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WO2025224559A1 - Laminated glazing for a vehicle having improved mechanical resistance to impacts - Google Patents

Laminated glazing for a vehicle having improved mechanical resistance to impacts

Info

Publication number
WO2025224559A1
WO2025224559A1 PCT/IB2025/053917 IB2025053917W WO2025224559A1 WO 2025224559 A1 WO2025224559 A1 WO 2025224559A1 IB 2025053917 W IB2025053917 W IB 2025053917W WO 2025224559 A1 WO2025224559 A1 WO 2025224559A1
Authority
WO
WIPO (PCT)
Prior art keywords
glass
laminated glazing
glass layer
glazing
layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/IB2025/053917
Other languages
French (fr)
Inventor
Osmar CURI GRADOS
Jorge A. Ramos
Erwin PAVOLINI
Sergio Carlos MORILLO MONTES
Antonella DELGADO PAUSIC
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
AGP America SA
Original Assignee
AGP America SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by AGP America SA filed Critical AGP America SA
Publication of WO2025224559A1 publication Critical patent/WO2025224559A1/en
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10036—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00—Layered products having a non-planar shape
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10082—Properties of the bulk of a glass sheet
    • B32B17/10119—Properties of the bulk of a glass sheet having a composition deviating from the basic composition of soda-lime glass, e.g. borosilicate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10128—Treatment of at least one glass sheet
    • B32B17/10137—Chemical strengthening
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10165—Functional features of the laminated safety glass or glazing
    • B32B17/10247—Laminated safety glass or glazing containing decorations or patterns for aesthetic reasons
    • B32B17/10256—Laminated safety glass or glazing containing decorations or patterns for aesthetic reasons created by printing techniques
    • B32B17/10266—Laminated safety glass or glazing containing decorations or patterns for aesthetic reasons created by printing techniques on glass pane
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
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    • B32B17/10339—Specific parts of the laminated safety glass or glazing being colored or tinted
    • B32B17/10348—Specific parts of the laminated safety glass or glazing being colored or tinted comprising an obscuration band
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    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10761—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing vinyl acetal
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
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    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/1077—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing polyurethane
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10788—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing ethylene vinylacetate
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    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10807—Making laminated safety glass or glazing; Apparatus therefor
    • B32B17/10889—Making laminated safety glass or glazing; Apparatus therefor shaping the sheets, e.g. by using a mould
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    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10807—Making laminated safety glass or glazing; Apparatus therefor
    • B32B17/10899—Making laminated safety glass or glazing; Apparatus therefor by introducing interlayers of synthetic resin
    • B32B17/10935—Making laminated safety glass or glazing; Apparatus therefor by introducing interlayers of synthetic resin as a preformed layer, e.g. formed by extrusion
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    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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    • B32B7/04—Interconnection of layers
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
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    • B32B2605/08—Cars

Definitions

  • the present invention falls in the field of a laminated glazing for a vehicle and, more particularly, it relates to a glazing with improved mechanical resistance to impacts.
  • Standard laminated glazing for a vehicle is conventionally comprised of two glass layers, a first glass layer that is disposed closer to the exterior of a vehicle and a second glass layer that is disposed closer to the interior of a vehicle, both being comprised of sodalime glass, and one bonding layer typically comprised of PVB that serves to permanently bond the two glass layers together.
  • Laminated glazing is mostly used in windshield positions to provide for safety of the vehicle occupants. This is because in case of debris or any external object hitting the windshield it protects the vehicle occupants from these objects. Additionally, if any of the glass layers of the windshield fails, the bonding layer holds the glass shards together avoiding injuries due to spalling. Moreover, the windshield (damaged or not) provides retention of vehicle occupants, in case of an accident such as a crash. Anytime a vehicle glazing is damaged it should be replaced. This translates into cost and down time for the vehicle owner.
  • Laminated glazing has another advantage over the conventional monolithic glazing which is that it may be comprised of performance interlayers laminated in between the glass layers. These performance interlayers may provide for instance sound dampening, anti-intrusion protection, solar control, cabin thermal comfort, light transmission control, heating for deicing and defogging, among other functionalities.
  • the cost for a laminated glazing comprising such functionalities, for example performance interlayers and electronic components and sensors, is elevated which is pushing the market to provide a laminated glazing with higher mechanical resistance to impacts and therefore decreasing costs associated with glazing replacement.
  • the prior-art has solved this problem by suggesting the use of different glass compositions other than soda-lime glass, preferably in the first glass layer of the laminated glazing.
  • glass compositions with higher mechanical resistance such as borosilicate glass
  • obscuration comprising a glass enamel, also called as black frit
  • the glass enamel is said to be “fired” or cured/vitrified.
  • the glass enamel chemically dissolves onto the glass layer surface and in doing so it produces surface defects. This makes the surface of the glass weaker, increasing the probability of breakage when suffering an impact.
  • One solution to this problem is to provide an obscuration using organic ink painted onto the glass layer, or by providing an opaque black plastic interlayer or insert in between the glass layers that can serve as obscuration.
  • the organic ink cannot withstand high temperatures. Therefore, the glass layer comprising the organic ink should be either cold-bent (a process well-known in the art) or the organic ink should be applied onto an already bent/curved glass layer. The latter option is a more complex process and therefore costly.
  • a laminated glazing comprising a first glass layer that is not comprised of soda-lime glass and having at least one area printed with a glass enamel wherein said glazing has improved mechanical resistance to impacts. It would also be advantageous to provide a method for producing such laminated glazing.
  • the present invention provides a solution to the aforementioned problems by providing a laminated glazing for a vehicle having improved mechanical resistance to impacts, the laminated glazing comprising at least two glass layers, a first glass layer 201 , that is not comprised of soda-lime glass, and a second glass layer 202.
  • the glazing also comprises at least one bonding layer 4 being disposed in between the interior surface(s) of the first and the second glass layers.
  • the first glass layer 201 has at least one area onto its internal surface 102 printed with a glass enamel.
  • the first glass layer 201 has softening temperature Tsof (°C), annealing temperature Tanf (°C), strain temperature Tstf (°C), and coefficient of thermal expansion CTEf(1/°C).
  • the second glass layer 202 has softening temperature Tso s (°C), annealing temperature Tan s (°C), strain temperature Tst s (°C), and coefficient of thermal expansion CTEs (1/°C).
  • the first glass layer 201 has a parameter TCf and the second glass layer 202 has a parameter Tc s , such that the difference, in absolute numbers, between Tc s and TCf is more than or equal to 2.
  • the parameter Tc s ,f is obtained by the following equation:
  • the at least one printed area of the first glass layer 201 has a flexural strength of at least 40 MPa at a probability of failure of 63.2 % according to the normative standard DIN 1288 ring on ring test.
  • the present invention also provides a method for manufacturing a laminated glazing for a vehicle having improved mechanical resistance to impacts, such method comprising the steps of providing at least two glass layers comprising a first glass layer having an exterior surface oriented towards the outside of the laminated glazing, an interior surface oriented towards the inside of the laminated glazing, having temperatures of softening Tsof, annealing Tanf and strain Tstf, coefficient of thermal expansion CTEf, and having at least one area onto said internal surface printed with a glass enamel.
  • the glazing having at least two glass layers also comprises a second glass layer having an interior surface oriented towards the inside of the laminated glazing, an exterior surface oriented towards the outside of the laminated glazing, having temperatures of softening Tso s , annealing Tan s and strain Tst s , and coefficient of thermal expansion CTEs.
  • the laminated glazing of the invention also comprises at least one bonding layer, being disposed between the interior surface(s) of the first and the second glass layers, wherein said first glass layer has a parameter TCf and the second glass layer has a parameter Tc s , according to wherein the difference between Tc s and TCf is more than or equal to 2, and wherein said at least one printed area of the first glass layer has a flexural strength of at least 40 MPa at the probability of failure of 63.2% according to the normative standard DIN 1288 ring on ring test.
  • the method of the invention also comprises the step of laminating said first and second glass layers with said at least one bonding layer, forming the laminated glazing of the invention.
  • Figure 1 illustrates a vehicle comprising the laminated glazing of the invention.
  • Figure 2 shows a generic realization of a cross section of the laminated glazing of the invention.
  • Figure 3 illustrates a laminated windshield having at least one printed area with a glass enamel comprising an obscuration.
  • Figure 4 shows flexural strength experimental results.
  • Figure 5 shows Table 1 with examples of glass compositions and the following parameters Tsof, s , Tanf, s , Tstf, s , and CTEf, s .
  • Figure 6 illustrates the support apparatus for the ball drop and sharp impact tests.
  • Figure 7 shows the results of sharp impact tests.
  • Figure 8 shows Table 2 with sharp impact test results.
  • Figure 9 shows the results of ball drop tests. REFERENCE NUMERALS OF DRAWINGS
  • layer shall include the common definition of the word, i.e.: a sheet, quantity, or thickness, of material, typically of some homogeneous substance.
  • stack refers to the arrangement in a pile manner of a plurality of layers forming the laminated glazing.
  • Laminates in general, are articles comprised of multiple layers of thin, relative to their length and width, material, with each thin layer having two oppositely disposed major faces, typically of uniform thickness, which are permanently bonded to one and other across at least one major face of each layer.
  • the layers of a laminate may alternately be described as sheets or plies.
  • the glass layers of a glazing may be referred to as panes.
  • Glazing should be understood as a product comprised of at least one layer of a transparent material, preferably glass, which serves to provide for the transmission of light and/or to provide for viewing of the side opposite to the viewer and which is mounted in an opening in a building, vehicle, wall or roof or other framing member or enclosure.
  • vehicle in the present invention includes, but is not limited to, road vehicles (e.g., cars, busses, trucks, agricultural and construction vehicles, cabin motorbikes), railway vehicles (e.g., locomotives, coaches), aircraft (e.g. airplanes, helicopters), boats, ships and the like.
  • road vehicles e.g., cars, busses, trucks, agricultural and construction vehicles, cabin motorbikes
  • railway vehicles e.g., locomotives, coaches
  • aircraft e.g. airplanes, helicopters
  • boats ships and the like.
  • the vehicle may be a road vehicle and more particularly a car.
  • the present invention provides a solution for a laminated glazing for a vehicle having improved mechanical resistance to impacts.
  • Figure 1 illustrates a top view of a vehicle 1 comprising a laminated glazing 100 of the invention such as a laminated windshield 2, a laminated sidelite 3, a laminated roof 8, or a laminated backlite 10.
  • a laminated glazing 100 of the invention such as a laminated windshield 2, a laminated sidelite 3, a laminated roof 8, or a laminated backlite 10.
  • the laminated glazing 100 comprises at least two glass layers, however more than two glass layers, such as three or four, can be comprised in such a glazing without departing from the spirit of the invention.
  • the at least two glass layers comprise: a first glass layer 201 that is not comprised of soda-lime glass, having an exterior surface 101 oriented towards the outside of the laminated glazing, an interior surface 102 oriented towards the inside of the laminated glazing, having temperatures of softening Tsof, annealing Tanf, and strain Tstf, coefficient of thermal expansion CTEf, and having at least one area onto said interior surface 102 printed with a glass enamel 6.
  • the first glass layer is disposed closer to the exterior of a vehicle, such that it can be considered an outer glass layer (facing the exterior of the vehicle).
  • the at least one printed area could be one, or a plurality of areas that are printed with a glass enamel forming an obscuration.
  • Obscurations are used, conventionally as a black band around the perimeter of the glazing to protect the sealing materials that fix the glazing to the vehicle body from UV light exposure and degradation. They also serve to hide electrical components, the edge of the interlayers, or any other components that should not be visible to an observer.
  • the obscuration needs to be opaque in the sense of difficulty to see through rather than blocking all light.
  • the typical obscuration light transmission is less than 5%, preferably less than 3%, and more preferably equal to 0%.
  • the at least one printed area is a black band obscuration 6 that is at least partially disposed around the perimeter of the glazing.
  • the at least one printed area is a black band obscuration as described above and it also comprises an obscuration 6 around a driver assistance system opening window such as an area intended to receive a sensor, a safety camera, or LIDAR.
  • the obscuration serves to hide any electrical components, supports, and brackets of such systems. This is illustrated in Figure 3.
  • the black band obscuration provided for the perimeter of the glazing could be connected to the obscuration of the opening window for the driver assistance system or it could be separated from it without departing from spirit of the invention.
  • the obscuration is a glass enamel (black frit) that is comprised of pigments, a carrier, binders and finely ground glass.
  • Standard black frit obscurations are optimized in their formulation to thermally match the glass layer which it is printed on.
  • the glass enamel is applied to the glass surface using a silk screen or ink jet printing process prior to heating and bending. During the heating and bending process, the finely ground glass in the frit softens and fuses to the glass surface. When this process takes place, the glass enamel is said to be “fired” also known as vitrified.
  • a fired black glass enamel normally increases surface defects. This happens because the glass enamel chemically dissolves onto the glass layer and in doing so it produces surface defects. This makes the surface weaker, increasing the probability of breakage. Testing has shown that glass with black frit fails at a stress level that is substantially lower than glass that does not have a fired black frit.
  • the first glass layer has at least one area printed with a glass enamel, wherein said glass enamel has a coefficient of thermal expansion (CTEe) ranging from 20 x 10’ 7 1/°C to 65 x 10’ 7 1/°C.
  • CTEe coefficient of thermal expansion
  • the glazing of the invention comprises at least one printed area of the first glass layer having a flexural strength of at least 40 MPa at a probability of failure of 63.2 % according to the normative standard DIN 1288 ring on ring test.
  • the inventors have discovered that when providing such first glass layer with an area printed with a glass enamel, and having such flexural strength, it results in improved mechanical resistance to impacts when said glass is assembled into the glazing of the invention.
  • This glass enamel composition is either currently available in the market or can be formulated by a skilled person to produce the first glass layer with said structural characteristic and suitable CTEe for glass compatibility .
  • the glazing of the invention comprises at least one printed area of the first glass layer having said area a flexural strength of at least 55 MPa at a probability of failure of 63.2 % according to the normative standard DIN 1288 ring on ring test.
  • Flexural strength was measured by performing the ring-on-ring test following the normative standard DIN 1288. According to this normative, two rings of 18 mm and of 90 mm of diameter were used: one for applying load (the loading ring) and the other one for supporting the sample (the support ring). Glass samples of 100 mm x 100 mm were placed one at a time centered above the support ring, while the loading ring was placed on top of the samples, ensuring alignment with the support ring. A load was then gradually applied to the center of the loading ring using a testing machine until sample breakage. A minimum of thirty samples were tested following the method described previously. The flexural strength probability is calculated based on the applied load and sample dimensions and displayed into a Weibull distribution of probability of failure.
  • Figure 4 shows flexural strength results obtained for three sets of samples of 100 mm x 100 mm size, the three sets comprising a glass layer having thermal properties of Glass 2 of Table 1 , having thickness of 3.8 mm; wherein the first set of samples (Glass printed obs) has the entire surface printed with a glass enamel formulation that matches the CTE of the glass and has improved flexural strength performance, a second set of samples (Glass printed std) having its entire surface printed with a standard glass enamel formulation currently available in the market for glass composition that is not soda-lime, and the third set of samples (Glass not printed) is not printed at all.
  • the flexural strength test should be performed by delaminating the first glass layer with the obscuration and cutting samples of 100 mm x 100 mm, such samples comprising at least one area printed with a glass enamel.
  • the laminated glazing 100 of the invention also comprises at least one second glass layer 202, having an interior surface 103 oriented towards the inside of the laminated glazing, an exterior surface 104 oriented towards the outside of the laminated glazing, having temperatures of softening Tso s , annealing Tan s , and strain Tst s , and coefficient of thermal expansion CTEs; and at least one bonding layer, being disposed between the interior surface(s), 102, and 103, of the first 201 and the second 202 glass layers.
  • the second glass layer is disposed closer to the interior of a vehicle (facing the interior of the vehicle).
  • the at least one second glass layer may have the CTEs ranging from 70 x 10' 7 1/°C to 105 x 10' 7 1/°C.
  • the at least one second glass layer is selected from soda lime, and aluminosilicate.
  • Figure 5 shows Table 1 with examples of ranges for CTE, T so , T an , T s t of the at least one first and at least one second glass layers.
  • the at least one bonding layer 4 has the primary function of bonding the major faces of adjacent layers of the glazing to each other.
  • it is comprised of a polymer film and may be selected from any of the following: polyvinyl butyral (PVB), ethylene vinyl acetate (EVA), thermoplastic polyurethane (TPU), polyolefin elastomers (PoE), or a combination thereof.
  • the thickness of the at least one bonding layer 4 is comprised between 0.3 mm and 2.0 mm, more preferably comprised between 0.5 mm and 1.0 mm, e.g., about 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm or 1.0 mm. More than one bonding layer 4 can be used such as two, three, or a plurality of bonding layers 4 without departing from the spirit of the invention.
  • the mechanical resistance to impacts is improved by selecting the correct combination of chemical composition of each one of the glass layers constituting the glazing;
  • the glazing of the invention has a first glass layer with a parameter TCf and the second glass layer with a parameter Tc s , according to such that the difference, in absolute numbers, between Tc s and TCf is more than or equal to 2.
  • the at least one first glass layer may have a CTEf ranging from 30 x 10' 7 1/°C to 50 x 10 -7 1/°C.
  • the at least one first glass layer is a borosilicate glass layer.
  • the first glass layer is a borosilicate glass and has a surface tensile stress below 8 MPa measured at 25 mm from the glass edge, and below 5 MPa when measured at the center of the glass. In one preferred embodiment the first glass layer is a borosilicate glass having a surface tensile stress measured at the center of the glass below 2 MPa.
  • the laminated glazing of the present invention is preferably a curved laminated glazing.
  • Curved laminated glazing can be achieved by thermally bending at least one or all the glass layers forming the glazing.
  • Thermal bending of glass involves heating the glass to the glass transition temperature range where it is bent to shape then cooling the glass to freeze in the change in shape. In this case, glass undergoes a permanent plastic deformation.
  • the glass can be slowly cooled to relieve stress, a process known as annealing, or can be rapidly cooled to heat strengthen, process known as tempering.
  • the second glass layer could also be thermally bent/curved or cold-bent.
  • Cold bending is a relatively recent technology in the automotive industry. As the name suggests, the glass is bent, while cold to its final shape, without the use of heat. However, as the glass only undergoes elastic deformation, at any point on the bent area of the glass one side, i.e. , major surface, of the glass will have a substantially higher level of stress than on the opposite side of the glass. If annealed glass is used, one side will be in compression and the other in tension.
  • Performance layers may also be used in the glazing.
  • Performance layers include but are not limited to films that provide a functionality to the glazing such as solar control (e.g., infrared blocking film), variable light transmission, Head up Display (HUD) imaging, HUD holographic (HoE) imaging, increased stiffness, increased structural integrity, improved penetration resistance, improved occupant retention, a chemical barrier/protection, tint, sunshade, obscuration for black band or for hiding and protecting integrated systems, color correction, and as a substrate for functional and aesthetic graphics.
  • solar control e.g., infrared blocking film
  • variable light transmission e.g., variable light transmission
  • HUD Head up Display
  • HoE HUD holographic
  • At least one performance layer is disposed in between the first and second glass layers of the glazing of the invention.
  • coatings can be applied to at least one of the glass layers of the invention and provide functionality to the laminated glazing such as infrared protection, UV protection, low-emissivity for thermal comfort, among others.
  • the glazing of the invention comprises a coating.
  • an infrared blocking layer is disposed between the first and second glass layers and is selected from the group of a film, or a coating.
  • the glazing of the invention having improved mechanical resistance to impacts could be advantageously comprised of photovoltaic devices, e.g., solar cells, that are laminated within the layers of the glazing.
  • the thickness of the at least one first glass layer 201 and at least one second glass layer 202 may vary widely and thus be ideally adapted to the requirements of the individual cases.
  • the thickness of the first glass layer and the second glass layer of the laminated glazing of the invention is lower than 5.0 mm, preferably comprised between 0.3 mm and 5.0 mm, such as between 0.5 mm and 4.0 mm or between 1.0 mm and 3.0 mm.
  • Possible examples of thicknesses of the glass layers are about 1.5 mm, 1.6 mm, 1.7 mm, 1.8 mm, 1.9 mm, 2.0 mm, 2.1 mm, 2.2 mm, 2.3 mm, 2.4 mm, 2.5 mm, 2.6 mm, 2.7 mm, 2.8 mm, 2.9 mm or 3.0 mm.
  • the first glass layer 201 has thickness tf (mm) and the second glass layer 202 has thickness t s (mm) that is preferably no lower than 0.5 mm, wherein the difference between tf and t s follows the equation below: tf 0 ⁇ tf - ts) * log ( ⁇ -) ⁇ 4.5
  • the difference between tf and t s follows the equation below:
  • the glazing of the invention has improved mechanical resistance to sharp impacts.
  • the sharp impact test consists of providing laminated samples 16 of dimensions of 300 mm x 300 mm and disposing them one at a time onto a steel base support 12 of similar dimensions such that each sample is disposed with the first glass layer 201 facing up and the second glass layer 202 facing down, and the sample edges are fixed against a steel frame 14.
  • the testing support used is described by the standard normative ECE R43 Annex 3 (2.1.1.3).
  • a rubber seal is disposed to protect the glass surface.
  • the support with sample can be illustrated in Figure 6 which shows a cross section of a sample mounted onto the support.
  • the samples are tested one at a time by having a Vickers diamond tip indenter weighing 14 g and being dropped from heights in increments of 0.1 m until breakage ranging from 0.5 m to 3.0 m.
  • Each sample of 300 x 300 mm has nine quadrants spaced 100 mm apart from each other. Each quadrant receives one impact at its center region.
  • the impact is performed by dropping a Vickers diamond tip indenter weighing 14g from a predetermined height starting from 0.5 m to a maximum of 3.0 m. For each impact, the dropping height is incremented by 0.1m until failure is detected. .
  • m [kg] is the weight of the indenter
  • g [m/s 2 ] is the gravity acceleration
  • h [m] is the height from where the indenter has been dropped.
  • the height of failure is identified when the impact causes a crack having a diameter larger than 7 mm.
  • the next impact test starts at a height of 0.2 m below the height of failure.
  • a minimum of thirty impact tests are performed .
  • the heights of failure for each one of the samples tested are recorded and plotted onto a graphic displaying a Weibull distribution with the probability of failure on the y axis and the energy of impact at failure is displayed on the x axis.
  • Figure 7 shows the results of a sharp impact test performed in a minimum of thirty samples of each configuration.
  • Sample STD is a 300 mm x 300 mm sample comprising two 2.1 mm thick soda-lime glass layers laminated with a 0.76 mm thick clear PVB bonding layer.
  • Sample 1 is a 300 mm x 300 mm sample comprised of a 3.8 mm thick borosilicate first glass layer having thermal properties of Glass 2 of Table 1 and a 0.7 mm thick aluminosilicate second glass layer, having thermal properties of Glass 4 of Table 1 , laminated with a 0.76 mm thick clear PVB bonding layer. The samples do not have a printed obscuration.
  • Sample 1 has resistance to a sharp impact of at least 0.1 J at a 10 % probability of failure when impacted with a 14 g Vickers-diamond tip indenter, whereas Sample STD has lower performance.
  • Full-size laminated glazing in the context of the invention, is considered a glazing having conventional dimensions.
  • Examples of full-size laminated glazing in the automotive industry are: conventional windshields of 1.5 m by 0.7 m, or large and panoramic windshields of 1.9 m by 1.9 m, conventional sidelites of 1.0 m to 0.5 m, conventional roofs of 1.5 m by 0.5 m, panoramic roofs of 1.5 m by 2.0 m, conventional backlites of 1.5 m to 0.5 m, and etc.
  • the sharp impact test should be performed on the external surface of the first glass layer such that it is 30 mm away from any of the edges of the glazing.
  • the full-size laminated glazing should be tested in multiple regions, as long as these regions are at least 100 mm apart and also 30 mm away from any edge of the glazing.
  • the full-size curved laminated glazing should be supported onto a steel base support of similar dimensions and curvature that provides support on all the periphery of the glazing.
  • a rubber seal is disposed in between the steel base and the laminated glazing to protect the glass surface. No steel frame is used.
  • FIG 8 (Table 2) summarizes the sharp impact test results obtained from four different full-size curved laminated glazing configurations.
  • Glazing 1 comprises a 3.8 mm thick borosilicate first glass layer having thermal properties described in Table 1 (Glass 1), a 0.7 mm thick aluminosilicate second glass layer having thermal properties described in Table 1 (Glass 4), laminated with a 0.76 mm thick clear PVB bonding layer.
  • Glazing 1 Obs has similar configuration, and further comprises a black band obscuration printed onto the internal surface of the borosilicate first glass layer using enamel.
  • Glazing 2 has a configuration that is similar to Glazing 1 , except that the borosilicate first glass layer has thermal properties of Glass 2 of Table 1.
  • Glazing 2 Obs has a configuration that is similar to Glazing 1 Obs, except that the borosilicate first glass layer has thermal properties of Glass 2 of Table 1. All glazing show improved sharp impact resistance, achieving at least 0.2 J at a 10 % probability of failure when impacted with a 14 g Vickers- diamond tip indenter.
  • the resistance to sharp impact is of at least 0.2 J at a 10 % probability of failure when impacted with a 14 g Vickers-diamond tip indenter.
  • the first glass layer is selected from the group of borosilicate glass, it can be chemically strengthened which further improves its mechanical resistance to blunt impact.
  • the ball drop impact test is a method used to evaluate the blunt impact resistance of automotive glass.
  • flat laminated glass samples of 300 mm x 300 mm are mounted horizontally to a supporting metallic fixture similar to the one used for sharp impact tests, except that now matching the dimensions of the ball drop laminated samples.
  • a steel spherical ball of 681 g of weight is dropped from predetermined heights onto the center of the glass sample.
  • the energy at breakage, in Joules is calculated based on the height at breakage and the ball weight. Failure is defined when any crack is originated after the impact in any or both of the glass layers.
  • the heights of failure for each one of the samples tested are recorded and plotted onto a graphic displaying a Weibull distribution with the probability of failure on one axis and the height of failure is converted into energy of impact and displayed on the other axis.
  • Figure 9 shows ball drop results for three types of samples of 300 mm x 300 mm of dimension, the first glass having thermal properties of Glass 2 of Table 1 (Glass inv), a glass having thermal properties of Glass 3 of Table 1 (Glass std), and the first glass having thermal properties of Glass 2 of Table 1 , however going through the process of with chemical strengthening treatment (Glass inv iox), all samples having the same thickness of 3.8 mm and being laminated with 0.76 mm clear PVB bonding layer, and 0.7 mm aluminosilicate as second glass layer.
  • the samples do not comprise any region printed with a glass enamel. It is evident that at 10 % probability of failure, the glass of the invention with chemical strengthening treatment has superior performance, resulting in energy of breakage of above 11 J, in comparison to approximately 4 J obtained for the glass samples without the chemical treatment.
  • Ball drop impact test can be performed onto full-size laminated glazing similarly to the sharp impact test
  • the at least one printed area has an obscuration painted with a porous glass enamel, such as the one disclosed in the prior art WO2023275806A1.
  • the porous structure allows for the molten salt from the chemical strengthening process to penetrate the glass enamel layer and to reach the surface of the glass.
  • Another aspect of the invention is a vehicle comprising the laminated glazing of the invention.
  • another aspect of the invention is a method for producing a laminated glazing for a vehicle having improved mechanical resistance.
  • the method comprises the following steps: providing at least two glass layers comprising: a first glass layer having an exterior surface oriented towards the outside of the laminated glazing, an interior surface oriented towards the inside of the laminated glazing, having temperatures of softening Tsof, annealing Tanf and strain Tstf, coefficient of thermal expansion CTEf, and having at least one area onto said internal surface printed with a glass enamel; a second glass layer having an interior surface oriented towards the inside of the laminated glazing, an exterior surface oriented towards the outside of the laminated glazing, having temperatures of softening Tso s , annealing Tan s and strain Tst s , and coefficient of thermal expansion CTEs; at least one bonding layer, being disposed between the interior surface(s) of the first and the second glass layers; wherein said first glass layer has a parameter TCf and the second glass layer has a parameter Tc s , according to where
  • the first glass layer is preferably thermally bent/curved prior to the lamination step.
  • the second glass layer could be cold-bent.
  • the second glass layer is provided flat and during the step of lamination it is forced to conform to the shape of the second glass layer.
  • the first glass layer could be chemically strengthened. In this case, after the step of providing the first glass layer having at least one area onto the internal surface printed with a porous glass enamel, said first glass layer goes through the following steps: thermal bending, and carrying out chemical strengthening process.
  • a laminated glazing wherein the first glass layer is a thermally curved borosilicate glass, having a black band printed with a black frit glass enamel and having thickness of 3.8 mm and having CTEf, Tsof, Tanf, and Tstf according to Glass 2 of the table 1 in Figure 3.
  • the laminate is also comprised of a PVB bonding layer having thickness of 0.76 mm, and the second glass layer is a cold-bent aluminosilicate glass having thickness of 0.7 mm chemically strengthened, having CTEs, Tso s , Tan s , and Tst s according to Glass 4 of the table 1 in Figure 3.
  • the temperature TCf is 2.7 °C and the temperature Tc s is 6.2 °C.
  • a laminated glazing wherein the first glass layer is a borosilicate glass, having a black band printed with a black frit glass enamel, having thickness of 3.3 mm with thermal properties of Glass 1 shown in the table 1 in Figure 3.
  • the glazing also has a 0.76 mm thick PVB layer as the bonding layer, and the second glass layer is an aluminosilicate glass of 1.1 mm chemically strengthened with thermal properties of Glass 4 shown in the table 1 in Figure 3.
  • the temperature TCf is 2.1 °C and the temperature Tc s is 5.3 °C.
  • a laminated glazing having a borosilicate glass of 3.8 mm of thickness as the first glass layer, a PVB of 0.76 mm of thickness for the bonding layer, and the second glass layer being an aluminosilicate glass of 0.7 mm of thickness that is chemically strengthened.
  • the first glass has a printed area on its internal surface 102.
  • the printed area has a flexural strength of 93 MPa for 63.2 % probability of failure that represents less than 50% reduction compared to the flexural strength of the clear area (see Figure 4).
  • the surface stress of the first glass layer measured at 25 mm from the edge is 4 MPa in average.
  • the surface stress of the first glass layer measured at the center of the surface is -3 MPa in average.

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Abstract

The present invention is a laminated glazing for a vehicle having improved mechanical resistance. The glazing of the invention is comprised of at least two glass layers, wherein the first glass layer has at least one printed area. The at least one printed area has a flexural strength of at least 40 MPa at a probability of failure of 63.2%.

Description

LAMINATED GLAZING FORA VEHICLE HAVING IMPROVED MECHANICAL RESISTANCE TO IMPACTS
FIELD OF THE INVENTION
The present invention falls in the field of a laminated glazing for a vehicle and, more particularly, it relates to a glazing with improved mechanical resistance to impacts.
BACKGROUND OF THE INVENTION
Standard laminated glazing for a vehicle is conventionally comprised of two glass layers, a first glass layer that is disposed closer to the exterior of a vehicle and a second glass layer that is disposed closer to the interior of a vehicle, both being comprised of sodalime glass, and one bonding layer typically comprised of PVB that serves to permanently bond the two glass layers together. Laminated glazing is mostly used in windshield positions to provide for safety of the vehicle occupants. This is because in case of debris or any external object hitting the windshield it protects the vehicle occupants from these objects. Additionally, if any of the glass layers of the windshield fails, the bonding layer holds the glass shards together avoiding injuries due to spalling. Moreover, the windshield (damaged or not) provides retention of vehicle occupants, in case of an accident such as a crash. Anytime a vehicle glazing is damaged it should be replaced. This translates into cost and down time for the vehicle owner.
Laminated glazing has another advantage over the conventional monolithic glazing which is that it may be comprised of performance interlayers laminated in between the glass layers. These performance interlayers may provide for instance sound dampening, anti-intrusion protection, solar control, cabin thermal comfort, light transmission control, heating for deicing and defogging, among other functionalities.
Another important trend in transportation is the move toward full autonomous operation. Today, most new vehicles come with some level of automated driver assistance system as standard equipment. Automated driver assistance systems are just one of the innovative technologies that the vehicle glazing has become an integral and essential part of. With the vehicle glazing occupying a large percent of the vehicle exterior and interior surface area, it is increasingly being integrated with the various sensors and other electronic components needed to enable such systems. Having a myriad of possibilities for functionality integration into the glazing, customers have been demanding laminated glazing not only in windshield by in other vehicle positions such as in roofs, sidelites, and backlites.
The cost for a laminated glazing comprising such functionalities, for example performance interlayers and electronic components and sensors, is elevated which is pushing the market to provide a laminated glazing with higher mechanical resistance to impacts and therefore decreasing costs associated with glazing replacement.
The prior-art has solved this problem by suggesting the use of different glass compositions other than soda-lime glass, preferably in the first glass layer of the laminated glazing.
However, even glass compositions with higher mechanical resistance, such as borosilicate glass, exhibit impact resistance problems in the areas of the glass layer where obscuration comprising a glass enamel, also called as black frit, is applied. During the bending of the glass layers by means of temperature, the glass enamel is said to be “fired” or cured/vitrified. During this process, the glass enamel chemically dissolves onto the glass layer surface and in doing so it produces surface defects. This makes the surface of the glass weaker, increasing the probability of breakage when suffering an impact.
One solution to this problem is to provide an obscuration using organic ink painted onto the glass layer, or by providing an opaque black plastic interlayer or insert in between the glass layers that can serve as obscuration.
This approach presents several drawbacks. Unlike the glass enamel that needs to be fired at high temperatures, normally during the step of glass layer bending, the organic ink cannot withstand high temperatures. Therefore, the glass layer comprising the organic ink should be either cold-bent (a process well-known in the art) or the organic ink should be applied onto an already bent/curved glass layer. The latter option is a more complex process and therefore costly.
It would be advantageous to have a laminated glazing comprising a first glass layer that is not comprised of soda-lime glass and having at least one area printed with a glass enamel wherein said glazing has improved mechanical resistance to impacts. It would also be advantageous to provide a method for producing such laminated glazing.
BRIEF SUMMARY OF THE INVENTION The present invention provides a solution to the aforementioned problems by providing a laminated glazing for a vehicle having improved mechanical resistance to impacts, the laminated glazing comprising at least two glass layers, a first glass layer 201 , that is not comprised of soda-lime glass, and a second glass layer 202. The glazing also comprises at least one bonding layer 4 being disposed in between the interior surface(s) of the first and the second glass layers.
The first glass layer 201 has at least one area onto its internal surface 102 printed with a glass enamel. The first glass layer 201 has softening temperature Tsof (°C), annealing temperature Tanf (°C), strain temperature Tstf (°C), and coefficient of thermal expansion CTEf(1/°C). The second glass layer 202 has softening temperature Tsos (°C), annealing temperature Tans (°C), strain temperature Tsts (°C), and coefficient of thermal expansion CTEs (1/°C).
The first glass layer 201 has a parameter TCf and the second glass layer 202 has a parameter Tcs, such that the difference, in absolute numbers, between Tcs and TCf is more than or equal to 2. The parameter Tcs,f is obtained by the following equation:
The at least one printed area of the first glass layer 201 has a flexural strength of at least 40 MPa at a probability of failure of 63.2 % according to the normative standard DIN 1288 ring on ring test.
The present invention also provides a method for manufacturing a laminated glazing for a vehicle having improved mechanical resistance to impacts, such method comprising the steps of providing at least two glass layers comprising a first glass layer having an exterior surface oriented towards the outside of the laminated glazing, an interior surface oriented towards the inside of the laminated glazing, having temperatures of softening Tsof, annealing Tanf and strain Tstf, coefficient of thermal expansion CTEf, and having at least one area onto said internal surface printed with a glass enamel.
The glazing having at least two glass layers also comprises a second glass layer having an interior surface oriented towards the inside of the laminated glazing, an exterior surface oriented towards the outside of the laminated glazing, having temperatures of softening Tsos, annealing Tans and strain Tsts, and coefficient of thermal expansion CTEs. The laminated glazing of the invention also comprises at least one bonding layer, being disposed between the interior surface(s) of the first and the second glass layers, wherein said first glass layer has a parameter TCf and the second glass layer has a parameter Tcs, according to wherein the difference between Tcs and TCf is more than or equal to 2, and wherein said at least one printed area of the first glass layer has a flexural strength of at least 40 MPa at the probability of failure of 63.2% according to the normative standard DIN 1288 ring on ring test.
After providing the layers, the method of the invention also comprises the step of laminating said first and second glass layers with said at least one bonding layer, forming the laminated glazing of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
These and other features and advantages of the invention will be seen more clearly from the following detailed description of a preferred embodiment provided only by way of illustrative and non-limiting example in reference to the attached drawings.
Figure 1 illustrates a vehicle comprising the laminated glazing of the invention.
Figure 2 shows a generic realization of a cross section of the laminated glazing of the invention.
Figure 3 illustrates a laminated windshield having at least one printed area with a glass enamel comprising an obscuration.
Figure 4 shows flexural strength experimental results.
Figure 5 shows Table 1 with examples of glass compositions and the following parameters Tsof,s, Tanf,s, Tstf,s, and CTEf,s.
Figure 6 illustrates the support apparatus for the ball drop and sharp impact tests.
Figure 7 shows the results of sharp impact tests.
Figure 8 shows Table 2 with sharp impact test results.
Figure 9 shows the results of ball drop tests. REFERENCE NUMERALS OF DRAWINGS
1 vehicle
2 laminated windshield
3 laminated sidelite
4 first bonding layer
6 obscuration/glass enamel
8 laminated roof
10 laminated backlite
12 a steel base support
14 steel frame
16 laminated sample
100 laminated glazing
101 exterior surface of first glass layer
102 interior surface of first glass layer
103 interior surface of second glass layer
104 exterior surface of second glass layer
201 first glass layer
202 second glass layer
DETAILED DESCRIPTION OF THE INVENTION
As will be appreciated by one skilled in the art, aspects of the present invention may be embodied as a product or method. The term “layer”, as used in this context, shall include the common definition of the word, i.e.: a sheet, quantity, or thickness, of material, typically of some homogeneous substance.
The term “stack” refers to the arrangement in a pile manner of a plurality of layers forming the laminated glazing.
Laminates, in general, are articles comprised of multiple layers of thin, relative to their length and width, material, with each thin layer having two oppositely disposed major faces, typically of uniform thickness, which are permanently bonded to one and other across at least one major face of each layer. The layers of a laminate may alternately be described as sheets or plies. In addition, the glass layers of a glazing may be referred to as panes.
The term “glazing” should be understood as a product comprised of at least one layer of a transparent material, preferably glass, which serves to provide for the transmission of light and/or to provide for viewing of the side opposite to the viewer and which is mounted in an opening in a building, vehicle, wall or roof or other framing member or enclosure.
The term “vehicle” in the present invention includes, but is not limited to, road vehicles (e.g., cars, busses, trucks, agricultural and construction vehicles, cabin motorbikes), railway vehicles (e.g., locomotives, coaches), aircraft (e.g. airplanes, helicopters), boats, ships and the like. For instance, the vehicle may be a road vehicle and more particularly a car.
The present invention provides a solution for a laminated glazing for a vehicle having improved mechanical resistance to impacts.
Figure 1 illustrates a top view of a vehicle 1 comprising a laminated glazing 100 of the invention such as a laminated windshield 2, a laminated sidelite 3, a laminated roof 8, or a laminated backlite 10.
A cross section of a generic realization of the invention is illustrated in Figure 2.
The laminated glazing 100 comprises at least two glass layers, however more than two glass layers, such as three or four, can be comprised in such a glazing without departing from the spirit of the invention. The at least two glass layers comprise: a first glass layer 201 that is not comprised of soda-lime glass, having an exterior surface 101 oriented towards the outside of the laminated glazing, an interior surface 102 oriented towards the inside of the laminated glazing, having temperatures of softening Tsof, annealing Tanf, and strain Tstf, coefficient of thermal expansion CTEf, and having at least one area onto said interior surface 102 printed with a glass enamel 6.
In one preferred embodiment the first glass layer is disposed closer to the exterior of a vehicle, such that it can be considered an outer glass layer (facing the exterior of the vehicle).
The at least one printed area could be one, or a plurality of areas that are printed with a glass enamel forming an obscuration. Obscurations are used, conventionally as a black band around the perimeter of the glazing to protect the sealing materials that fix the glazing to the vehicle body from UV light exposure and degradation. They also serve to hide electrical components, the edge of the interlayers, or any other components that should not be visible to an observer. The obscuration needs to be opaque in the sense of difficulty to see through rather than blocking all light. The typical obscuration light transmission is less than 5%, preferably less than 3%, and more preferably equal to 0%.
In one embodiment the at least one printed area is a black band obscuration 6 that is at least partially disposed around the perimeter of the glazing. In another embodiment the at least one printed area is a black band obscuration as described above and it also comprises an obscuration 6 around a driver assistance system opening window such as an area intended to receive a sensor, a safety camera, or LIDAR. In this case the obscuration serves to hide any electrical components, supports, and brackets of such systems. This is illustrated in Figure 3. The black band obscuration provided for the perimeter of the glazing could be connected to the obscuration of the opening window for the driver assistance system or it could be separated from it without departing from spirit of the invention.
Conventionally, in the automotive industry the obscuration is a glass enamel (black frit) that is comprised of pigments, a carrier, binders and finely ground glass. Standard black frit obscurations are optimized in their formulation to thermally match the glass layer which it is printed on. The glass enamel is applied to the glass surface using a silk screen or ink jet printing process prior to heating and bending. During the heating and bending process, the finely ground glass in the frit softens and fuses to the glass surface. When this process takes place, the glass enamel is said to be “fired” also known as vitrified. A fired black glass enamel normally increases surface defects. This happens because the glass enamel chemically dissolves onto the glass layer and in doing so it produces surface defects. This makes the surface weaker, increasing the probability of breakage. Testing has shown that glass with black frit fails at a stress level that is substantially lower than glass that does not have a fired black frit.
In one embodiment the first glass layer has at least one area printed with a glass enamel, wherein said glass enamel has a coefficient of thermal expansion (CTEe) ranging from 20 x 10’7 1/°C to 65 x 10’7 1/°C.
The glazing of the invention comprises at least one printed area of the first glass layer having a flexural strength of at least 40 MPa at a probability of failure of 63.2 % according to the normative standard DIN 1288 ring on ring test.
The inventors have discovered that when providing such first glass layer with an area printed with a glass enamel, and having such flexural strength, it results in improved mechanical resistance to impacts when said glass is assembled into the glazing of the invention. This glass enamel composition is either currently available in the market or can be formulated by a skilled person to produce the first glass layer with said structural characteristic and suitable CTEe for glass compatibility .
In one preferred embodiment, the glazing of the invention comprises at least one printed area of the first glass layer having said area a flexural strength of at least 55 MPa at a probability of failure of 63.2 % according to the normative standard DIN 1288 ring on ring test.
Flexural strength was measured by performing the ring-on-ring test following the normative standard DIN 1288. According to this normative, two rings of 18 mm and of 90 mm of diameter were used: one for applying load (the loading ring) and the other one for supporting the sample (the support ring). Glass samples of 100 mm x 100 mm were placed one at a time centered above the support ring, while the loading ring was placed on top of the samples, ensuring alignment with the support ring. A load was then gradually applied to the center of the loading ring using a testing machine until sample breakage. A minimum of thirty samples were tested following the method described previously. The flexural strength probability is calculated based on the applied load and sample dimensions and displayed into a Weibull distribution of probability of failure.
Figure 4 shows flexural strength results obtained for three sets of samples of 100 mm x 100 mm size, the three sets comprising a glass layer having thermal properties of Glass 2 of Table 1 , having thickness of 3.8 mm; wherein the first set of samples (Glass printed obs) has the entire surface printed with a glass enamel formulation that matches the CTE of the glass and has improved flexural strength performance, a second set of samples (Glass printed std) having its entire surface printed with a standard glass enamel formulation currently available in the market for glass composition that is not soda-lime, and the third set of samples (Glass not printed) is not printed at all.
It becomes clear from Figure 4, that the first set of samples (Glass printed obs) has a flexural strength above 40 MPa at 63.2 % probability of failure. In fact, the flexural strength obtained was about 93 MPa.
When evaluating a full-size laminated glazing the flexural strength test should be performed by delaminating the first glass layer with the obscuration and cutting samples of 100 mm x 100 mm, such samples comprising at least one area printed with a glass enamel.
The laminated glazing 100 of the invention also comprises at least one second glass layer 202, having an interior surface 103 oriented towards the inside of the laminated glazing, an exterior surface 104 oriented towards the outside of the laminated glazing, having temperatures of softening Tsos, annealing Tans, and strain Tsts, and coefficient of thermal expansion CTEs; and at least one bonding layer, being disposed between the interior surface(s), 102, and 103, of the first 201 and the second 202 glass layers.
In one preferred embodiment the second glass layer is disposed closer to the interior of a vehicle (facing the interior of the vehicle).
The at least one second glass layer may have the CTEs ranging from 70 x 10'7 1/°C to 105 x 10'7 1/°C. In one embodiment the at least one second glass layer is selected from soda lime, and aluminosilicate.
Figure 5 shows Table 1 with examples of ranges for CTE, Tso, Tan, Tst of the at least one first and at least one second glass layers.
The at least one bonding layer 4 has the primary function of bonding the major faces of adjacent layers of the glazing to each other. In the present invention it is comprised of a polymer film and may be selected from any of the following: polyvinyl butyral (PVB), ethylene vinyl acetate (EVA), thermoplastic polyurethane (TPU), polyolefin elastomers (PoE), or a combination thereof.
Preferably, the thickness of the at least one bonding layer 4 is comprised between 0.3 mm and 2.0 mm, more preferably comprised between 0.5 mm and 1.0 mm, e.g., about 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm or 1.0 mm. More than one bonding layer 4 can be used such as two, three, or a plurality of bonding layers 4 without departing from the spirit of the invention.
Additionally with the above-mentioned properties, the mechanical resistance to impacts is improved by selecting the correct combination of chemical composition of each one of the glass layers constituting the glazing;
The glazing of the invention has a first glass layer with a parameter TCf and the second glass layer with a parameter Tcs, according to such that the difference, in absolute numbers, between Tcs and TCf is more than or equal to 2.
There is a limited number of combinations of temperature of softening, annealing and strain, along with CTE, that results in such parameter TCf,s condition. For instance, the at least one first glass layer may have a CTEf ranging from 30 x 10'7 1/°C to 50 x 10-7 1/°C. In one preferred embodiment the at least one first glass layer is a borosilicate glass layer.
In the automotive industry, accepted values for surface tensile stress of the glass layer should be below 10 MPa at any given region of the surface. Anything above may lead to spontaneous glass breakage during manipulation, installation and usage in the vehicle. However, low CTE glass compositions, such as CTE below 50 x 10'7 1/°C, may lead to increased surface tensile stress. This problem is normally solved by controlling the cooling and annealing processes of the first glass layer such as to achieve acceptable surface tensile stresses.
In one embodiment the first glass layer is a borosilicate glass and has a surface tensile stress below 8 MPa measured at 25 mm from the glass edge, and below 5 MPa when measured at the center of the glass. In one preferred embodiment the first glass layer is a borosilicate glass having a surface tensile stress measured at the center of the glass below 2 MPa.
The laminated glazing of the present invention is preferably a curved laminated glazing.
Curved laminated glazing can be achieved by thermally bending at least one or all the glass layers forming the glazing. Thermal bending of glass involves heating the glass to the glass transition temperature range where it is bent to shape then cooling the glass to freeze in the change in shape. In this case, glass undergoes a permanent plastic deformation. The glass can be slowly cooled to relieve stress, a process known as annealing, or can be rapidly cooled to heat strengthen, process known as tempering.
For a glazing comprising a first glass layer thermally bent, the second glass layer could also be thermally bent/curved or cold-bent. Cold bending is a relatively recent technology in the automotive industry. As the name suggests, the glass is bent, while cold to its final shape, without the use of heat. However, as the glass only undergoes elastic deformation, at any point on the bent area of the glass one side, i.e. , major surface, of the glass will have a substantially higher level of stress than on the opposite side of the glass. If annealed glass is used, one side will be in compression and the other in tension.
Performance layers may also be used in the glazing. Performance layers include but are not limited to films that provide a functionality to the glazing such as solar control (e.g., infrared blocking film), variable light transmission, Head up Display (HUD) imaging, HUD holographic (HoE) imaging, increased stiffness, increased structural integrity, improved penetration resistance, improved occupant retention, a chemical barrier/protection, tint, sunshade, obscuration for black band or for hiding and protecting integrated systems, color correction, and as a substrate for functional and aesthetic graphics.
In one embodiment at least one performance layer is disposed in between the first and second glass layers of the glazing of the invention.
Additionally, or in place of a performance layer, coatings can be applied to at least one of the glass layers of the invention and provide functionality to the laminated glazing such as infrared protection, UV protection, low-emissivity for thermal comfort, among others.
In one embodiment the glazing of the invention comprises a coating.
In one particular realization of this embodiment, an infrared blocking layer is disposed between the first and second glass layers and is selected from the group of a film, or a coating.
The glazing of the invention having improved mechanical resistance to impacts could be advantageously comprised of photovoltaic devices, e.g., solar cells, that are laminated within the layers of the glazing.
The thickness of the at least one first glass layer 201 and at least one second glass layer 202 may vary widely and thus be ideally adapted to the requirements of the individual cases. In an embodiment, the thickness of the first glass layer and the second glass layer of the laminated glazing of the invention is lower than 5.0 mm, preferably comprised between 0.3 mm and 5.0 mm, such as between 0.5 mm and 4.0 mm or between 1.0 mm and 3.0 mm. Possible examples of thicknesses of the glass layers are about 1.5 mm, 1.6 mm, 1.7 mm, 1.8 mm, 1.9 mm, 2.0 mm, 2.1 mm, 2.2 mm, 2.3 mm, 2.4 mm, 2.5 mm, 2.6 mm, 2.7 mm, 2.8 mm, 2.9 mm or 3.0 mm.
It has been found that the correct combination of glass thickness also improves mechanical resistance to impacts. In the present invention, the first glass layer 201 has thickness tf (mm) and the second glass layer 202 has thickness ts (mm) that is preferably no lower than 0.5 mm, wherein the difference between tf and ts follows the equation below: tf 0 < tf - ts) * log (^-) < 4.5
In one preferred embodiment, the difference between tf and ts follows the equation below:
1.0 < tf - ts) * log (^) < 3.1
The glazing of the invention has improved mechanical resistance to sharp impacts. The sharp impact test consists of providing laminated samples 16 of dimensions of 300 mm x 300 mm and disposing them one at a time onto a steel base support 12 of similar dimensions such that each sample is disposed with the first glass layer 201 facing up and the second glass layer 202 facing down, and the sample edges are fixed against a steel frame 14. The testing support used is described by the standard normative ECE R43 Annex 3 (2.1.1.3). In between the steel base support and steel frame and the glass sample a rubber seal is disposed to protect the glass surface. The support with sample can be illustrated in Figure 6 which shows a cross section of a sample mounted onto the support.
The samples are tested one at a time by having a Vickers diamond tip indenter weighing 14 g and being dropped from heights in increments of 0.1 m until breakage ranging from 0.5 m to 3.0 m. Each sample of 300 x 300 mm has nine quadrants spaced 100 mm apart from each other. Each quadrant receives one impact at its center region. The impact is performed by dropping a Vickers diamond tip indenter weighing 14g from a predetermined height starting from 0.5 m to a maximum of 3.0 m. For each impact, the dropping height is incremented by 0.1m until failure is detected. . The heights of failure are recorded and converted to energy of impact [J] considering the following equation: E = m x g x h
Wherein, m [kg] is the weight of the indenter, g [m/s2] is the gravity acceleration, and h [m] is the height from where the indenter has been dropped. The height of failure is identified when the impact causes a crack having a diameter larger than 7 mm. When failure is detected, the next impact test starts at a height of 0.2 m below the height of failure. A minimum of thirty impact tests are performed .The heights of failure for each one of the samples tested are recorded and plotted onto a graphic displaying a Weibull distribution with the probability of failure on the y axis and the energy of impact at failure is displayed on the x axis.
For example, when one sample having nine quadrants is tested, each quadrant having a number Q1, Q2, Q3, .., Q9, Q1 is tested at h = 0.1 m, Q2 is tested at h =0.2 m, Q3 is tested at h = 0.3 m, Q4 is tested at h = 0.4 m, and failure happens at Q4. In this example, Q5 is tested at h = 0.2 m, Q6 is tested at h = 0.3 m, Q7 is tested at h = 0.4 m, Q8 is tested at h = 0.5 m and failure happens at Q8. Q9 is tested at h = 0.3. The heights of failure that are recorded are the heights for Q4 and Q8, i.e., h = 0.3 m and h = 0.4 m, respectively.
Figure 7 shows the results of a sharp impact test performed in a minimum of thirty samples of each configuration. Sample STD is a 300 mm x 300 mm sample comprising two 2.1 mm thick soda-lime glass layers laminated with a 0.76 mm thick clear PVB bonding layer. Sample 1 is a 300 mm x 300 mm sample comprised of a 3.8 mm thick borosilicate first glass layer having thermal properties of Glass 2 of Table 1 and a 0.7 mm thick aluminosilicate second glass layer, having thermal properties of Glass 4 of Table 1 , laminated with a 0.76 mm thick clear PVB bonding layer. The samples do not have a printed obscuration. It can be seen from the sharp impact results that Sample 1 has resistance to a sharp impact of at least 0.1 J at a 10 % probability of failure when impacted with a 14 g Vickers-diamond tip indenter, whereas Sample STD has lower performance.
Full-size laminated glazing, in the context of the invention, is considered a glazing having conventional dimensions. Examples of full-size laminated glazing in the automotive industry are: conventional windshields of 1.5 m by 0.7 m, or large and panoramic windshields of 1.9 m by 1.9 m, conventional sidelites of 1.0 m to 0.5 m, conventional roofs of 1.5 m by 0.5 m, panoramic roofs of 1.5 m by 2.0 m, conventional backlites of 1.5 m to 0.5 m, and etc. When evaluating a full-size curved laminated glazing the sharp impact test should be performed on the external surface of the first glass layer such that it is 30 mm away from any of the edges of the glazing. The full-size laminated glazing should be tested in multiple regions, as long as these regions are at least 100 mm apart and also 30 mm away from any edge of the glazing. The full-size curved laminated glazing should be supported onto a steel base support of similar dimensions and curvature that provides support on all the periphery of the glazing. A rubber seal is disposed in between the steel base and the laminated glazing to protect the glass surface. No steel frame is used.
Figure 8 (Table 2) summarizes the sharp impact test results obtained from four different full-size curved laminated glazing configurations. Glazing 1 comprises a 3.8 mm thick borosilicate first glass layer having thermal properties described in Table 1 (Glass 1), a 0.7 mm thick aluminosilicate second glass layer having thermal properties described in Table 1 (Glass 4), laminated with a 0.76 mm thick clear PVB bonding layer. Glazing 1 Obs has similar configuration, and further comprises a black band obscuration printed onto the internal surface of the borosilicate first glass layer using enamel. Glazing 2 has a configuration that is similar to Glazing 1 , except that the borosilicate first glass layer has thermal properties of Glass 2 of Table 1. Glazing 2 Obs has a configuration that is similar to Glazing 1 Obs, except that the borosilicate first glass layer has thermal properties of Glass 2 of Table 1. All glazing show improved sharp impact resistance, achieving at least 0.2 J at a 10 % probability of failure when impacted with a 14 g Vickers- diamond tip indenter.
In one preferred embodiment of the glazing of the invention the resistance to sharp impact is of at least 0.2 J at a 10 % probability of failure when impacted with a 14 g Vickers-diamond tip indenter.
Surprisingly, the inventors have discovered that for a full-size laminated glazing the resistance to sharp impacts is similar when comparing the glazing of the invention printed with a glass enamel and a glazing with similar configuration, but without any printing. Even though the flexural strength results (Figure 4) show a difference in mechanical performance when comparing glass samples with different obscurations, it is the combination of first and second glass layers having specific features in addition to the obscuration of choice that results into the laminated glazing of the invention with improved mechanical resistance to impacts (Figure 8). The mechanical resistance of the glazing of the invention is also improved for blunt impact test, when compared to standard laminated glazing.
It was found surprisingly that when the first glass layer is selected from the group of borosilicate glass, it can be chemically strengthened which further improves its mechanical resistance to blunt impact.
The ball drop impact test is a method used to evaluate the blunt impact resistance of automotive glass. In this test, flat laminated glass samples of 300 mm x 300 mm are mounted horizontally to a supporting metallic fixture similar to the one used for sharp impact tests, except that now matching the dimensions of the ball drop laminated samples. During the test, a steel spherical ball of 681 g of weight is dropped from predetermined heights onto the center of the glass sample. The energy at breakage, in Joules, is calculated based on the height at breakage and the ball weight. Failure is defined when any crack is originated after the impact in any or both of the glass layers. The heights of failure for each one of the samples tested are recorded and plotted onto a graphic displaying a Weibull distribution with the probability of failure on one axis and the height of failure is converted into energy of impact and displayed on the other axis.
Figure 9 shows ball drop results for three types of samples of 300 mm x 300 mm of dimension, the first glass having thermal properties of Glass 2 of Table 1 (Glass inv), a glass having thermal properties of Glass 3 of Table 1 (Glass std), and the first glass having thermal properties of Glass 2 of Table 1 , however going through the process of with chemical strengthening treatment (Glass inv iox), all samples having the same thickness of 3.8 mm and being laminated with 0.76 mm clear PVB bonding layer, and 0.7 mm aluminosilicate as second glass layer. The samples do not comprise any region printed with a glass enamel. It is evident that at 10 % probability of failure, the glass of the invention with chemical strengthening treatment has superior performance, resulting in energy of breakage of above 11 J, in comparison to approximately 4 J obtained for the glass samples without the chemical treatment.
Ball drop impact test can be performed onto full-size laminated glazing similarly to the sharp impact test
When the borosilicate first glass layer is chemically strengthened, the at least one printed area has an obscuration painted with a porous glass enamel, such as the one disclosed in the prior art WO2023275806A1. The porous structure allows for the molten salt from the chemical strengthening process to penetrate the glass enamel layer and to reach the surface of the glass. Another aspect of the invention is a vehicle comprising the laminated glazing of the invention.
Yet, another aspect of the invention is a method for producing a laminated glazing for a vehicle having improved mechanical resistance. The method comprises the following steps: providing at least two glass layers comprising: a first glass layer having an exterior surface oriented towards the outside of the laminated glazing, an interior surface oriented towards the inside of the laminated glazing, having temperatures of softening Tsof, annealing Tanf and strain Tstf, coefficient of thermal expansion CTEf, and having at least one area onto said internal surface printed with a glass enamel; a second glass layer having an interior surface oriented towards the inside of the laminated glazing, an exterior surface oriented towards the outside of the laminated glazing, having temperatures of softening Tsos, annealing Tans and strain Tsts, and coefficient of thermal expansion CTEs; at least one bonding layer, being disposed between the interior surface(s) of the first and the second glass layers; wherein said first glass layer has a parameter TCf and the second glass layer has a parameter Tcs, according to wherein the difference between Tcs and TCf is more than or equal to 2 °C, and wherein said at least one printed area of the first glass layer has a flexural strength of at least 40 MPa at a probability of failure of 63.2% when compared to the area that is not printed according to the normative standard DIN 1288 ring on ring test; and laminating said first and second glass layers with said at least one bonding layer.
The first glass layer is preferably thermally bent/curved prior to the lamination step. In one embodiment the second glass layer could be cold-bent. In this case the second glass layer is provided flat and during the step of lamination it is forced to conform to the shape of the second glass layer. In another embodiment the first glass layer could be chemically strengthened. In this case, after the step of providing the first glass layer having at least one area onto the internal surface printed with a porous glass enamel, said first glass layer goes through the following steps: thermal bending, and carrying out chemical strengthening process.
Herein follows a few examples or realization of the invention.
EXAMPLE 1 :
A laminated glazing wherein the first glass layer is a thermally curved borosilicate glass, having a black band printed with a black frit glass enamel and having thickness of 3.8 mm and having CTEf, Tsof, Tanf, and Tstf according to Glass 2 of the table 1 in Figure 3. The laminate is also comprised of a PVB bonding layer having thickness of 0.76 mm, and the second glass layer is a cold-bent aluminosilicate glass having thickness of 0.7 mm chemically strengthened, having CTEs, Tsos, Tans, and Tsts according to Glass 4 of the table 1 in Figure 3. The temperature TCf is 2.7 °C and the temperature Tcs is 6.2 °C.
EXAMPLE 2:
A laminated glazing wherein the first glass layer is a borosilicate glass, having a black band printed with a black frit glass enamel, having thickness of 3.3 mm with thermal properties of Glass 1 shown in the table 1 in Figure 3. The glazing also has a 0.76 mm thick PVB layer as the bonding layer, and the second glass layer is an aluminosilicate glass of 1.1 mm chemically strengthened with thermal properties of Glass 4 shown in the table 1 in Figure 3. The temperature TCf is 2.1 °C and the temperature Tcs is 5.3 °C.
EXAMPLE 3:
A laminated glazing having a borosilicate glass of 3.8 mm of thickness as the first glass layer, a PVB of 0.76 mm of thickness for the bonding layer, and the second glass layer being an aluminosilicate glass of 0.7 mm of thickness that is chemically strengthened. The first glass has a printed area on its internal surface 102. The printed area has a flexural strength of 93 MPa for 63.2 % probability of failure that represents less than 50% reduction compared to the flexural strength of the clear area (see Figure 4). The surface stress of the first glass layer measured at 25 mm from the edge is 4 MPa in average. The surface stress of the first glass layer measured at the center of the surface is -3 MPa in average.
It shall be noted that the idea of the invention is not limited to the embodiments described above but may be implemented in an entirely different fashion in different embodiments.

Claims

CLAIMS What is claimed is:
1 . A laminated glazing for a vehicle with improved mechanical resistance to impacts, the glazing comprising: at least two glass layers comprising a first glass layer having an exterior surface oriented towards the outside of the laminated glazing, an interior surface oriented towards the inside of the laminated glazing, having temperatures of softening Tsof (in °C), annealing Tanf (in °C) and strain Tstf (in °C), coefficient of thermal expansion CTEf (in 1/°C), and having at least one area onto said internal surface printed with a glass enamel; a second glass layer having an interior surface oriented towards the inside of the laminated glazing, an exterior surface oriented towards the outside of the laminated glazing, having temperatures of softening Tsos (in °C), annealing Tans (in °C) and strain Tsts (in °C), and coefficient of thermal expansion CTEs (in 1/°C); at least one bonding layer, being disposed between the interior surface(s) of the first and the second glass layers; and wherein said first glass layer has a parameter TCf and the second glass layer has a parameter Tcs, according to wherein the difference, in absolute numbers, between Tcs and TCf is more than or equal to 2, and wherein said at least one printed area of the first glass layer has a flexural strength of at least 40 MPa at a probability of failure of 63.2% according to the normative standard DIN 1288 ring on ring test.
2. The laminated glazing of any of the preceding claims, wherein the glazing has a resistance to a sharp impact of at least 0.1 J at a 10 % probability of failure when impacted with a 14 g Vickers-diamond tip indenter about 30 mm away from the edge of the glazing.
3. The laminated glazing of any of the preceding claims, wherein the glazing is a curved laminated glazing.
4. The laminated glazing of any of the preceding claims, wherein the second glass layer is cold-bent.
5. The laminated glazing of any of the preceding claims, wherein the second glass layer is selected from soda-lime, and aluminosilicate.
6. The laminated glazing of any of the preceding claims, wherein the at least one bonding layer is comprised of a polymer film, is selected from any of the following polyvinyl butyral (PVB), ethylene vinyl acetate (EVA), thermoplastic polyurethane (TPU), polyolefin elastomers (PoE), and/or a combination thereof.
7. The laminated glazing of any of the preceding claims, further comprising an infrared blocking layer disposed between the first and second glass layers and selected from the group of a film, and a coating.
8. The laminated glazing of any of the preceding claims, wherein the first glass layer has thickness tf (in mm) and the second glass layer has thickness ts (in mm) that is no lower than 0.5 mm, wherein the difference between tf and ts follows the equation below tf
0 < tf - ts) * log (^) < 4.5
9. The laminated glazing of any one of the preceding claims, wherein the second glass layer is chemically strengthened.
10. The laminated glazing of any of the preceding claims, wherein the first glass layer is a borosilicate glass that is chemically strengthened and the at least one printed area is printed with a glass enamel that is porous.
11. The laminated glazing of any one of the preceding claims, wherein the first glass layer is a borosilicate glass, and has a surface tensile stress below 8 MPa measured at 25 mm from the glass edge and below 5 MPa when measured at the center of the glass.
12. The laminated glazing of any one of the preceding claims, wherein the glass enamel has a coefficient of thermal expansion CTEe ranging between 20 x 10'7 1/°C and 65 x 10'7 1/°C.
13. The laminated glazing any one of the preceding claims, further comprising photovoltaic devices laminated in between the first and second glass layers.
14. The laminated glazing of any one of the preceding claims is a windshield, sidelite, roof, or backlite.
15. A vehicle comprising the laminated glazing of any one of claims 1 to 13.
16. A method for manufacturing a laminated glazing for a vehicle with improved mechanical resistance, the method comprising the steps of: providing at least two glass layers comprising: a first glass layer having an exterior surface oriented towards the outside of the laminated glazing, an interior surface oriented towards the inside of the laminated glazing, having temperatures of softening Tsof (in °C), annealing Tanf (in °C) and strain Tstf (in °C), coefficient of thermal expansion CTEf (in 1/°C), and having at least one area onto said internal surface printed with a glass enamel; a second glass layer having an interior surface oriented towards the inside of the laminated glazing, an exterior surface oriented towards the outside of the laminated glazing, having temperatures of softening Tsos (in °C), annealing Tans (in °C) and strain Tsts (in °C), and coefficient of thermal expansion CTEs (in 1/°C); at least one bonding layer, being disposed between the interior surface(s) of the first and the second glass layers; wherein said first glass layer has a parameter TCf and the second glass layer has a parameter Tcs, according to wherein the difference between Tcs and TCf is more than or equal to 2 °C, and wherein said at least one printed area of the first glass layer has a flexural strength of at least 40 MPa at a probability of failure of 63.2% according to the normative standard DIN 1288 ring on ring test; and laminating said first and second glass layers with said at least one bonding layer.
17. The method of claim 16, wherein after the step of providing the first glass layer said first glass layer goes through the following step of thermal bending and curing of the glass enamel.
18. The method of any of claims 16 and 17, wherein the first glass layer has at least one area onto said internal surface that is printed with a glass enamel, and after the step of bending, the first glass layer is subjected to a chemical strengthening process.
19. The method of any of claims 16 to 18, wherein before the step of lamination, the second glass layer is thermally curved.
20. The method of any of claims 16 to 18, wherein during the step of lamination, the second glass layer is a flat layer and goes through cold-bending by conforming to the shape of the first glass layer.
PCT/IB2025/053917 2024-04-23 2025-04-15 Laminated glazing for a vehicle having improved mechanical resistance to impacts Pending WO2025224559A1 (en)

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US202463637824P 2024-04-23 2024-04-23
US63/637,824 2024-04-23

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023275806A1 (en) 2021-06-29 2023-01-05 Agp America S.A. Chemically strengthened laminate with obscuration and method of manufacture
US20230123130A1 (en) * 2021-10-14 2023-04-20 Schott Ag Glass panes or laminates having a coating on at least one side and pastes for producing such a coating
WO2023224799A1 (en) * 2022-05-18 2023-11-23 Corning Incorporated Decorative enamel for automotive glasses and associated methods

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023275806A1 (en) 2021-06-29 2023-01-05 Agp America S.A. Chemically strengthened laminate with obscuration and method of manufacture
US20230123130A1 (en) * 2021-10-14 2023-04-20 Schott Ag Glass panes or laminates having a coating on at least one side and pastes for producing such a coating
WO2023224799A1 (en) * 2022-05-18 2023-11-23 Corning Incorporated Decorative enamel for automotive glasses and associated methods

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