TWI649286B - Light-weight hybrid glass laminates - Google Patents

Abstract

A glass laminate comprises an outer glass sheet, an inner glass sheet and a polymeric intermediate layer formed between the outer glass sheet and the inner glass sheet. The outer glass sheet may be a thin chemically strengthened glass sheet or may be a chemically strengthened glass sheet, the polymer intermediate layer may have a thickness of less than 1.6 mm, and the inner glass sheet may be a chemically strengthened glass sheet. Or thin chemically strengthened glass sheets.

Description

Lightweight blended glass laminate [Reciprocal Reference Related Applications]

The present application claims the priority of U.S. Patent Application Serial No. 13/937,707 filed on Jul. 9, 2013, which is filed on Sep. Light-Weight Hybrid Glass Laminates, U.S. Patent No. 13/247,182, part of the continuation, co-pending application, and claiming the US patent non-provisional application, and the US patent is not a provisional application. The priority of US Patent Provisional Application No. 61/500,766, filed on June 24, 2011, is hereby incorporated by reference. The text of each of the above-identified applications is hereby incorporated by reference in its entirety in its entirety in its entirety in its entirety in its entirety.

The present invention relates generally to glass laminates, and more particularly to hybrid glass laminates comprising chemically strengthened outer glass panels and chemically strengthened inner glass panels. Such hybrid laminates are characterized by light weight, good sound-damping performance, and high impact resistance. In particular, the disclosed hybrid laminate meets commercially applicable impact test specifications for non-windshield applications.

Glass laminates can be used as windows and glazing for architectural and transportation applications, including automobiles, railway vehicles and aircraft. As used herein, a mosaic glass is a transparent or translucent portion of a wall or other structure. Common types of mosaic glass used in architectural and automotive applications include clear and colored glass, including laminated glass. A mosaic glass comprising a stack of opposing glass sheets separated by a plasticized polyvinyl butyral (PVB) sheet can be used, for example, for windows, windshield or sunroof. In certain applications, glass laminates with high mechanical strength and sound-attenuating properties are desirable to provide a safe barrier while reducing sound transmission from external sources.

In many vehicle applications, fuel savings depend on vehicle weight. Therefore, it is desirable to reduce the weight of the inlaid glass for such applications without compromising strength and sound insulation properties. In this regard, the glass laminate is advantageous in terms of mechanical strength to external impact events, such as intentive intrusion or contact with stones or hail; and the glass laminate can also appropriately eliminate internal impact events. The resulting energy (and fracture) is also advantageous, such as for example contact with a passenger during a collision. Furthermore, government regulations are increasingly requiring vehicles on the road to have higher fuel mileage and lower carbon dioxide emissions. Therefore, more and more efforts are focused on reducing the weight of these vehicles while maintaining current government and industrial safety standards. Non-glass window materials, such as polycarbonate, have been developed which reduce the weight of the vehicle but do not provide adequate resistance to environmental, debris and other considerations. However, embodiments of the present disclosure may provide substantial weight reduction, safety compliance, effective durability, and reduced tearing potential in vehicle crash events (laceration potential). In view of the above, a thin, lightweight mosaic glass that is more durable and has a sound absorbing characteristic relative to thicker, heavier mosaic glass is contemplated.

In accordance with one aspect of the invention, a glass laminate includes an outer glass sheet, an inner glass sheet, and a polymeric intermediate layer formed between the outer glass sheet and the inner glass sheet. In order to optimize the impact performance of the glass laminate, the outer glass sheet comprises chemically strengthened glass and may have a thickness of less than or equal to 1 mm, while the inner glass sheet comprises non-chemically strengthened glass and may have less than or equal to 2.5. The thickness of mm. In an embodiment, the polymeric intermediate layer (eg, polyvinyl butyral or PVB) may have a thickness of less than or equal to 1.6 mm. The disclosed hybrid glass laminate construction can advantageously react to impact and distribute stress. For example, the disclosed glass laminates are capable of providing superior impact resistance and blocking breakage in response to external impact events, and are capable of reacting to internal shock events to properly eliminate energy and cracking.

An unrestricted embodiment of the present disclosure provides a glass laminate structure having a chemically strengthened outer glass sheet, a chemically strengthened inner glass sheet, and at least one polymeric intermediate layer on the outer glass sheet and the inner glass sheet Between, wherein the inner glass sheet has a thickness ranging from about 0.5 mm to about 1.5 mm, and wherein the outer glass sheet has a thickness ranging from about 1.5 mm to about 3.0 mm.

Another non-limiting embodiment of the present disclosure provides a glass laminate structure having a chemically strengthened outer glass sheet, a chemically strengthened inner glass sheet, and at least one polymer intermediate layer in the outer glass sheet and Between the glass sheets, wherein the inner glass layer has a surface compressive stress of between about 250 MPa and about 900 MPa.

Additional features and advantages of the subject matter will be set forth in the description which follows. The features and advantages of the present invention are set forth in the Detailed Description, the claims and the claims.

It is to be understood that the foregoing general description of the embodiments of the present invention The drawings are included to provide a further understanding of the present disclosure, and such drawings are incorporated in and constitute a part of this specification. The drawings illustrate various embodiments and, together with the description,

10‧‧‧Laminated structure

12‧‧‧ outer layer

13‧‧‧ surface

14‧‧‧Intermediate

15‧‧‧ surface

16‧‧‧ inner layer

17‧‧‧ surface

19‧‧‧ Surface

100‧‧‧ glass laminate

110‧‧‧External glass

112‧‧‧External surface

114‧‧‧Internal surface

120‧‧‧Internal glass

122‧‧‧External surface

124‧‧‧Internal surface

130‧‧‧ polymer interlayer

200‧‧‧ glass laminate

The presently preferred forms are shown in the drawings for the purposes of illustration and description.

1 is a schematic diagram of an exemplary flat hybrid glass laminate in accordance with certain embodiments of the present disclosure.

2 is a schematic view of an exemplary bend-mixed glass laminate in accordance with other embodiments of the present disclosure.

3 is a schematic view of an exemplary bend-mixed glass laminate in accordance with a further embodiment of the present disclosure.

Figure 4 is an exemplary bend in accordance with additional embodiments of the present disclosure. A schematic view of a folded-in glass laminate.

In the following description, the same element symbols refer to the same or corresponding parts in the various views in the drawings. It should also be understood that, unless otherwise indicated, terms such as "top", "bottom", "outward", "inward" are used for convenience and should not be understood. For limiting terms. In addition, whenever a group is described as comprising at least one of the group of elements and combinations of elements, it is understood that the group can include any number of such elements (independently or in combination with each other), They consist of or consist of their elements.

Similarly, whenever a group is described as being composed of at least one of the group of elements or combinations of elements, it is understood that the group can be constructed by any number of the elements individually or in combination with each other. Ranges of values include both upper and lower limits of the range, unless stated otherwise. As used herein, the indefinite article "a", "an" and "the" "."

The following description of the disclosure is to be construed as merely illustrative of the invention It will be appreciated by those skilled in the art that many changes can be made to the embodiments described herein while still obtaining the beneficial results of the present disclosure. It is also apparent that certain desirable benefits of the present disclosure may be obtained by selecting certain features of the present disclosure without the use of other features. Therefore, the workers in the technical field of the present invention will recognize that there are many possible modifications and modifications to the present disclosure, and In some cases, these modifications and modifications are even desirable and should be part of the cost disclosure. Therefore, the following description is provided as an illustration of the subject matter of the disclosure, and is not a limitation of the disclosure.

It will be appreciated by those skilled in the art that many modifications of the exemplary embodiments described herein are possible without departing from the spirit and scope of the disclosure. Therefore, the description should not be construed as limited to the examples given herein, but the full breadth of protection provided by the scope of the accompanying claims and their equivalents. In addition, it is possible to use certain features of the present disclosure without the corresponding use of other features. Therefore, the following description of the exemplary or illustrative embodiments is provided for the purpose of the description of the disclosure, and is not intended to limit the scope of the disclosure.

The glass laminates disclosed herein are assembled to include an outer chemically strengthened glass sheet and an inner chemically strengthened glass sheet. As defined herein, when a glass laminate is used, the outer glass sheet will approach or contact the environment, while the inner glass sheet will approach or contact the structure of the glass laminate or the interior of the vehicle (eg, a car) (eg, ,cockpit).

An example glass laminate is shown in Figure 1. The glass laminate 100 includes an outer glass sheet 110, an inner glass sheet 120, and a polymer intermediate layer 130. The polymeric intermediate layer can be directly in physical contact (eg, laminated) to each of the respective outer and inner glass sheets. The outer glass sheet 110 has an outer surface 112 and an inner surface 114. By analogy, the inner glass sheet 120 has an outer surface 122 and an inner surface 124. As shown in the illustrated embodiment, the inner surface 114 of the outer glass sheet 110 and the inner surface 124 of the inner glass sheet 120 are individually in contact with the polymeric intermediate layer 130.

During use, it is desirable for the glass laminate to react to external shock events to resist cracking. However, in response to internal shock events, such as when the glass laminate is struck by a passenger of the vehicle, it is desirable for the glass laminate to retain passengers in the vehicle and still eliminate energy after impact to minimize injury. The ECE R43 head type test simulates an impact event occurring within a vehicle that is a routine test of a laminated mosaic glass fracture that requires a specific internal impact.

Without wishing to be bound by theory, when one panel of the glass sheet/polymer interlayer/glass sheet laminate is impacted, the opposing surfaces of the impacted sheet and the inner surface of the opposing sheet enter a state of tension. The calculated stress distribution of the glass/polymer interlayer/glass sheet laminate under the biaxial load shows that the tensile stress in the opposite surface of the impacted sheet may be equivalent to (or even slightly greater than) the low load. The magnitude of the tensile stress experienced at the outer surface of the opposing sheet at the loading rate. However, for high load rates (which are typically experienced in automotive applications), the amount of tensile stress at the outer surface of the opposing sheet may be much greater than the tensile stress at the opposite surface of the sheet being impacted. As disclosed herein, impact resistance to both external and internal impact events can be optimized by assembling the hybrid glass laminate with a chemically strengthened outer glass sheet and a chemically strengthened inner glass sheet.

Suitable internal glass sheets are non-chemically strengthened glass sheets such as soda-lime glass. The inner glass piece can be heat strengthened as the case may be. In embodiments where soda lime glass is used as the chemically strengthened glass sheet, conventional decorative materials and methods (e.g., glass frit crucible and screen printing) can be used, which simplifies the glass laminate manufacturing process. Tinted lime-lime glass flakes can be incorporated into the hybrid glass laminate to achieve electromagnetic spectrum Expected transmission and/or attenuation.

A suitable outer glass sheet can be chemically strengthened by an ion exchange process. In this process, ions at or near the surface of the glass sheet are typically exchanged with larger metal ions from the salt bath by dipping the glass sheet in the molten salt bath for a predetermined period of time. In one embodiment, the temperature of the molten salt bath is about 430 ° C and the predetermined time is about 8 hours. Incorporating larger ions into the glass strengthens the glass sheet by establishing compressive stress in the vicinity of the surface area. The corresponding tensile stress is induced in the central region of the glass while the compressive stress is balanced. An exemplary ion exchangeable glass suitable for use in forming a hybrid glass laminate is an alkali aluminosilicate glass or an alkali aluminoborosilicate glass, although other glass compositions are contemplated. As used herein, "ion exchangeable" means that the glass is capable of exchanging cations at or near the surface of the glass with larger or smaller cations of a larger size. An exemplary glass composition comprises SiO ₂ , B ₂ O ₃ and Na ₂ O, wherein (SiO ₂ + B ₂ O ₃ ) 66 mol.%, and Na ₂ O 9 mol.%. In an embodiment, the glass sheet comprises at least 6 wt.% alumina. In a further embodiment, the glass flakes comprise one or more alkaline earth oxides such that the alkaline earth oxide is present in an amount of at least 5 wt.%. In certain embodiments, a suitable glass composition further comprises at least one of K ₂ O, MgO, and CaO. In a particular embodiment, the glass may comprise 61 to 75 mol.% SiO ₂ ; 7 to 15 mol.% Al ₂ O ₃ ; 0 to 12 mol.% B ₂ O ₃ ; 9 to 21 mol.% Na ₂ O 0 to 4 mol.% of K ₂ O; 0 to 7 mol.% of MgO; and 0 to 3 mol.% of CaO.

A further exemplary glass composition suitable for use in forming a hybrid glass laminate may comprise: 60 to 70 mol.% SiO ₂ ; 6 to 14 mol.% Al ₂ O ₃ ; 0 to 15 mol.% B ₂ O ₃ ; To 15 mol.% of Li ₂ O; 0 to 20 mol.% of Na ₂ O; 0 to 10 mol.% of K ₂ O; 0 to 8 mol.% of MgO; 0 to 10 mol.% of CaO; 0 to 5 mol.% ZrO ₂ ; 0 to 1 mol.% of SnO ₂ ; 0 to 1 mol.% of CeO ₂ ; less than 50 ppm of As ₂ O ₃ ; and less than 50 ppm of Sb ₂ O ₃ ; 12 mol.% (Li ₂ O+Na ₂ O+K ₂ O) 20 mol.%, and 0 mol.% (MgO+CaO) 10 mol.%.

Still further example glass compositions may comprise: 63.5 to 66.5 mol.% SiO ₂ ; 8 to 12 mol.% Al ₂ O ₃ ; 0 to 3 mol.% B ₂ O ₃ ; 0 to 5 mol.% Li ₂ O; 8 to 18 mol.% of Na ₂ O; 0 to 5 mol.% of K ₂ O; 1 to 7 mol.% of MgO; 0 to 2.5 mol.% of CaO; 0 to 3 mol.% of ZrO ₂ ; 0.25 mol.% of SnO ₂ ; 0.05 to 0.5 mol.% of CeO ₂ ; less than 50 ppm of As ₂ O ₃ ; and less than 50 ppm of Sb ₂ O ₃ ; 14 mol.% (Li ₂ O+Na ₂ O+K ₂ O) 18 mol.%, and 2 mol.% (MgO+CaO) 7 mol.%.

In a particular embodiment, the alkali aluminosilicate glass may comprise alumina, at least one alkali metal, and in certain embodiments further comprises greater than 50 mol.% SiO ₂ , and in other embodiments at least 58 mol. % SiO ₂ , and in still other embodiments further comprising at least 60 mol.% SiO ₂ , wherein the ratio Wherein the components in the ratio are expressed in mol.% and the modifiers are alkali metal oxides. In a particular embodiment, the glass may comprise (or consist essentially of, or consist of: 58 to 72 mol.% of SiO ₂ ; 9 to 17 mol.% of Al ₂ O ₃ ; 2 to 12 moles) .% of B ₂ O ₃ ; 8 to 16 mol.% of Na ₂ O; and 0 to 4 mol.% of K ₂ O, wherein ratio

In another embodiment, the alkali aluminosilicate glass may comprise (or consist essentially of, or consist of) 61 to 75 mol.% SiO ₂ ; 7 to 15 mol.% Al ₂ O ₃ 0 to 12 mol.% of B ₂ O ₃ ; 9 to 21 mol.% of Na ₂ O; 0 to 4 mol.% of K ₂ O; 0 to 7 mol.% of MgO; and 0 to 3 mol.% of CaO.

In still another embodiment, the alkali aluminosilicate glass substrate may comprise (or consist essentially of, or consist of of: 60 to 70 mol.% of SiO ₂ ; 6 to 14 mol.% of Al ₂ O) ₃ ; 0 to 15 mol.% of B ₂ O ₃ ; 0 to 15 mol.% of Li ₂ O; 0 to 20 mol.% of Na ₂ O; 0 to 10 mol.% of K ₂ O; 0 to 8 mol.% of MgO 0 to 10 mol.% of CaO; 0 to 5 mol.% of ZrO ₂ ; 0 to 1 mol.% of SnO ₂ ; 0 to 1 mol.% of CeO ₂ ; less than 50 ppm of As ₂ O ₃ ; and less than 50 ppm Sb ₂ O ₃ ; 12 mol.% Li ₂ O+Na ₂ O+K ₂ O 20 mol.%, and 0 mol.% MgO+CaO 10 mol.%.

In still another embodiment, the alkali aluminosilicate glass may comprise (or consist essentially of, or consist of) 64 to 68 mol.% SiO ₂ ; 12 to 16 mol.% Na ₂ O; 8 to 12 mol.% of Al ₂ O ₃ ; 0 to 3 mol.% of B ₂ O ₃ ; 2 to 5 mol.% of K ₂ O; 4 to 6 mol.% of MgO; and 0 to 5 mol.% of CaO, wherein : 66mol.% SiO ₂ +B ₂ O ₃ +CaO 69 mol.%; Na ₂ O+K ₂ O+B ₂ O ₃ +MgO+CaO+SrO>10 mol.%; 5 mol.% MgO+CaO+SrO 8 mol.%; (Na ₂ O+B ₂ O ₃ )-Al ₂ O ₃ 2 mol.%; 2 mol.% Na ₂ O-Al ₂ O ₃ 6 mol.%; and 4 mol.% (Na ₂ O+K ₂ O)-Al ₂ O ₃ 10 mol.%.

In certain embodiments, the chemically strengthened glass and the chemically strengthened glass may be treated in batches with from 0 to 2 mol.% of at least one fining agent selected from the group consisting of Na ₂ SO ₄ , NaCl, NaF, NaBr, K _{2 .} A group of SO ₄ , KCl, KF, KBr, and SnO ₂ .

In an exemplary embodiment, the sodium ions in the chemically strengthened glass can be replaced by potassium ions from the molten bath, whereas other alkali metal ions (such as ruthenium or osmium) having a larger atomic radius can replace the glass. Small alkali metal ions. According to a particular embodiment, the smaller alkali metal ions in the glass can be replaced by Ag ⁺ ions. Similarly, other alkali metal salts (such as, but not limited to, sulfates, halides, and the like) can be used in the ion exchange process.

The substitution of larger ions for smaller ions below the relaxation temperature of the glass network creates an ion distribution across the surface of the glass, resulting in a stress profile. The larger volume of incoming ions creates compressive stress (CS) on the glass surface and creates tension (central tension, or CT) at the center of the glass. The compressive stress is related to the central tension, which is expressed in the following relationship: Where t is the total thickness of the glass sheet and DOL is the exchange depth, also known as the layer depth.

According to various embodiments, a hybrid glass laminate comprising ion exchange glass possesses a range of desirable properties including light weight, high impact resistance, and improved sound attenuation.

In one embodiment, the chemically strengthened glass sheet may have a surface compressive stress of at least 300 MPa (eg, at least 400, 450, 500, 550, 600, 650, 700, 750 or 800 MPa), a layer depth of at least about 20 μm (eg, at least about 20, 25, 30, 35, 40, 45, or 50 μm), and/or greater than 40 MPa (eg, greater than 40, 45, or 50 MPa) ) but below the center tension of 100 MPa (eg below 100, 95, 90, 85, 80, 75, 70, 65, 60 or 55 MPa).

The chemically strengthened glass sheet may have an elastic modulus ranging from about 60 GPa to 85 GPa (e.g., 60, 65, 70, 75, 80 or 85 GPa). The modulus of elasticity of the glass sheet and the polymeric intermediate layer can affect both the mechanical properties (e.g., deflection and strength) and acoustic performance (e.g., transmission loss) of the resulting glass laminate.

Exemplary glass sheet forming methods include a fusion draw and a slot draw process, both of which are examples of a down-draw process that also includes a float process. These methods can be used to form both chemically strengthened glass and chemically strengthened glass sheets. The fusion and drag process uses a traction channel with channels for receiving molten glass raw materials. The channel has a helium that is on either side of the channel and opens at the top along the long side of the channel. When the channel is filled with molten material, the molten glass overflows through the crucible. Due to gravity, the molten glass flows down the outer surface of the traction groove. These outer side surfaces extend downwardly and inwardly such that the outer side surfaces meet at the edges below the drag grooves. The two flowing glass surfaces meet at this edge to fuse and form a single flow sheet. The fusion-drawing method provides the advantage that the outer surfaces of the resulting glass sheets are not in contact with any of the components of the apparatus since the two glass films flowing over the channels are fused together. Therefore, the surface properties of the fused traction glass sheet are not affected by such contact. influences.

The slot traction method is different from the fusion traction method. Here, the molten raw material glass is supplied to the drawing groove. The bottom of the traction trough has an open slot with a nozzle that extends the length of the slot. The molten glass flows through the slots/nozzles and is drawn down into a continuous sheet and into the annealing zone. The slot-drawing process provides a sheet that is thinner than the fusion-drawing process because only a single sheet is drawn through the slot rather than the two sheets that are fused together.

The down-draw process produces glass sheets of uniform thickness with relatively pure surfaces. Since the strength of the glass surface is controlled by the amount and size of surface defects, a clean surface with extremely low contact has a high initial strength. When this high strength glass is subsequently chemically strengthened, the resulting strength will be higher than the strength of the polished and polished surface. The downwardly drawn glass can be drawn to a thickness of less than about 2 mm. In addition, the downwardly drawn glass has a very flat and smooth surface that can be used for its end use without the need for costly grinding and polishing.

In the floating glass process, a glass sheet characterized by a smooth surface and a uniform thickness is produced by floating molten glass on a bed of molten metal (generally tin). In the exemplary process, the molten glass fed to the surface of the molten tin bed forms a floating ribbon. As the glass ribbon flows along the tin bath, the temperature gradually decreases until the solid glass slides from the tin to the roller. Once exiting the bath, the glass sheets can be further cooled and annealed to reduce internal stresses.

Glass flakes can be used to form the glass laminate. As defined herein, a hybrid glass laminate comprises an outwardly facing chemically strengthened glass sheet, an inwardly facing chemically strengthened glass sheet, and a polymer formed between the glass sheets. Floor. The polymeric intermediate layer can comprise a monolithic polymer sheet, a multilayer polymeric sheet or a composite polymeric sheet. The polymeric intermediate layer can be, for example, a plasticized polyvinyl butyral sheet.

The glass laminate can be adapted to provide light penetrating barriers in buildings and automotive openings, such as mosaic glass for automobiles. Glass laminates can be formed using a variety of processes. In an exemplary embodiment, the assembly involves laying a first glass sheet, placing a polymeric intermediate layer (such as a PVB sheet), laying a second glass sheet, and then trimming excess PVB for the edge of the glass sheet. The step of tackling can then include the steps of dissipating most of the air from the interface and partially bonding the PVB to the glass sheet. The finishing step is typically performed at elevated temperatures and pressures which complete the bonding of the glass sheets to the polymeric intermediate layer. In the above embodiments, the first sheet may be a chemically strengthened glass sheet, and the second sheet may be a chemically strengthened glass sheet, or may be reversed from this configuration.

A thermoplastic material such as PVB can be applied as a preformed polymeric intermediate layer. In certain embodiments, the thermoplastic layer can have a thickness of at least 0.125 mm (eg, 0.125, 0.25, 0.38, 0.5, 0.7, 0.76, 0.81, 1, 1.14, 1.19, or 1.2 mm). The thermoplastic layer can have a thickness of less than or equal to 1.6 mm (eg, from 0.4 to 1.2 mm, such as about 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, or 1.2 mm). The thermoplastic layer can cover substantially (or preferably) substantially all of the two opposing glass major faces. The thermoplastic layer also covers the edge faces of the glass. The glass sheets in contact with the thermoplastic layer can be heated above the thermoplastic softening point, for example at least 5 ° C or 10 ° C above the softening point to promote adhesion of the thermoplastic material to the respective glass sheets. This heating step can be performed under pressure with the glass contacting the thermoplastic layer.

Selected commercial polymer interlayer materials are summarized in Table 1, which also provides the glass transition temperature and modulus for each product sample. The glass transition temperature and modulus are determined from the technical data sheet obtained by the vendor or by using the DSC 200 differential scanning calorimeter (Seiko Instruments Corp., Japan) or for glass conversion and modulus data. The ASTM D638 method is determined. A further description of an acrylic/silicone resin material for use in an ISD resin is disclosed in U.S. Patent No. 5,624,763, the disclosure of which is incorporated herein by reference. This article.

One or more polymeric intermediate layers can be incorporated into the hybrid glass laminate. A plurality of intermediate layers can provide complementary or distinct functionality including adhesion promotion, acoustic control, control of UV transmission, tinting, coloration, and/or IR transmission control.

The polymeric intermediate layer may have an elastic modulus ranging from about 1 MPa to 75 MPa (eg, about 1, 2, 5, 10, 15, 20, 25, 50, or 75 MPa). The elastic modulus of the standard PVB intermediate layer may be about 15 MPa at a load rate of 1 Hz, and the acoustic modulus of the acoustic grade PVB intermediate layer may be about 2 MPa.

During the lamination process, the intermediate layer is typically heated to a temperature effective to soften the intermediate layer, which promotes the intermediate layer to conformally engage the various surfaces of the glass sheet. For PVB, the lamination temperature can be about 140 °C. The movable polymer chain in the intermediate layer material develops adhesion to the surface of the glass to promote adhesion. The elevated temperature also accelerates the diffusion of residual air and/or moisture from the glass polymer interface.

The application of pressure promotes both the flow of the intermediate layer material and the formation of bubbles which can be additionally induced by the combined vapor pressure of air and water captured at the interface. In order to suppress bubble formation, heat and pressure are simultaneously applied to the assembly in an autoclave.

Hybrid glass laminates can provide advantageous benefits including attenuating noise, reducing UV and/or IR light transmission, and/or enhancing the aesthetic appeal of the window. The individual glass sheets constituting the disclosed glass laminate and the resulting laminate may be characterized by one or more characteristics including composition, density, Thickness, surface weights, and various properties including optical properties, sound absorbing properties, and mechanical properties, while mechanical properties such as impact resistance. Various aspects of the disclosed hybrid glass laminate are described herein.

The hybrid glass laminate can be adapted for use as, for example, a window or mosaic glass, and the hybrid glass laminate can be assembled into any suitable size and dimension. In some embodiments, the glass laminate has a length and width (eg, 0.1, 0.2, 0.5, 1, 2, or 5 m) that varies independently from 10 cm to 1 m or more. The glass laminate may independently have an area greater than 0.1 m ² , such as greater than 0.1, 0.2, 0.5, 1, ² , 5, 10 or 25 m ² .

The glass laminate can be substantially flat or shaped for use in certain applications. For example, the glass laminate can be formed into a bent or shaped component for use with a windshield or cover plate. The structure of the shaped glass laminate can be simple or complex. In some embodiments, the shaped glass laminate can have a complex curvature wherein the glass sheets have distinct radii of curvature in two separate directions. It is thus possible to characterize such a shaped glass sheet with "cross curvature" which is curved along an axis parallel to a given dimension and also curved along an axis perpendicular to the same dimension. For example, a typical automotive sunroof has a specification of 0.5 m times 1.0 m and has a radius of curvature of 2 to 2.5 m along the minor axis and a radius of curvature of 4 to 5 m along the long axis.

A shaped glass laminate in accordance with certain embodiments may be defined by a bending factor, wherein the bending factor for a given component is equal to the radius of curvature along a given axis divided by the length of the axis. Therefore, for an exemplary car sunroof with a radius of curvature of 2 m and 4 m on each axis of 0.5 m and 1.0 m, along each The bending factor of the shaft is 4. The shaped glass laminate can have a bending factor ranging from 2 to 8, such as 2, 3, 4, 5, 6, 7, or 8.

An exemplary patterned glass laminate 200 is shown in FIG. The patterned laminate 200 comprises an outer (chemically strengthened) glass sheet 110 formed at the bulging surface of the laminate, while an inner (no chemically strengthened) glass sheet 120 is formed On the concave surface of the laminate. However, it will be appreciated that the embossed surface of the embodiment not shown may comprise a chemically strengthened glass sheet, while the opposing concave surface may comprise a chemically strengthened glass sheet.

Figure 3 is a cross-sectional illustration of a further embodiment of the present disclosure. Figure 4 is a perspective view of an additional embodiment of the present disclosure. Referring to Figures 3 and 4, and as discussed in the preceding paragraphs, the example laminate structure 10 can include an inner layer 16 of chemically strengthened glass (e.g., Gorilla® Glass). This inner layer 16 may have been subjected to heat treatment, ion exchange and/or annealing. The outer layer 12 can be a chemically strengthened glass sheet such as conventional soda lime glass, annealed glass, and the like. The laminate 10 can also include a polymeric intermediate layer 14 positioned between the outer glass layer and the inner glass layer. The inner glass layer 16 can have a thickness of less than or equal to 1.0 mm and have a residual surface CS level between about 250 MPa and about 350 MPa, and a DOL greater than 60 microns. In another embodiment, the inner layer 16 preferably has a CS level of about 300 MPa. In one embodiment, the intermediate layer 14 can have a thickness of approximately 0.8 mm. Exemplary intermediate layer 14 can include, but is not limited to, polyvinyl butyral or other suitable polymeric materials as described herein. In additional embodiments, any surface of outer layer 12 and/or inner layer 16 may be acid etched to enhance durability against external impact events. For example, in one embodiment, the first surface 13 of the outer layer 12 may be acid etched and/or the other surface of the inner layer 17 Can be etched by acid. In another embodiment, the first surface 15 of the outer layer may be acid etched and/or the other surface 19 of the inner layer may be acid etched. Such an embodiment thus provides a laminate construction that is substantially lighter in construction than conventional laminates and meets the specifications for impact requirements. Exemplary thicknesses of outer layer 12 and/or inner layer 16 may range from 0.5 mm to 1.5 mm to 2.0 mm or more.

In a preferred embodiment, the thin chemically strengthened inner layer 16 can have a surface stress between about 250 MPa and 900 MPa, and can have a thickness ranging from 0.5 to 1.0 mm. In this embodiment, the outer layer 12 can be an annealed (non-chemically strengthened) glass having a thickness from about 1.5 mm to about 3.0 mm or greater. Of course, outer layer 12 and inner layer 16 can have different thicknesses in individual laminate structures 10. Another preferred embodiment of the exemplary laminate structure can include a 0.7 mm inner layer of chemically strengthened glass, a polyvinyl butyral layer having a thickness of about 0.76 mm, and an outer layer of an annealed glass of 2.1 mm.

The exemplified glass layer can be made by fusion splicing, as outlined above, or as described in U.S. Patent Nos. 7,666,511, 4,483,700, and 5,674,790, each of which is incorporated herein by reference. These tempered glasses are then chemically strengthened. An example chemically strengthened glass layer can thus have a deep DOL of CS and can exhibit high flexural strength, scratch resistance, and impact resistance. Exemplary embodiments may also include acid etched or flashed surfaces to increase impact resistance and increase the strength of such surfaces by reducing the size and severity of defects on these surfaces. If the etch occurs immediately prior to lamination, the strengthening benefits of the etch or flash process can be maintained on the surface bonded to the intermediate layer.

One embodiment of the present disclosure provides an exemplary glass laminate structure having a chemically strengthened inner glass sheet, a chemically strengthened inner glass sheet, and at least one polymeric intermediate layer that is externally Between the glass piece and the inner glass piece. The polymeric intermediate layer can be a single polymer sheet, a multilayer polymer sheet or a composite polymer sheet. Further, the polymer intermediate layer may include, for example, but not limited to, PVB, polycarbonate, acoustic PVB, ethylene vinyl acetate (EVA), thermoplastic polyurethane (TPU), ions. A material such as an ionomer, a thermoplastic material, and a combination of the foregoing materials. The inner glass sheet can have a thickness ranging from about 0.5 mm to about 1.5 mm, and the outer glass sheet can have a thickness ranging from about 1.5 mm to about 3.0 mm. In other embodiments, the inner glass sheet can have a thickness of between about 0.5 mm to about 0.7 mm, the polymeric intermediate layer can have a thickness of between about 0.4 to about 1.2 mm, and/or the outer glass sheet. It may have a thickness of about 2.1 mm. In another embodiment, the inner glass sheet can include one or more alkaline earth oxides such that the alkaline earth oxide is present in an amount of at least about 5 wt.%. The inner glass sheet can also include at least about 6 wt.% alumina. In additional embodiments, the outer glass sheet comprises, but is not limited to, a material such as soda lime glass and annealed glass. The example laminate can have an area greater than 1 m ² and can be utilized as a windshield, sunroof or cover sheet for a car. In a further embodiment, the inner glass layer can have a surface compressive stress between about 250 MPa and about 900 MPa, or in another embodiment, a surface compressive stress between about 250 MPa and about 350 MPa, and greater than DOL of compressive stress of about 20 μm. Certain embodiments may acid etch any number of glass sheet surfaces or acid etch any portion of the glass sheet surface.

Another embodiment of the present disclosure provides a glass laminate junction Having a chemically strengthened inner glass sheet, a chemically strengthened inner glass sheet, and at least one polymer intermediate layer between the outer glass sheet and the inner glass sheet, wherein the inner glass layer has A surface compressive stress between about 250 MPa and about 900 MPa. In an additional embodiment, the inner glass layer can have a surface compressive stress between about 250 MPa and about 350 MPa, and a DOL greater than about 20 [mu]m compressive stress. Exemplary thicknesses of the inner glass sheet can range from about 0.5 mm to about 1.5 mm, and the thickness of the outer glass sheet can range from about 1.5 mm to about 3.0 mm. Exemplary polymeric interlayers may be comprised of, but are not limited to, PVB, polycarbonate, acoustic PVB, EVA, TPU, ionomer, thermoplastic materials, and combinations of the foregoing, and/or may have A thickness of between about 0.4 and about 1.2 mm.

Accordingly, embodiments of the present disclosure can provide a means to reduce the weight of automotive mosaic glass while maintaining optical and security requirements by using thinner glass materials. Conventional laminated windshields can account for 62% of the total mosaic glass weight; however, by utilizing a 0.7-mm thick chemically strengthened inner layer plus a 2.1-mm thick chemically strengthened outer layer, for example, It can reduce the weight of the windshield by 33%. Further, it has been found that the use of a 1.6-mm thick chemically strengthened outer layer plus a 0.7-mm thick chemically strengthened inner layer results in a total weight savings of 45%. Thus, the use of an exemplary laminate structure in accordance with an embodiment of the present disclosure allows the laminated windshield to pass all institutional safety requirements, including resistance to internal penetration and external objects, and appropriate bending energy can be generated Accepted Head Impact Criteria (HIC) values. In addition, the exemplary outer layer composed of annealed glass provides an acceptable pattern of cracking (caused by impact from external objects) and causes breakage or cracking in the event of impact. At the same time, there is still continuous visibility through the windshield. Studies have also shown that the use of chemically strengthened glass as the inner surface of an asymmetric windshield provides additional benefits: a lower tear than the possibility of tearing due to passenger impacted annealed windshields possibility.

Methods for bending and/or modeling glass laminates can include gravity bending, compression against bending, and methods of blending of the foregoing. In a conventional method of bending a thin and flat glass sheet into a curved shape such as a windshield of a car, the cold and pre-cut single or multiple sheets of glass are placed in a rigid, pre-formed bending fixture. The perimeter is supported on the surface. The bending jig can be made by using metal or refractory material. In an exemplary method, an articulating bending fixture can be used. Before bending, the glass is generally supported only at some points of contact. The glass is typically heated by exposing the glass to a high temperature in a lehr to soften the glass such that gravity sag or slump the glass to conform to the peripheral support surface. Substantially the entire support surface will then substantially contact the perimeter of the glass.

A related art is compression bending in which a single flat glass sheet is heated to a temperature substantially corresponding to the softening point of the glass. The heated sheet is then pressed or shaped to a desired curvature between the male and female molded members having complementary contoured surfaces. The molded component molding surfaces may include vacuum or air jet columns to engage the glass sheets. In various embodiments, the contoured surface can be assembled to substantially contact the entire corresponding glass surface. Alternatively, one or both of the opposing styling surfaces may contact the respective glass surface on discrete areas or contact the respective glass surface at discrete contact points. For example, the master molding surface can be an annular surface. In various embodiments, a combination of gravity bending and compression bending techniques can be used.

The total thickness of the glass laminate may range from about 2 mm to 5 mm, wherein the outer and/or inner chemically strengthened glass sheets may have a thickness of 1 mm or less (eg, from 0.5 to 1 mm, such as 0.5, 0.6, 0.7, 0.8, 0.9 or 1mm). Further, the inner and/or outer chemically strengthened glass sheet may have a thickness of 2.5 mm or less (for example, from 1 to 2 mm, such as 1, 1.5, 2, or 2.5 mm). In various embodiments, the total thickness of the glass sheets in the glass laminate is less than 3.5 mm (eg, less than 3.5, 3, 2.5, or 2.3 mm).

Exemplary glass laminate structures are illustrated in Table 2, wherein the abbreviation GG refers to a chemically strengthened aluminosilicate glass sheet, the term "glass" refers to a chemically strengthened soda lime (SL) glass sheet, and PVB refers to polyethylene. Alcohol butyral, PVB can be regarded as acoustic grade PVB (A-PVB).

Applicants have shown that the glass laminate structures disclosed herein have excellent durability, impact resistance, toughness, and scratch resistance. As is known to those skilled in the art, the strength and mechanical impact effectiveness of glass sheets or laminates is limited by defects in the glass, including both surface and internal defects. When the glass laminate is impacted, the impact point is in a compressed state, and the ring or hoop around the impact point and the opposite side of the impacted sheet are in a stretched state. In general, the origin of the failure will be at the sputum (usually on the glass surface), or at or near the highest tension point. This can happen on the opposite side, but it can happen inside the ring. If the crucible in the glass is in a stretched state during an impact event, the crucible will likely propagate and the glass will generally break. Thus, a high compressive stress magnitude and a deep compressive stress depth (layer depth) are preferred.

One or both of the surfaces of the chemically strengthened glass sheets used in the disclosed hybrid glass laminate are in a compressed state due to chemical strengthening. The incorporation of compressive stress in the near surface area of the glass can inhibit crack propagation and breakage of the glass sheet. The tensile stress from the impact must exceed the surface compressive stress at the tip of the crucible to allow the propagation and breakage of the crucible. In various embodiments, the high compressive stress of the chemically strengthened glass sheet and the deep layer depth enable the use of thinner glass than in the absence of chemically strengthened glass.

In the case of a hybrid glass laminate, the laminate structure of the hybrid glass laminate can be in the event of a reaction mechanical shock compared to a thicker monolithic chemically strengthened glass or a thicker chemically strengthened glass laminate. Further deflection without breakage. This increased deflection allows more energy to be delivered to the intermediate layer of the laminate, which reduces the energy reaching the opposite side of the glass. therefore, The hybrid glass laminates disclosed herein are capable of withstanding higher impact energy than monolithic non-chemically strengthened glass or chemically strengthened glass laminates of similar thickness.

In addition to the mechanical properties of the laminate structure, those skilled in the art will appreciate that the laminate structure can be used to attenuate sound waves. The hybrid glass laminates disclosed herein can substantially reduce sound transmission while using thinner (and lighter) structures that also possess the desired mechanical properties of many inlaid glass applications.

The acoustic performance of laminates and mosaic glass is typically impacted by the flexural vibration of the mosaic glass structure. Without wishing to be bound by theory, the human response to sound is typically between 500 Hz and 5000 Hz, corresponding to a wavelength of about 0.1 to 1 m in air and a wavelength of 1 to 10 m in the glass. For a mosaic glass structure having a thickness of less than 0.01 m (<10 mm), the transmission mainly occurs through the bending vibration of the vibration and the acoustically coupled mosaic glass. The laminated mosaic glass structure can be designed to convert energy from the inlaid glass bending mode into shear strain in the polymer intermediate layer. In glass laminates using thinner glass sheets, the greater compliance of the thinner glass allows for greater vibrational amplitudes, which in turn can impart greater shear strain to the intermediate layer. The low shear resistance of most viscoelastic polymer interlayer materials means that the intermediate layer will promote attenuation through high shear strain, and high shear strain will be converted into heat under the influence of molecular chain slip and relaxation.

In addition to the thickness of the glass laminate, the nature of the glass sheet comprising the laminate may also affect the sound absorbing properties. For example, if there is a slight but significant difference between the chemically strengthened glass sheet and the chemically strengthened glass sheet at the interface between the glass and the polymer interlayer, this difference helps the higher shear in the polymer layer. change. Similarly, in addition to the obvious compositional differences between aluminosilicate glass and soda lime glass, aluminosilicate glass and soda lime glass have different physical and mechanical properties, including modulus, Poisson's ratio, density. Etc. These properties can cause different acoustic responses.

example

Glass and ceramic material strengths have been measured using conventional biaxial strength tests (eg, three or four point bend tests). However, because the measured intensity depends on the edge effect and on the monolithic material, interpretation of the biaxial strength test results can be challenging.

On the other hand, the biaxial bending test can be used to provide strength assessment without regard to edge induced phenomena. In the biaxial bending test, the glass laminate was supported near the periphery of the glass laminate and at three or more points equidistant from the center of the glass laminate, and then the laminate was loaded in a central position. The position of the maximum tensile stress thus occurs at the center of the surface of the laminate, and it is advantageous that the position is independent of the edge condition.

An exemplary flat hybrid glass laminate was subjected to a standardized biaxial bending test (ECE R43 headform, as detailed in Annex 7/3). As explained further below, when the glass laminate of the present invention (Sample 1) was subjected to impact on the side without chemical strengthening (soda lime), the two glass sheets were broken. However, when the sample 1 glass laminate was impacted on the chemically strengthened side, in 50% of the tested samples, the chemically strengthened glass flakes broke but the chemically strengthened glass flakes remained intact.

In one test, the internal (no chemically strengthened) glass piece 120 was subjected to a high load rate impact. Upon reaction, the interior surface 124 of the inner glass sheet 120 The outer surface 112 of the outer glass sheet 110 is in a stretched state. When the amount of tensile stress on the outer surface 112 is greater than the tensile stress at the inner surface 124, in this assembled form, a moderate tensile stress on the inner surface 124 is sufficient to rupture the chemically strengthened glass sheet 120, and The increased tensile stress on the outer surface 112 is sufficient to also rupture the chemically strengthened glass sheet 110. When the glass piece breaks, the PVB intermediate layer deforms but does not allow the head impact device to penetrate the glass laminate. This is a satisfactory response under the ECE R43 head requirement.

In the related test, the external (chemically strengthened) glass sheet 110 was instead impacted. Upon reaction, the inner surface 114 of the outer glass sheet 110 experiences a moderate tensile stress while the outer surface 122 of the inner glass sheet 120 experiences a higher magnitude of stress. In this assembly, the elevated stress on the outer surface 122 of the internally chemically strengthened glass sheet 120 initiates cracking of the chemically strengthened glass sheet. However, moderate tensile stress on the inner surface 114 of the outer glass sheet 110 may not be sufficient to overcome the ion exchange induced compressive stress in the near surface area of the chemically strengthened glass. In the laboratory experiments, only two of the six tested samples had high load rate impacts causing the chemically strengthened glass sheet 110 to break. Of the remaining four samples, no chemically strengthened glass sheet 120 broke but the chemically strengthened glass sheet 110 remained intact. All of the samples of the present invention exceed the impact requirements of non-windshields proposed by the ECE R43 head type requirements.

Comparative samples A and B were also subjected to a biaxial bending test. Comparative Sample A contained a symmetric configuration of a 1 mm chemically strengthened glass sheet / 0.76 mm standard PVB / 1 mm chemically strengthened glass sheet, which showed no breakage and thus failed to meet the need for ECE R43 to break the glass laminate.

Comparative sample B contains 1.5mm soda lime glass / 0.76mm Symmetrical construction of standard PVB/1.5mm soda lime glass sheets. In the results of the biaxial bending test, the two glass sheets were broken, and thus Comparative Sample B passed the ECE R43 standard (Annex 7/3). However, no matter which glass sheet is impacted, the two glass sheets in the comparative sample B glass laminate are broken, so that it is impossible to provide a firm mechanical resistance to external impact, and the stable mechanical resistance described herein is in the hybrid laminate. Realized in the matter. It is also noted that during testing, the recoil (i.e., bounce) of the head shape is greater than sample 1 in the comparative sample B, which implies that the comparative configuration does not effectively eliminate energy as in the example of the present invention.

Head Impact Index (HIC) is a well-known metric that can be used to assess the safety of glass laminates. The HIC value is dimensionless and can be correlated with the likelihood of injury from impact. For internal shock events, a lower HIC value is desired.

For an exemplary flat hybrid glass laminate, the average HIC value for the impact on the chemical-free side of the 1.6 mm SL/0.8 mm A-PVB/0.7 mm GG stack is 175, while for 0.7 mm GG/0.8 mm A- The average HIC value of the chemically strengthened side impact of the PVB/1.6 mm SL stack was 381. For automotive mosaic glass applications, it is advantageous to have an average HIC value for the impact on the chemically strengthened (outer) side that is higher than the average HIC value for the impact without the chemically strengthened side. For example, the chemically enhanced side HIC value can be greater than or equal to 400 (eg, greater than or equal to 400, 450, or 500), while the chemically enhanced side HIC value can be less than or equal to 400 (eg, less than or equal to 400, 350, 300, 250, 200, 150 or 100) such that the HIC value on the chemically strengthened side is at least 50 greater than the value on the non-chemically strengthened side (eg, at least 50, 100, 150 or 200).

Although this description may include many specific examples, these specific examples should not be The description of the scope of the invention is to be construed as a description of the features of the particular embodiments. Some of the features described so far in the individual embodiments of the foregoing are also combinable and implemented in a single embodiment. Conversely, many of the features described in the context of a single embodiment can be implemented independently in various embodiments or in any suitable sub-combination. Also, although features may be described above as acting in a particular combination, and even initially claimed, in some instances, one or more features from the claimed combination may depart from the combination and claimed The combination can be directed to the deformation of the sub-combination or sub-combination.

Similarly, although the operation of the present invention is depicted in a particular order in the drawings or drawings, this should not be understood that these operations must be performed in the specific order or sequence shown, and should not be construed as necessarily The operation to achieve the desired result. In some cases, multiplex and parallel processing may be advantageous.

Ranges may be expressed herein as "about" a particular value and/or to "about" another particular value. When such a range is expressed, a plurality of examples include from the one particular value and/or to the other particular value. Similarly, when a plurality of numerical values are expressed as approximations by using the antecedent "about", it should be understood that the particular value may form another embodiment. It will be further appreciated that the endpoints of each of the ranges are obviously associated with the other endpoint and are independent of the other endpoint.

It should also be noted that the description herein means that the components of the disclosure are "configured" or "adapted to" in a particular manner. In this regard, such components are "assembled" or "adapted" to perform a particular property, or act in a specific manner, and such description is a structural description in contrast to the description of the intended use. In more detail, in this article, the component is "packed" The reference object of the means of "forming" or "fitting" the component is to mark the existing physical condition of the component, and in this regard, the definition of the structural feature of the component is clearly stated.

A variety of lightweight hybrid glass laminates have been described by the various configurations and embodiments illustrated in the drawings.

Although the preferred embodiment of the present disclosure has been described, it is understood that the described embodiments are merely illustrative and that the scope of the invention should be defined solely by the scope of the accompanying claims. In general, many variations and modifications occur naturally when the overall range of equivalents is met.

Claims (20)

A glass laminate structure comprising: a chemically strengthened outer glass sheet; a chemically strengthened inner glass sheet; and at least one polymeric intermediate layer between the outer glass sheet and the inner glass sheet, wherein the interior The glass sheet has a thickness ranging from about 0.5 mm to about 1.5 mm, wherein the outer glass sheet has a thickness ranging from about 1.5 mm to about 3.0 mm, and wherein the polymeric intermediate layer has a range from about 1 MPa to about 75 MPa. One of the elastic modulus. The glass laminate structure of claim 1 wherein the inner glass sheet comprises one or more alkaline earth oxides such that one of the alkaline earth oxides is present in an amount of at least about 5 wt.%. The glass laminate structure of claim 1 wherein the inner glass sheet comprises at least about 6 wt.% alumina. The glass laminate structure of claim 1 wherein the inner glass sheet has a thickness of between about 0.5 mm to about 0.7 mm. The glass laminate structure of claim 1, wherein the polymer intermediate The layer comprises a single polymer sheet, a multilayer polymer sheet or a composite polymer sheet. The glass laminate structure of claim 1, wherein the polymer intermediate layer comprises a material selected from the group consisting of poly vinyl butyral (PVB), polycarbonate, acoustic PVB, ethylene vinyl acetate ( One of a group consisting of ethylene vinyl acetate (EVA), a thermoplastic polyurethane (TPU), an ionomer, a thermoplastic material, and a combination of the foregoing materials. The glass laminate structure of claim 1 wherein the polymeric intermediate layer has a thickness of between about 0.4 and about 1.2 mm. The glass laminate structure of claim 1, wherein the outer glass sheet comprises a material selected from the group consisting of soda-lime glass and annealed glass. The glass laminate structure of claim 1 wherein the outer glass sheet has a thickness of about 2.1 mm. The glass laminate structure of claim 1, wherein the glass laminate has an area greater than 1 m ² . The glass laminate structure of claim 1, wherein the glass laminate is a windshield, a sunroof or a cover (cover) Plate). The glass laminate structure of claim 1 wherein the inner glass layer has a surface compressive stress of between about 250 MPa and about 900 MPa. The glass laminate structure of claim 1, wherein the inner glass layer has a surface compressive stress between about 250 MPa and about 350 MPa, and the compressive stress has a DOL greater than about 20 μm. The glass laminate structure of claim 1, wherein a surface of the outer glass layer adjacent to the intermediate layer is acid etched. The glass laminate structure of claim 1, wherein a surface of the inner glass layer opposite the intermediate layer is acid etched. A glass laminate structure comprising: a chemically strengthened outer glass sheet; a chemically strengthened inner glass sheet; and at least one polymer intermediate layer between the outer glass sheet and the inner glass sheet, wherein the inner portion The glass layer has a surface compressive stress of between about 250 MPa and about 900 MPa, wherein the polymeric intermediate layer has an elastic modulus ranging from about 1 MPa to about 75 MPa, and Wherein a surface of the inner glass sheet constitutes an inner surface of an automotive laminate. The glass laminate structure of claim 16, wherein the inner glass layer has a surface compressive stress between about 250 MPa and about 350 MPa, and the compressive stress has a DOL greater than about 20 μm. The glass laminate structure of claim 16, wherein the inner glass sheet has a thickness ranging from about 0.5 mm to about 1.5 mm, and wherein the outer glass sheet has a thickness ranging from about 1.5 mm to about 3.0 mm. . The glass laminate structure of claim 16, wherein the polymer intermediate layer comprises a material selected from the group consisting of poly vinyl butyral (PVB), polycarbonate, acoustic PVB, ethylene vinyl acetate ( One of a group consisting of ethylene vinyl acetate (EVA), a thermoplastic polyurethane (TPU), an ionomer, a thermoplastic material, and a combination of the foregoing materials. The glass laminate structure of claim 16 wherein the polymeric intermediate layer has a thickness of between about 0.4 and about 1.2 mm.