polymer sheet (140, 240, 340), and laminating a first glass sheet (11, 21, 31) and a second glass sheet (12, 22, 32) by means of a laminating intermediate layer (14, 24, 34) comprising the polymer sheet (140, 240, 340).

14. The method according to the preceding claim, wherein the decorative coating (16, 26, 36) is printed by inkjet printing technology, particularly using inks that are polymerizable or crosslinkable under ultraviolet radiation.

15. The method according to the preceding claim, wherein the plurality of stacked organic ink layers (161, 162, 163, 261, 262, 263, 361, 362, 363) are printed simultaneously in a single pass.

Images