JP2020128331A - Light-weight hybrid glass laminates - Google Patents

Abstract

To provide a glass laminate of thin, light-weight glazing that possesses the durability and sound-damping properties associated with thicker, heavier glazing.SOLUTION: A glass laminate structure 10 comprises: a non-chemically strengthened external glass sheet 12; a chemically strengthened internal glass sheet 16; and at least one polymer interlayer 14 formed between the external glass sheet 12 and the internal glass sheet 16. The internal glass sheet 16 has a thickness from 0.5 mm to 1.5 mm, and a modulus of elasticity from 60 GPa to 85 GPa. The external glass sheet 12 has a thickness from 1.5 mm to 3 mm. The internal glass sheet 12 contains an alkali aluminosilicate glass. The internal glass sheet 12 contains one or more alkaline earth oxides such that the content of the alkaline earth oxides is at least 5 mass%.SELECTED DRAWING: Figure 4

Description

Description of related application

This application claims the benefit of priority under 35 USC 35 199 of US Provisional Patent Application No. 61/500766 filed June 24, 2011, September 28, 2011 Filed under No. 13/274182, a nonprovisional application entitled "Lightweight Composite Laminated Glass", which is a continuation-in-part application and is a co-pending application of 35 USC §120. Claims the benefit of priority in US patent application Ser. No. 13/937,707, filed July 9, 2013, which claims the benefit of priority below, and the content of each of these applications is relied upon. , All quoted here.

FIELD OF THE DISCLOSURE The present disclosure relates generally to glass laminates and, more particularly, to hybrid laminated glass that includes chemically tempered outer glazing and non-chemically tempered inner glazing. Such composite laminated glass will be characterized by light weight, good sound damping performance, and high impact resistance. In particular, the disclosed laminated laminated glass meets the criteria of an industrially applicable impact test for applications other than windshields.

Laminated glass can be used as windows and glazing in architectural applications and transportation applications including automobiles, rail vehicles and airplanes. As used herein, a glazing is a transparent or translucent member of a wall or other structure. Common types of glazing used in architectural and automotive applications include clear glass and tinted glass, including laminated glass. For example, a laminated glazing consisting of opposing glass sheets separated by soft poly(vinyl butyral) (PVB) can be used as a window, windshield, or sunroof. In some applications, laminated glass having high mechanical strength and acoustic damping properties is desirable to provide a safe barrier while reducing acoustic transmission from external sources.

In many vehicle applications, fuel economy is a function of vehicle weight. Therefore, it is desirable to reduce the mass of glazing for such applications without compromising strength and acoustic damping properties. In this regard, the laminated glass is mechanically robust with respect to external contact events such as attempted hatching or contact with stones or hail, but as a result of internal impact events such as contact with passengers during a collision. It may be convenient to dissipate the energy (and cracks) of the appropriate. Moreover, government regulations require road vehicles to have better fuel economy and lower carbon dioxide emissions. Therefore, further efforts are being made to reduce the weight of these vehicles while maintaining current government and industry safety standards. Non-glass window materials such as polycarbonate have been developed. Although these materials reduce vehicle weight, they do not exhibit adequate resistance to environmental debris and other concerns. However, embodiments of the present disclosure provide substantial weight reduction, safety compliance, effective durability and reduced likelihood of laceration in the event of a vehicle crash.

In view of the above, a thin lightweight glazing with durability and sound damping properties associated with thicker and heavier glazing is desirable.

According to one aspect of the present disclosure, a laminated glass comprises an outer glass plate, an inner glass plate, and a polymer intermediate layer formed between the outer and inner glass plates. In order to optimize the impact behavior of the laminated glazing, the outer glazing may consist of chemically tempered glass and have a thickness of 1 mm or less, while the inner glazing consists of non-chemically tempered glass and 2.5 mm. It may have the following thickness: In embodiments, the polymeric interlayer (eg, poly(vinyl butyral) or PVB) can have a thickness of 1.6 mm or less. Conveniently, the disclosed composite laminated glass structure can distribute stress to impact. For example, the disclosed laminated glass can provide excellent impact resistance, resist fracture to external impact events, yet properly dissipate energy and properly fracture to internal impact events.

One non-limiting embodiment of the present disclosure is a laminated glass structure having a non-chemically strengthened outer glass sheet, a chemically strengthened inner glass sheet and at least one polymer interlayer intermediate the outer and inner glass sheets. And a laminated glass structure having an inner glass sheet thickness ranging from about 0.5 mm to about 1.5 mm and an outer glass sheet thickness ranging from about 1.5 mm to about 3.0 mm.

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

Additional features and advantages of the claimed subject matter are set forth in the following detailed description, some of which will be readily apparent to those skilled in the art from that description, or the following detailed description, the claims. It will be appreciated by the practice of the claimed subject matter, including the scope, as well as the attached drawings.

Both the foregoing general description and the following detailed description present embodiments of the present disclosure, which may provide an overview or skeleton for understanding the nature and features of the claimed subject matter. It will be understood that it is intended. The accompanying drawings are included to provide a further understanding of the present disclosure and are included in and constitute a part of this specification. The drawings illustrate various embodiments and, together with the description, serve to explain the principles and operation of the claimed subject matter.

While the presently preferred form is shown in the drawings for purposes of explanation, it will be understood that the embodiments disclosed and discussed herein are not limited to the precise arrangements and instrumentalities shown.
Illustration of an exemplary flat composite laminated glass according to some embodiments of the present disclosure Explanatory drawing of an exemplary bent composite laminated glass according to another embodiment of the present disclosure Explanatory view of an exemplary bent composite laminated glass according to yet another embodiment of the present disclosure. Illustration of an exemplary bent composite laminated glass according to a further embodiment of the present disclosure

In the following description, like reference characters refer to like or corresponding parts throughout the several views of the drawings. Unless stated otherwise, terms such as "top", "bottom", "outward", "inward" are for convenience only and should not be considered limiting. Moreover, whenever a group is described as comprising at least one of a plurality of components and combinations thereof, the groups are listed either individually or in combination with each other. It will be appreciated that any number of these components may be included, consist essentially of, or consist of.

Similarly, whenever a group is described as consisting of at least one of a plurality of components and combinations thereof, the groups are those listed either individually or in combination with each other. It will be appreciated that it may consist of any number of components. Unless stated otherwise, a range of values includes both the upper and lower limits of the range, if listed. As used herein, a noun refers to "at least one" or "one or more," unless otherwise specified.

The following description of the present disclosure is provided as teachings enabling its implementation and the best mode currently known thereof. Those skilled in the art will recognize that many modifications can be made to the embodiments described herein while still obtaining the beneficial results of this disclosure. It will also be apparent that some of the desired benefits of the present disclosure may be obtained without selecting some of the features of the present disclosure and utilizing other features. Accordingly, one of ordinary skill in the art will recognize that many modifications and adaptations of the present disclosure are possible and may even be desirable in certain circumstances and are a part of the present disclosure. Therefore, the following description is provided by way of illustration of the principles of the disclosure and not limitation thereof.

One skilled in the art will recognize that many modifications to the exemplary embodiments described herein are possible without departing from the spirit and scope of this disclosure. Therefore, the description is not intended to be, and should not be construed as limited to, the examples given, but it should be understood that all of the protection provided by the appended claims and their equivalents. Range should be provided. Moreover, some of the features of the present disclosure may be used without corresponding use of other features. Accordingly, the following description of illustrative or illustrative embodiments is provided for the purpose of demonstrating the principles of the disclosure and may include modifications thereof and substitutions thereof, rather than limitation thereof.

The laminated glass disclosed herein is configured to include an outer chemically strengthened glass plate and an inner non-chemically strengthened glass plate. As defined herein, when the laminated glazing is in actual use, the outer glazing is close to or in contact with the environment, while the inner glazing is the structure or vehicle (eg , Close to or in contact with the interior of a car (eg a passenger compartment).

An exemplary laminated glass is shown in FIG. The laminated glass 100 includes an outer glass plate 110, an inner glass plate 120, and a polymer intermediate layer 130. The polymeric interlayer may be in direct physical contact (eg, laminated) with each of the respective outer and inner glass sheets. The outer glass plate 110 has an outer surface 112 and an inner surface 114. In a similar context, the inner glass pane 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 each in contact with a polymer intermediate layer 130.

During use, laminated glass desirably resists cracking in response to external impact events. However, in the event of an internal impact event, such as when a vehicle occupant bumps into the laminated glass, the laminated glass keeps the occupant in the vehicle and still provides energy in a collision to minimize injury. Dissipation is desirable. The ECE R43 head test, which simulates a collision event originating from inside the vehicle, is a regulatory test that requires the laminated glazing to crack under certain internal collisions.

Without intending to be bound by theory, when one laminated glass of glass plate/polymer interlayer/glass plate is impacted, the opposite side of the impacted plate, as well as the opposite side The outer surface of the plate is placed in tension. Due to the stress distribution calculated for the glass sheet/polymer interlayer/glass sheet laminated glass under biaxial loading, the magnitude of the tensile stress on the opposite side of the impacted sheet is It will be comparable (or even slightly larger) to the magnitude of the tensile stress experienced on the outer surface. However, at high loading rates, which is a characteristic of shocks typically experienced in automobiles, the magnitude of the tensile stress at the outer surface of the opposite plate depends on the tensile stress at the opposite surface of the shocked plate. Would be much larger than As disclosed herein, a composite laminated glass is configured to have a chemically strengthened outer glass sheet and a non-chemically strengthened inner glass sheet to optimize impact resistance with respect to both external and internal impact events. be able to.

A suitable inner glass sheet is a non-chemically strengthened glass sheet such as soda lime glass. If necessary, the inner glass plate may be heat strengthened. In embodiments where soda lime glass is used as the non-chemically strengthened glass sheet, conventional decorative materials and methods (eg, glass frit enamel and screen printing) can be used, which simplifies the laminated glass manufacturing process. Can be To achieve the desired transmission and/or attenuation across the electromagnetic spectrum, tinted soda lime glass plates can be incorporated into composite laminated glass.

A suitable outer glass plate may be chemically strengthened by an ion exchange process. In this process, the ions at or near the surface of the glass plate are generally exchanged for larger metal ions from the salt bath by immersing the glass plate in a molten salt bath for a period of time. In one embodiment, the temperature of the molten salt bath is about 430°C and the predetermined period of time is about 8 hours. The incorporation of larger ions into the glass strengthens the plate by creating compressive stress in the area near the surface. A corresponding tensile stress is induced in the central region of the glass to balance its compressive stress.

Exemplary ion-exchangeable glasses suitable for forming composite laminated glass are alkali aluminosilicate glasses or alkali aluminoborosilicate glasses, although other glass compositions are also contemplated. As used herein, "ion-exchangeable" means that a glass refers to cations located at or near the surface of the glass as cations of the same valence, larger or smaller in size. It means that it can be exchanged. One example glass composition comprises SiO ₂ , B ₂ O ₃ and Na ₂ O, where (SiO ₂ +B ₂ O ₃ ) ≧66 mol %, and Na ₂ O ≧9 mol %. In one example, the glass plate comprises at least 6% by weight aluminum oxide. In yet another embodiment, the glass plate contains one or more alkaline earth oxides such that the content of alkaline earth oxides is at least 5% by weight. Suitable glass compositions, in some embodiments, further comprise at least one of K ₂ O, MgO, and CaO. In a particular embodiment, the glass is 61 to 75 mol% of SiO _2, 7 to 15 mol% of Al ₂ O _3, 0 to 12 mol% of B ₂ O _3, 9 to 21 mol% of Na ₂ O, it may include 0 to 4 mol% of K ₂ O, 0 to 7 mol% of MgO, and 0-3 mol% of CaO.

Yet another exemplary glass composition suitable for forming a composite laminated glass, 60 to 70 mol% of SiO _2, having 6 to 14 mole% Al ₂ O _3, 0-15 mol% B ₂ O ₃ , 15 mol% of Li ₂ O, 0 to 20 mol% of Na ₂ O, 0 mol% of K ₂ O, 0 to 8 mol% of MgO, 0 mol% of CaO, 0 to 5 ZrO ₂ mole%, 0-1 mol% of SnO _2, comprises 0-1 mole% of CeO _2, 50 ppm of less than As ₂ O _3, and Sb ₂ O ₃ of less than 50 ppm, 12 mol% ≦ (Li ₂ O+Na ₂ O+K ₂ O)≦20 mol %, and 0 mol%≦(MgO+CaO)≦10 mol %.

Still another exemplary glass composition is 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. % of 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, from 0 to 3 mol% ZrO ₂ , 0.05 to 0.25 mol% SnO ₂ , 0.05 to 0.5 mol% CeO ₂ , less than 50 ppm As ₂ O ₃ , and less than 50 ppm 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 particular embodiments, the alkali aluminosilicate glass comprises alumina, at least one alkali metal, and in some embodiments greater than 50 mol% SiO ₂ , and in other embodiments at least 58%. Mol% SiO ₂ , in yet another embodiment, at least 60 mol% SiO ₂ , wherein the ratio (Al ₂ O ₃ +B ₂ O ₃ )/Σ modifier >1, where In ratios, the components are expressed in mol% and the modifier is an alkali metal oxide. The glass In a particular embodiment, 58 to 72 mol% of SiO _2, 9 to 17 mol% of Al ₂ O _3, 2 to 12 mol% of B ₂ O _3, 8 to 16 mol% of Na ₂ O, and 0 to 4 mol% K ₂ O, consisting essentially of, or consisting of, the ratio (Al ₂ O ₃ +B ₂ O ₃ )/Σ modifier>1.

In another embodiment, the alkali aluminosilicate glass is 61 to 75 mol% of SiO _2, 7 to 15 mol% of 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% K ₂ O, 0 to 7 mol% MgO, and 0 to 3 mol% CaO.

In yet another embodiment, the alkali aluminosilicate glass is 60 to 70 mol% of SiO _2, having 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 mol% of K ₂ O, 0 to 8 mol% of MgO, 0 mol% of CaO, 0 to 5 mol% of ZrO ₂ , 0 to 1 mol% SnO ₂ , 0 to 1 mol% CeO ₂ , less than 50 ppm 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 yet another embodiment, the alkali aluminosilicate glass is 64 to 68 mol% of SiO _2, 12 to 16 mol% of Na ₂ O, 8 to 12 mol% of Al ₂ O _3, 0 to 3 mole% Of B ₂ O ₃ , 2-5 mol% K ₂ O, 4-6 mol% MgO, and 0-5 mol% CaO, consisting essentially of or consisting of 66 mol. %≦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%, and 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 some embodiments, the chemically strengthened glass as well as the non-chemically strengthened glass is selected from the group comprising Na ₂ SO ₄ , NaCI, NaF, NaBr, K ₂ SO ₄ , KCl, KF, NKr, and SnO _2. At least one fining agent is batch compounded in an amount of 0 to 2 mol %.

In one exemplary embodiment, the sodium ions in the chemically strengthened glass can be replaced by potassium ions from the molten batch, but other alkali metal ions with a larger atomic radius, such as rubidium and cesium, cause the glass to be displaced. It does not matter even if the smaller alkali metal ion in the inside is replaced. According to certain embodiments, 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 may be used in the ion exchange process.

When the smaller ions are replaced by the larger ones at a temperature below which the glass network can relax, a distribution of ions over the surface of the glass is created, which results in a stress profile. The larger volume of entrained ions creates a compressive stress (CS) on the surface of the glass and a tension in the center (central tension, or CT). This compressive stress has the following relational expression:

Is related to the central tension, where t is the total thickness of the glass sheet and DOL is the exchange depth, also referred to as the layer depth.

According to various embodiments, composite laminated glass, including ion-exchanged glass, has a number of desirable properties including lightweight, high impact resistance, and improved acoustic damping.

In one exemplary embodiment, the chemically strengthened glass sheet has a surface compressive stress of at least 300 MPa, such as at least 400, 450, 500, 550, 600, 650, 700, 750 or 800 MPa, at least about 20 μm (eg, at least Layer depth of 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 less than 100 MPa (eg, 100, 95). , 90, 85, 80, 75, 70, 65, 60, or 55 MPa).

The elastic modulus of the chemically strengthened glass plate can range from about 60 MPa to 85 GPa (eg, 60, 65, 70, 75, 80 or 85 GPa). The elastic modulus of the glass sheet and the polymeric interlayer can affect both the mechanical properties (eg, flexure and strength) and acoustic performance (eg, transmission loss) of the resulting laminated glass.

Examples of the glass plate forming method include a fusion draw method and a slot draw method, both of which are examples of the down draw method, and a float method. These methods can be used to form both chemically and non-chemically strengthened glass sheets. The fusion draw process uses a drawing tank having a passage for receiving the molten glass raw material. The passage has weirs open on the top side along the length of the passage on either side of the passage. When the passages are filled with molten material, the molten glass overflows the weir. The molten glass flows down to the outer surface of the drawing tank due to gravity. These outer surfaces extend downward and inward so that they join at the lower edge of the drawing tank. Two flowing glass surfaces join and fuse at this edge to form a single flowing plate. The fusion draw method presents the advantage that neither of the outer surfaces of the resulting glass sheet touches any part of the device, because the two glass films flowing over the passages fuse together. Therefore, the surface properties of the glass plate produced by the fusion draw method are not affected by such contact.

The slot draw method is distinguished from the fusion draw method. Here, the molten glass raw material is supplied to the drawing tank. At the bottom of the drawing tank there is an open slot with a nozzle that extends the length of the slot. The molten glass flows through the slots/nozzles and is pulled downwards as a continuous plate into the slow cooling zone. The slot draw method can provide a thinner plate than the fusion draw method because only one plate is pulled through the slot rather than the two plates fused together.

The downdraw method produces a glass sheet having a relatively solid surface and a uniform thickness. Since the strength of the glass plate is controlled by the amount and size of surface scratches, a solid surface with minimal contact has a high initial strength. When the high strength glass is then chemically strengthened, the resulting strength can be higher than that of the lapped and polished surface. Downdraw glass can be drawn to a thickness of less than about 2 mm. Moreover, down-drawn glass has a very smooth surface that can be used for end use without costly grinding and polishing.

In the float process, glass sheets characterized by a smooth surface and uniform thickness are produced by suspending molten glass on a bed of molten metal, typically tin. In the exemplary process, molten glass provided on 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 plate is lifted from the tin to the rollers. Once away from the tin bath, the glass plate can be further cooled and slowly cooled to reduce internal stress.

Glass plates can be used to form the laminated glass. As defined herein, composite laminated glass comprises an outward facing chemically strengthened glass sheet, an inward facing non-chemically strengthened glass sheet, and a polymeric interlayer formed between the glass sheets. The polymeric intermediate layer may comprise a monolithic polymer plate, a multilayer polymer plate, or a composite polymer plate. The polymer intermediate layer can be, for example, a soft poly(vinyl butyral) plate.

Laminated glass can be adapted to provide an optically clear barrier to structural openings and automotive openings, such as automotive glazing. Laminated glass can be formed using a wide variety of processes. In an exemplary embodiment, the assembly includes placing a first glass sheet, overlaying a polymeric interlayer such as a PVB sheet, placing a second glass sheet, and then over-growing the edges of the glass sheet. The step of cutting off PVB is included. The bonding step may include displacing most of the air from the interface to partially bond the PVB to the glass plate. The finishing process, typically performed at elevated temperature and pressure, completes the bonding of the glass sheets to each polymeric interlayer. In the previous embodiment, the first glass plate can be a chemically strengthened glass plate, the second glass plate can be a non-chemically strengthened glass plate, and vice versa.

Thermoplastic materials such as PVB may be applied as the preformed polymeric interlayer. The thermoplastic layer, in some embodiments, is at least 0.125 mm (eg, 0.125, 0.25, 0.38, 0.5, 0.7, 0.76, 0.81, 1, 1. It may have a thickness of 14, 1.19 or 1.2 mm). The thermoplastic layer has a thickness of 1.6 mm or less (eg, about 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1 or 1.2 mm, etc. It may have a thickness of 0.4 to 1.2 mm). The thermoplastic layer may cover most, or preferably substantially all, of the two opposing major surfaces of the glass. The thermoplastic layer may also cover the edge of the glass. The glass plate in contact with the thermoplastic layer may have a softening point, such as a temperature at least 5° C. or 10° C. above the softening point of the thermoplastic material, to facilitate bonding of the thermoplastic material to the respective glass plate. It may be heated to a higher temperature. The heating may be carried out on the glass which is in contact with the thermoplastic layer under pressure.

Selected commercial polymeric interlayer materials are summarized in Table 1. The table also includes the glass transition temperature and elastic modulus for each product sample. The glass transition temperature and elastic modulus data were obtained from technical data available from the manufacturer, or the glass transition temperature and elastic modulus were measured using a DSC200 differential scanning calorimeter (Seiko Instruments Inc., Japan). Or by the ASTM D638 method. Further description of the acrylic/silicone resin material used for the ISD resin is disclosed in US Pat. No. 5,624,763, and description of the sound insulation improving PVB resin is disclosed in JP-A-5-138840. , Their contents are all quoted here.

The composite laminated glass may incorporate one or more polymeric interlayers. The multiple interlayers will provide complementary or discrete functionality, including adhesion promotion, acoustic control, UV transmission control, tinting, tinting and/or IR transmission control.

The elastic modulus of the polymer interlayer can range from about 1 MPa to 75 MPa (eg, about 1, 2, 5, 10, 15, 20, 25, 50 or 75 MPa). At a loading rate of 1 Hz, the elastic modulus of a standard PVB interlayer can be about 15 MPa, and that of sound insulation grade PVB can be about 2 MPa.

During the laminating process, the interlayer is generally heated to a temperature effective to soften the interlayer, which promotes conformal mating of the interlayer to the respective surface of the glass sheet. It For PVB, the laminating temperature can be about 140°C. The mobile polymer chains within the interlayer material form bonds with the glass surface, which promotes adhesion. High temperatures also accelerate the diffusion of residual air and/or moisture from the glass-polymer interface.

The application of pressure promotes the flow of the interlayer material and suppresses the formation of bubbles that could otherwise be induced by the total vapor pressure of water and air trapped at the interface. Heat and pressure are simultaneously applied to the assembly in the autoclave to suppress bubble formation.

Composite laminated glass can provide beneficial effects, including attenuation of acoustic noise, reduction of UV and/or IR light transmission, and/or structure of the aesthetic appeal of window openings. The individual glass sheets that make up the disclosed laminated glass, as well as the formed laminated glass, have one or more attributes including composition, density, thickness, profilometry, and optical attenuation, sound attenuation, and impact resistance. It is characterized by various properties including mechanical properties such as. Various aspects of the disclosed composite laminated glass are described herein.

Composite laminated glass can be adapted for use as, for example, windows or glazings and can be configured in any suitable size and dimensions. In embodiments, the laminated glass has lengths and widths that independently vary from 10 cm to 1 m or more (eg, 0.1, 0.2, 0.5, 1, 2, or 5 m). Laminated glass may independently have an area of greater than 0.1 m ² , such as greater than 0.1, 0.2, 0.5, 1, ² , 5, 10, or 25 m ² .

Laminated glass can be substantially flat or shaped for a particular application. For example, laminated glass can also be formed as a bent or molded piece for use as a windshield or cover plate. The structure of the molded laminated glass may be simple or complicated. In certain embodiments, the laminated glass may have complex curvatures, with the glass panes having distinct radii of curvature in two independent directions. Therefore, such shaped glass sheet has a "cross curvature" in which the glass is bent along an axis parallel to a given dimension and also along an axis perpendicular to the same dimension. (cross curvature)". For example, automobile sunroofs are typically about 0.5 m x 1.0 m and have 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 major axis.

Molded laminated glass according to an embodiment can be defined by a bending modulus, where the bending modulus of a given part is equal to the radius of curvature along that axis divided by the length of the given axis. Therefore, for an exemplary automotive sunroof having radii of curvature of 2 m and 4 m along the respective axes of 0.5 m and 1.0 m, respectively, the bending modulus along each axis is 4. Molded laminated glass can have a flexural modulus ranging from 2 to 8 (eg, 2, 3, 4, 5, 6, 7, or 8).

An exemplary molded laminated glass 200 is shown in FIG. The formed laminated glass 200 includes an outer (chemically strengthened) glass plate 100 formed on a convex surface of the laminated glass, while an inner (non-chemically strengthened) glass plate 120 is formed on a concave surface of the laminated glass. However, it will be appreciated that the convex surface of the unillustrated embodiment may include a non-chemically strengthened glass sheet, while the opposite concave surface may include a chemically strengthened glass sheet.

FIG. 3 is a cross-sectional view of yet another embodiment of the present disclosure. FIG. 4 is a perspective view of a further embodiment of the present disclosure. With reference to FIGS. 3 and 4, as discussed in the previous paragraph, the exemplary laminated structure 10 may have an inner layer 16 of chemically strengthened glass, eg, Gorilla® Glass. This inner layer 16 may be heat treated, ion exchanged and/or annealed. The outer layer 12 may be a non-chemically strengthened glass plate such as conventional soda lime glass, annealed glass. Laminated structure 10 may also have a polymeric interlayer 14 intermediate the outer and inner glass layers. The inner layer 16 of glass may have a thickness of 1.0 mm or less and have a residual surface CS level of between about 250 MPa and about 350 MPa and a DOL of greater than 60 micrometers. In another embodiment, the inner layer 16 preferably has a CS level of about 300 MPa. In one embodiment, the thickness of the intermediate layer 14 can be about 0.8 mm. Exemplary intermediate layer 14 includes, but is not limited to, polyvinyl butyral or other suitable polymeric material described herein. In a further embodiment, both the outer and/or inner layers 12, 16 surfaces may be acid etched to improve resistance to external impact events. For example, in one embodiment, the first surface 13 of the outer layer 12 can be acid etched and/or another surface 17 of the inner layer can be acid etched. In another embodiment, the first surface 15 of the outer layer can be acid etched and/or another surface 19 of the inner layer can be acid etched. Therefore, such an embodiment can provide a laminate structure that is significantly lighter than conventional laminate structures and complies with regulatory impact requirements. Exemplary thicknesses of the outer and/or inner layers 12, 16 may range from 0.5 mm to 1.5 mm to 2.0 mm or more.

In a preferred embodiment, this thin chemically strengthened inner layer 16 may have a surface stress of between about 250 MPa and about 900 MPa and may range in thickness 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 of about 1.5 mm to about 3.0 mm or greater. Of course, the thickness of the outer and inner layers 12, 16 can be different in each laminated structure 10. Another preferred embodiment of the exemplary laminate structure may have an inner layer of chemically strengthened glass of 0.7 mm, a polyvinyl butyral layer having a thickness of about 0.76 mm, and an outer layer of annealed glass of 2.1 mm. is there.

Exemplary glass layers are generally described above, as described in US Pat. Nos. 7,666,511, 4,483,700, and 5,674,790, each of which is incorporated herein by reference. It can be manufactured by fusion drawing and then chemically strengthening such drawn glass. Therefore, the exemplary chemically strengthened glass layer can have a deep DOL of CS and can exhibit high flexural strength, scratch resistance and impact resistance. Example embodiments may also include acid-etched or flared surfaces for increased impact resistance, by reducing the size and extent of scratches on these surfaces, The strength of such surfaces can also be increased. If etched just prior to lamination, the benefits of enhanced etching or heating can be maintained at the surface that is bonded to the intermediate layer.

One embodiment of the present disclosure provides an exemplary laminated glazing structure having a non-chemically strengthened outer glass sheet, a chemically strengthened inner glass sheet, and at least one polymeric intermediate layer intermediate the outer and inner glass sheets. To do. The polymer intermediate layer can be a single polymer plate, a multilayer polymer plate, or a composite polymer plate. Further, the polymeric interlayer is made from materials such as, but not limited to, PVB, polycarbonate, sound insulating PVB, ethylene vinyl acetate (EVA), thermoplastic polyurethane (TPU), ionomers, thermoplastic materials, and combinations thereof. Can be configured. The inner glass sheet can have a thickness of about 0.5 mm to about 1.5 mm, and the outer glass sheet can have a thickness of about 1.5 mm to about 3.0 mm. In other embodiments, the inner glass sheet can have a thickness of about 0.5 mm to about 0.7 mm, the polymeric interlayer can have a thickness of about 0.4 mm to about 1.2 mm, and/or Alternatively, the thickness of the outer glass plate can be about 2.1 mm. In another embodiment, the inner glass pane may include one or more alkaline earth oxides such that the content of alkaline earth oxides is at least about 5% by weight. The inner glass sheet can also include at least about 6% by weight aluminum oxide. In additional embodiments, the outer glass pane is composed of materials such as, but not limited to, soda lime glass and annealed glass. The exemplary laminate can have an area of greater than 1 m ^{2 and} can be used as a vehicle windshield, sunroof or cover plate. The inner glass layer, in yet another embodiment, has a surface compressive stress of between about 250 MPa and about 900 MPa, or in another embodiment, a surface compressive stress of between about 250 MPa and about 350 MPa and greater than about 20 μm. It may have a compressive stress DOL. Some embodiments may acid etch some or any part of the surface of the glass sheets.

Another embodiment of the present disclosure is a laminated glass structure having a non-chemically strengthened outer glass sheet, a chemically strengthened inner glass sheet, and at least one polymer interlayer intermediate the outer and inner glass sheets, A laminated glass structure is provided in which the inner glass sheet has a surface compressive stress between about 250 MPa and about 900 MPa. In additional embodiments, the inner glass sheet can have a surface compressive stress of between about 250 MPa and about 350 MPa and a DOL of compressive stress greater than about 20 μm. Exemplary thicknesses of the inner glass sheet may range from about 0.5 mm to about 1.5 mm, and outer glass sheet thicknesses may range from about 1.5 mm to about 3.0 mm. Exemplary polymeric interlayers may be composed of materials such as, but not limited to, PVB, polycarbonate, sound insulating PVB, EVA, TPU, ionomers, thermoplastic materials, and/or combinations thereof, and/or about 0.4 mm. Can have a thickness of about 1.2 mm.

Thus, the embodiments of the present disclosure will provide a means to reduce the weight of automotive glazings by using thinner glass materials while maintaining optical and safety requirements. .. Conventional laminated windshields will account for 62% of the total weight of a vehicle's glazing; however, for example, using a 0.7 mm thick chemically strengthened inner layer with a 2.1 mm thick non-chemically strengthened outer layer. The weight of the windshield can be reduced by 33%. Further, it has been found that the use of a 1.6 mm thick non-chemically strengthened outer layer with a 0.7 mm thick chemically strengthened inner layer results in a total weight savings of 45%. Thus, using the exemplary laminate construction according to embodiments of the present disclosure, the laminated windshield provides proper bending to provide penetration resistance for inner and outer objects and an acceptable Head Injury Criteria (HIC) value. Will be able to pass all regulatory safety requirements, including Moreover, the exemplary outer layer composed of annealed glass presents an acceptable failure pattern caused by the impact of an external object, which is operable through the windshield in the event of chipping or cracking as a result of that impact. It will allow continuous visibility. Research has also shown that the use of chemically strengthened glass as the inner surface of asymmetric windshields provides the additional benefit of reduced laceration potential compared to the lacerations caused by occupants hitting the windshield in conventional annealing. Proven.

Methods of bending and/or shaping laminated glass can include gravity bending, press bending, and composite methods thereof. In the conventional method of gravity bending a thin flat glass sheet into a curved shape, such as an automobile windshield, one or a number of cold pre-cut glass sheets on a rigid preformed peripheral support surface of a bending installation. Place the boards. Bending equipment may be manufactured using metal or refractory materials. In the illustrated method, articulated bending equipment may be used. Prior to bending, the glass is typically supported only at some contacts. The glass is usually heated by exposure to high temperatures in an annealing kiln, which softens the glass and allows gravity to cause the glass to hang or drop to conform to the surrounding support surface. Then, generally all substantially the supporting surface is in contact with the perimeter of the glass.

A related technique is press bending in which a flat glass plate is heated to a temperature substantially corresponding to the softening point of the glass. The heated plate is then pressed or molded to the desired curvature between male and female mold members having complementary molding surfaces. The molding surface of the mold member may include a vacuum or air jet for engaging the glass sheet. In embodiments, the shaping surface may be configured to contact substantially all of the corresponding glass surface. Alternatively, one or both of the opposing molding surfaces may contact the respective glass surface over discrete areas or at discrete contacts. For example, the female mold member may be a ring-shaped surface. In embodiments, a combination of gravity bending and press bending techniques may be used.

The total thickness of the laminated glass can range from about 2 mm to 5 mm, where the outer and/or inner chemically strengthened glass sheets have a thickness of 1 mm or less (eg, 0.5, 0.6, 0.7, 0). 0.8, 0.9 or 1 mm, eg 0.5 to 1 mm). Furthermore, the inner and/or outer non-chemically tempered glass sheets may have a thickness of 2.5 mm or less (eg 1, 1.5, 2 or 2.5 mm, eg 1 to 2.5 mm). Alternatively, it may have a thickness of 2.5 mm or more. In embodiments, the total thickness of the glass sheet in the laminated glass is less than 3.5 mm (eg, 3.5, 3, 2.5 or 2.3 mm).

An exemplary laminated glass structure is shown in Table 2, where GG refers to chemically strengthened aluminosilicate glass sheet, and the term "glass" refers to non-chemically strengthened soda lime (SL) glass sheet, PVB refers to poly(vinyl butyral), which may optionally be sound insulating grade PVB (A-PVB).

Applicants have shown that the laminated glass structures disclosed herein have excellent durability, impact resistance, toughness, and scratch resistance. As will be appreciated by those skilled in the art, the strength and mechanical impact performance of glass sheets or laminated glass is limited by defects in the glass, including both surface and internal defects. When a laminated glass is impacted, the point of impact is in compression, while the ring or "hoop" around the point of impact, as well as the opposite surface of the impacted plate, is in tension. Generally, the point of failure is a flaw, usually on the glass surface, at or near the point of highest tension. This will occur on the opposite face, but can occur in the ring. If the flaw in the glass becomes under tension during an impact event, the flaw will probably propagate and the glass will generally break. Therefore, a large magnitude and depth of compressive stress (layer depth) are preferred.

One or both surfaces of the chemically strengthened glass sheet used in the disclosed composite laminated glass is under compression due to chemical strengthening. Providing compressive stress in a region close to the surface of the glass can prevent crack propagation and breakage of the glass sheet. The tensile stress from impact must exceed the compressive stress on the surface at the tip of the wound, as the damage propagates and damage occurs. In embodiments, the high compressive stress and large layer depth of chemically strengthened glass sheets allow the use of thinner glass than in the case of non-chemically strengthened glass sheets.

In the case of composite laminated glass, the laminated glass structure can flex much more than mechanically shocked non-reinforced tempered glass sheets or thicker non-chemically tempered laminated glass without breaking under mechanical shock .. This additional deflection allows more energy transfer to the interlayer of the laminated glass, which can reduce the energy reaching the opposite side of the glass. As a result, the composite laminated glass disclosed herein can withstand higher impact energy than monolithic non-chemically strengthened glass sheets or non-chemically strengthened laminated glass of similar thickness.

In addition to its mechanical properties, as will be appreciated by those skilled in the art, laminated structures can be used to attenuate sound waves. The composite laminated glass disclosed herein can dramatically reduce acoustic transmission while using thinner (lighter) structures with the mechanical properties required for many glazing applications.

The acoustic performance of laminates and glazing is generally affected by the bending vibrations of the glazing structure. Without being bound by theory, the human acoustic response generally peaks between 500 Hz and 5000 Hz, which corresponds to wavelengths of about 0.1-1 m in air and 1-10 m in glass. For glazing structures with a thickness of less than 0.01 m (<10 mm), the transmission is mainly due to the coupling of vibrations and sound waves into bending vibrations. Laminated glazing structures can be designed to convert energy from bending modes of glazing into shear strain within the polymer interlayer. In laminated glass utilizing thinner glass sheets, the greater compliance of thinner glass allows for greater amplitude, which in turn can impart greater shear strain to the interlayer. The low shear resistance of the most viscoelastic polymeric interlayer materials means that the interlayer promotes damping by high shear strains that are converted to heat under the influence of chain slip and relaxation.

In addition to the thickness of the laminated glass, the properties of the glass plates that make up the laminated glass will also affect the sound attenuation characteristics. For example, between a chemically tempered glass plate and a non-chemically tempered glass plate, there will be a small but significant difference at the glass-polymer interlayer interface that contributes to greater shear strain in the polymer interlayer. Also, in addition to the apparent compositional differences, aluminosilicate and soda-lime glasses will have different physical and mechanical properties, including elastic modulus, Poisson's ratio, density, etc., which will result in different acoustic responses. ..

Conventional uniaxial strength tests, such as the three-point or four-point bending test, have been used to measure the strength of glass and ceramic materials. However, the interpretation of uniaxial strength test results can be challenging because the measured strength depends on the edge effect as well as the bulk material.

On the other hand, a biaxial bending test can be used to provide strength ratings regardless of edge-induced phenomena. In the biaxial bending test, the laminated glass is supported at three or four points close to the periphery equidistant from the center, and then the laminated glass is loaded at the center position. Therefore, the location of maximum tensile stress conveniently occurs at the center of the surface of the laminated glass and is independent of edge conditions.

The exemplary flat composite laminated glass was subjected to a standard biaxial bending test (ECE R43 head test detailed in Annex 7/3). As explained further below, when the laminated glass of the present invention (Sample 1) was impacted on the non-chemically strengthened (soda lime) side, both glass sheets were damaged. However, when the laminated glass of Sample 1 was impacted on the chemically strengthened side, the non-chemically strengthened glass plate broke, but the chemically strengthened glass plate remained intact in 50% of the tested samples.

In one test, a high load velocity impact is directed at the inner (non-chemically strengthened) glass sheet 120. In response, both the inner surface 124 of the inner glass sheet 120 and the outer surface 112 of the outer glass sheet 110 are placed in tension. Since the magnitude of the tensile stress on the outer surface 112 is greater than the tensile stress on the inner surface 124, a milder tensile stress on the inner surface 124 in this configuration is sufficient to break the non-chemically tempered glass sheet 120. On the other hand, the high tensile stress on the outer surface 112 is likewise sufficient to damage the chemically strengthened glass sheet 110. The PVB interlayer deforms, but prevents the head impact device from penetrating the laminated glass as the glass sheet breaks. This is a satisfactory response under the ECE R43 head requirement.

In the relevant test, the impact is instead directed at the outer (chemically strengthened) glass sheet 110. In response, the inner surface 114 of the outer glass sheet 110 experiences mild tensile stress and the outer surface 122 of the inner glass sheet 120 experiences a greater amount of stress. In this configuration, the large stress on the outer surface 122 of the inner non-chemically strengthened glass sheet 120 causes the non-chemically strengthened glass sheet to break. However, the mild tensile stress of the inner surface 114 of the outer glass sheet 110 will not be sufficient to overcome the ion exchange-induced compressive stress in the region near the surface of the chemically strengthened glass. In a laboratory experiment, high load velocity impacts resulted in only two out of the six samples tested breaking the chemically strengthened glass sheet 110. In the remaining four samples, the non-chemically strengthened glass plate 120 broke, but the chemically strengthened glass plate 110 remained intact. All of the inventive samples exceeded the non-windshield impact requirements stated by ECE R43 head requirements.

Biaxial bending tests were also performed on Comparative Samples A and B. The comparative sample A consisting of a symmetrical structure of 1 mm thick chemically strengthened glass plate/0.76 mm thick standard PVB/1 mm thick chemically strengthened glass plate shows no breakage and therefore the laminated glass must be broken ECE It failed the requirements of R43.

Comparative sample B consists of a symmetrical structure of 1.5 mm thick soda lime glass plate/0.76 mm thick standard PVB/1.5 mm thick soda lime glass plate. Both glass plates failed as a result of the biaxial bending test, therefore comparative sample B passed the ECE R43 standard (Annex 7/3). However, both glass panes of the laminated glass of Comparative Sample B broke regardless of which plate was impacted, thus providing a robust mechanical resistance to the external impact realized on composite laminated glass. could not. During the test, head rebound (i.e., rebound) was greater in Comparative Sample B than in Sample 1, indicating that the Comparative Structure did not dissipate energy as effectively as the Examples of the present invention. I also found out what I had suggested.

Head Injury Criteria (HIC) is a conventional metric that can be used to assess the safety of laminated glass. The HIC value is a dimensionless quantity, which can be correlated to the likelihood of injury as a result of impact. Lower HIC values are desirable for internal shock events.

For the exemplary flat composite laminated glass, the average HIC value for impact on the non-chemically strengthened side of a 1.6 mm thick SL/0.8 mm thick A-PVB/0.7 mm thick GG laminate is 175. On the other hand, the average HIC value for the impact on the chemically strengthened side of the 0.7 mm thick GG/0.8 mm thick A-PVB/1.6 mm thick SL laminate was 381. For automotive glazing applications, the average HIC value for impact on the chemically strengthened side (outside) is advantageously greater than the average HIC value for impact on the non-chemically strengthened side. For example, the HIC value on the chemically strengthened side is at least 400 (eg, 400 or more), such that the HIC value on the chemically strengthened side is at least 50 (eg, at least 50, 100, 150 or 200) greater than the HIC value on the non-chemically strengthened side. , 450 or 500 or more), and the HIC value on the non-chemically strengthened side can be 400 or less (eg, 400, 350, 300, 250, 200, 150 or 100) or less.

While this description will contain many specifics, these should not be construed as limitations on its scope, but rather as descriptions of features that may be particular to a particular embodiment. Certain features that have been described above in the context of separate embodiments can also be implemented in combination in one embodiment. Conversely, various features that are described in the context of one embodiment can also be implemented in multiple embodiments separately or in any suitable subcombination. Furthermore, one or more features from the claimed combination may be characterized as previously described as operating in a particular combination, and even as initially claimed as such. Features may, in some cases, be deleted from the combination, and the claimed combination may relate to sub-combinations or variations of sub-combinations.

Similarly, while the operations are shown in the drawings or figures in a particular order, this is done such that the operations are performed in the particular order or sequence illustrated, or to obtain the desired result. Therefore, it should not be understood as requiring all of the illustrated operations to be performed. In some environments, multitasking operations and parallel processing may be convenient.

Ranges can be expressed herein as from "about" one particular value, and/or to "about" another particular value. When such a range is expressed, an example includes from the one particular value and/or to the other particular value. Similarly, it will be appreciated that when a value is expressed as an approximation using the antecedent "about," the particular value forms another aspect. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint and independent of the other endpoint.

It is also noted that the recitations herein refer to components of the disclosure that are “configured” or “adapted” to function in a particular fashion. In this regard, such components are “configured” or “adapted” to embody a particular property or to enable them in a particular fashion, where such These enumerations are structural enumerations rather than intended use enumerations. More specifically, a listing herein of the manner in which a component is "configured" or "adapted" refers to the existing physical condition of the component and, therefore, the structural condition of the component. It should be interpreted as a clear listing of features.

Various lightweight composite laminated glasses have been described, as shown in various configurations and embodiments shown in the drawings.

While the preferred embodiments of the present disclosure have been described, the described embodiments are merely illustrative, and the scope of the present invention is intended to cover the equivalents, many variations and modifications that one of ordinary skill It is to be understood that, where the full scope is allowed, it should be defined only by the appended claims.

10 Laminated structure 12 Outer layer 14 Intermediate layer 16 Inner layer 100 Laminated glass 110 Outer glass plate 120 Inner glass plate 130 Polymer intermediate layer 200 Molded laminated glass

Claims (6)

Non-chemically strengthened outer glass plate,
A chemically strengthened inner glass sheet, and at least one polymer intermediate layer intermediate the outer glass sheet and the inner glass sheet;
In a laminated glass structure with
The inner glass plate has a thickness of 0.5 mm to 1.5 mm and an elastic modulus of 60 GPa to 85 GPa,
The thickness of the outer glass plate ranges from 1.5 mm to 3 mm,
The inner glass plate contains an alkali aluminosilicate glass,
The inner glass plate contains one or more kinds of alkaline earth oxides so that the content of alkaline earth oxides is at least 5% by mass.
Laminated glass structure. The laminated glass structure according to claim 1, wherein the thickness of the polymer intermediate layer is 0.4 mm to 1.2 mm. The laminated glass structure according to claim 1 or 2, wherein the outer glass plate is composed of a material selected from the group consisting of soda-lime glass and annealed glass. The laminated glass structure according to any one of claims 1 to 3, wherein the laminated glass structure is an automobile windshield, a sunroof or a cover plate. The laminated glass structure according to any one of claims 1 to 4, wherein the inner glass sheet has a surface compressive stress of between 250 MPa and 900 MPa. The laminated glass structure according to any one of claims 1 to 5, wherein the inner glass sheet has a surface compressive stress between 250 MPa and 350 MPa and a DOL with a compressive stress of more than 20 µm.

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