• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
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    • 专利摘要:
    curved bulletproof glass made of glass, glass ceramics or mechanically curved ceramics in the impact face layer. the present invention discloses a curved bulletproof composite made of glass, glass ceramics or flexible ceramics in the impact face layer, in order to be mechanically curved during a lamination process through low heat (temperature) and pressure. composites may consist of one or more layers of glass, glass ceramics or ceramics curved by gravity or heat in one or more intermediate layers. furthermore, the present invention describes a process for producing the glass of the present invention, which comprises the following steps: a) dimensioning (cutting) glass or glass ceramic in the impact face layer and intermediate layers for the geometry or shape of the curved bulletproof composite; b) finish the edge of the glass, glass ceramics or ceramics; c) individually bend the intermediate layers of glass or glass ceramics by means of gravity and temperature; d) perform an ion exchange process for one or more glasses and / or glass-ceramic materials of the impact face layer and intermediate layers; e) paint the black stripe with organic paint on the impact face layer and / or one of the intermediate layers; f) assemble the impact face layer, the intermediate layers, the adhesive materials and the internal plastic layer; and g) mechanically bending during the pressure and heat lamination the impact face layer, the intermediate layers, the adhesive materials and the internal plastic layer.
    公开号:BR112014027982B1
    申请号:R112014027982-9
    申请日:2013-05-09
    公开日:2021-03-23
    发明作者:Mario Arturo Benjamín Mannheim Astete；Juan Pablo Suarez Cuervo；Juvénal Tobias Benitez Palmeth；Juan Carlos Espinosa Rojas
    申请人:Agp America S.A.；
    IPC主号:
    专利说明:

    [0001] 001 The present invention is related to the production of curved bulletproof composites, which incorporate glass, glass-ceramic or transparent materials on the impact face layer, in which the curvature of the materials used in the impact face layer is obtained mechanically during the pressure and temperature (heat) lamination process. 2. DESCRIPTION OF ART
    [0002] 002 A conventional bulletproof composite consists of a set of different layers of soda-lime glass1, which are linked together by adhesive layers, which are generally polymers, and in general have a layer of polycarbonate on the inside of the composite .
    [0003] 003 Referring to Figure 1, the architecture of a bulletproof composite commonly found in art is shown. Starting from the outside to the inside ("outside" means the space from which a bullet is normally fired; similarly, "inside" refers to the space protected by the bulletproof composite), there is a layer of glass the impact face that receives the impact of the projectile (1), which is fixed to other intermediate layers (2) of glass, which is fixed by means of several adhesive layers (3) and an internal layer (4) made of any high impact resistant plastic material.
    [0004] 004 Materials other than traditional soda-lime glass have been incorporated into the glass layer of the impact face (1) in recent bulletproof designs.
    [0005] 005 For example, WO 2007/032961 A2 considers the use of aluminum and lithium silicate (LAS) in the impact face layer (1) of Figure 1. Likewise, the PCT / US documents 2010/053106, US 7,875,565 and US 2010/0275767 contemplate the use of glass-ceramic materials2 in the impact face layer (1). Other transparent ceramic materials considered for the impact face layer (1) of the bulletproof composite include: polycrystalline aluminum oxinitrate (ALON), single crystal aluminum oxide (Sapphire) and spinel (MgAl2O4). However, ceramic materials are not massively used in the design and production of bulletproof glass, due to the high cost of these materials compared to soda-lime glass, borosilicate glass and glass-ceramic materials, as established in US patent application 2010 / 0275767.
    [0006] 006 The plurality of glass ceramic materials on the impact face layer US 2010/0275767 is also adhered to a coating layer comprising a shatter resistant material and an intermediate layer between the impact face layer and the impact layer. coating, wherein the intermediate layer may include an insulating material, such as a polymer, gas or liquid. The state of the art does not disclose any information about composites with different materials in the impact face layer and intermediate layers to be used in curved bulletproof composites.
    [0007] 007 The cost of ceramics can be 2,500 times higher than that of soda-lime glass, 115 times higher than that of borosilicate glass and 30 times more expensive than glass-ceramic materials. One of the most important mechanical properties considered for the selection of material to be used in the impact face layer of the bulletproof glass composite is the hardness. Hardness can be understood as a measure of the amount of force required to permanently change the shape of a material. In this sense, a harder material can erode or remove material from a softer material. In the present invention, it is desirable to have harder materials such as the impact face layer, in order to corrode projectile materials, deform their mass and therefore reduce their kinetic energy.
    [0008] 008 The main differences between glass, glass-ceramic and ceramic materials considered candidates to be introduced in bulletproof composites are: molecular structure, transparency and hardness. As such, the molecular structure of the glass is completely amorphous, so there is no organized molecular matrix; the above feature makes the glass transparent over the entire visible light spectrum. With regard to glass-ceramic materials, there is a hybrid molecular structure, part amorphous and part crystalline and, therefore, the transparency of these materials within the visible light spectrum is less than that of glass, and the hardness of these materials is greater than that hardness of the glass. In addition, transparent ceramic materials have a crystalline and molecular structure of superior hardness when compared to glass and glass-ceramic materials. The transparency of these materials is limited. Two of the main disadvantages of transparent ceramic materials, which can be included in bulletproof composites, are their high cost and the limited availability of large sizes (surface less than 0.5 m2).
    [0009] 009 Continuing with Figure 1, the material conventionally used in the intermediate layers of glass (2) is the same glass used in the impact layer glass layer (1). However, with the new concept of using a material harder than glass (soda-lime or borosilicate) in the impact face layer (1), the efficient use of glass in the intermediate layers (2) of the Figure 1. The number and thickness of the intermediate layers (2) used in the bulletproof composite depends on the type of ammunition that needs to be stopped, and therefore the more kinetic energy the projectile carries, the greater the number of intermediate layers needed or a greater thickness of them. The use of borosilicate glass3 as intermediate layers (2) may represent an advantage in the design of bulletproof composites, since borosilicate glass has a lower density than soda-lime glass and, thus, contributes to the reduction of density in the area of ballistic formulations. However, the cost of borosilicate glass is higher than the cost of soda-lime glass. No evidence is found in the state of the art of curved bulletproof composites in which the material used in the impact face layer (1) and in the intermediate layers (2) is the same type of glass ceramic or in which the ceramic glass used in the impact face layer (1) is different from the glass ceramic used in the intermediate layers (2). Likewise, no evidence is found in the state of the art of curved multilayer ballistic composites, in which ceramic materials are used in the impact face layer (1) and in the intermediate layers (2).
    [0010] As mentioned above, the adhesive layers (3) function as bonding layers (1), (2) and (4). These layers also reduce crack propagation and increase the ability of the bulletproof composite to withstand multiple impacts, keeping all the layers that make up the composite together, as described in US Patent No. 2009/0136702. The most used materials to join the layers are: polyurethane (PU), ethylene-vinyl acetate (EVA), ionomers and poly (vinyl butyrate) (PVB) or special PVB, PU or other polymers.
    [0011] 0011 The inner layer (4) works to contain shrapnel from the impact face layer (1) and intermediate layers (2) generated during impacts and absorbs residual kinetic energy that the projectile keeps after crossing the impact face layer (1 ), the intermediate layers (2) and the adhesive layers (3). The way in which the inner layers (4) absorb energy is through plastic deformation (deformation); the material conventionally used in the inner layer (4) is polycarbonate. Other materials that can be used in the inner layer (4) are as follows: various types of polyacrylates, polyethylenes, polyureas, rigid polyurethanes and polyesters, as illustrated in US 2010/0275767. However, US 2010/0275767 does not solve the problem of flexing the material that employs different softening temperatures, in order to provide parallelism between the impact face layer and the intermediate layers, avoid the spacing between said layers and avoid breaks during the heat and pressure lamination process.
    [0012] 0012 The production process of curved bulletproof composites using soda-lime or borosilicate glass or other ceramic or glass ceramic in the impact face layer (1) and in the intermediate layers (2) (Figure 1), comprises the following essential steps:
    [0013] 0013 a) dimension (cut) the glass or glass ceramics of the impact face layer (1) and intermediate layers (2) according to the geometry or shape of the curved bulletproof composite. Sinter the ceramic material of the impact face layer (1) according to the shape of the curved bulletproof composite to be produced.
    [0014] 0014 b) grinding the edge of the glass, glass ceramics or ceramics, that is, the impact face layer (1) and the intermediate layers (2);
    [0015] 0015 c) paint the black stripe with glass enamels, which are a type of inorganic paint, on the glass used in the impact face layer (1) and / or one of the glasses used in the intermediate layers (2);
    [0016] 0016 d) simultaneously bend, through gravity and temperature, the impact face layer (1) and the intermediate layers (2);
    [0017] 0017 e) perform an ion exchange process of one or more glasses and / or glass-ceramic materials of the impact face layer (1) and the intermediate layers (2);
    [0018] 0018 f) assemble the impact face layer (1), the intermediate layers (2), the adhesive layers (3) and the inner layer (4); and
    [0019] 0019 g) to laminate by pressure and temperature (heat) the impact face layer (1), the intermediate layers (2), the adhesive layers (3) and the inner layer (4); bend the inner layer (4) by pressure and temperature.
    [0020] 0020 a) Adjust (dimension) the glass or glass ceramic layer of the impact face (1) and the intermediate layers (2) to the shape of the curved bulletproof composite. Sinter the ceramic material of the impact face layer (1) according to the shape of the curved bulletproof composite to be produced: the glass and transparent glass-ceramic materials that can be used in the impact face layer (1) and in the intermediate layers (2) of Figure 1, they are obtained as large flat sheets (about 2 x 3 m). The above description, in order to increase the productivity of the manufacturer's glass or glass ceramics, guarantees the flat shape of the sheet and maintains good optical properties. Companies that manufacture bulletproof glass must cut flat sheets received from glass or glass ceramic manufacturers in order to obtain the number of layers in sizes and shapes required for parts intended for production. Unlike glass or glass-ceramic materials, ceramic materials have to be manufactured in the required size and final shape, due to the difficulty in machining these materials, due to their hardness.
    [0021] 0021 b) Grinding the edge of the glass, glass ceramics or ceramics: after the process of cutting materials incorporated in the impact face layer (1) and in the intermediate layers (2) (Figure 1), the edges must be ground. The purpose of this grinding process is to reduce the size of the cracks generated when cutting glass and glass-ceramic materials. Grinding the edges reduces the risk of breakage due to the presence of defects. Ceramic materials must be supplied with an edge finish.
    [0022] 0022 c) Paint the stripe black using glass enamels on the glass used in the impact face layer (1) and / or one on the glasses used in the intermediate layers (2): curved bulletproof composites for automotive use require a black stripe in the perimeter, having two main objectives. The first objective is to absorb the UV sunlight that vehicles are subjected to when outside, since this light denatures the adhesives used for fixing the bulletproof composites to the vehicle body and compromises the proof composite bond. bullet / bodywork. The black stripe on the perimeter absorbs UV sunlight and prevents the said sunlight from reaching the adhesives, in order to ensure that the bulletproof composite remains adhered to the vehicle bodies. The second objective of the black stripe on the perimeter of bulletproof composites is aesthetic, as it hides the link between the impact face layer (1) and the intermediate layers (2), which comprise the bulletproof composite. Therefore, it can be avoided to determine for what type of ammunition the said bulletproof composite was designed through a simple external visual inspection of the vehicle. The biggest disadvantage of painting the black stripe on the perimeter of bulletproof composites using glass enamels is the loss of mechanical strength of the glass when painted using this type of paint. When painting annealed glass (absence of internal stresses) using glass enamels, it loses about 60% of its mechanical strength and, therefore, armor manufacturers design bulletproof composites with a high thickness of the impact face layer ( 1); glass with thicknesses greater than 4 mm in the impact face layer (1) are conventionally used in order to resist the weight of the entire part and tensions generated when the vehicle is in motion.
    [0023] 0023 The use of glass enamels for the production of the black stripe is preferred by bulletproof glass manufacturers because these paints have a high resistance to scratches, which allows a glass to have a flange (impact face layer ( 1), that is, glass of a larger size than the glass of intermediate layers (2), as illustrated in Figure 1) easily installed in bulletproof car bodies. Glass flanges painted with glass enamels can be installed in direct contact with the vehicle body, without any high risk of scratching the black stripe. Armored vehicle assembly companies prefer that the thickness of the glass used in the impact face layer (1) be the same thickness as the glass with which the vehicles were originally made, since this feature allows the installation of bulletproof composite on vehicle bodies without the need to make changes to the body. Figure 3 illustrates how a bulletproof composite that has a flange is mounted on a vehicle door; the impact face layer (1), the intermediate layers (2), the adhesive layers (3) and the inner layer (4) that comprise the bulletproof composite can be appreciated. In addition, the black stripe (5) is shown on the perimeter; the thickness of the glass enamels is not proportional to the thickness of the other components in the drawing, the gasket (6) used to seal the inside of the vehicle from the outside when the bulletproof composite is in the upper position and the inside of the door and external panel (7).
    [0024] 0024 d) Bend the impact face layer (1) and the intermediate layers (2) simultaneously by means of gravity and temperature: once the impact face layer of glass and / or glass ceramics (1) and the intermediate layers (2) to be used in the ballistic composite are dimensioned and ground, these must be curved. The bulging process of the impact face layer (1) and the intermediate layer (2) of glass and glass ceramics must ensure perfect parallelism between the layers to be used. In Figure 4, a glass layer matrix configuration is shown schematically, which comprises a bulletproof composite, in order to be curved by gravity and temperature. As shown in Figure 4, the bulletproof composite is composed of glass in the impact face layer (1) and in two layers of the same type of glass used in the impact face layer (1) and intermediate layers (2) . During the simultaneous bulging process by gravity and temperature, each of the layers of glass that comprise the piece form a determined radius of curvature, calculated from the same center. For example: the glass layer of the impact face layer (1) forms a radius of curvature of 2,000 mm, one of the glass layers of the intermediate layer (2) forms a radius of curvature of 1,994 mm and the other a radius of curvature. curvature of 1,988 mm. The difference between the radii of curvature is necessary to ensure parallelism between the layers and to reduce the risk of breakage during the pressure and temperature lamination process.
    [0025] 0025 Figure 4 illustrates how the radii of curvature are calculated in each of the layers of glass, glass ceramics or ceramics that will be used in the bulletproof composite; as noted, the radius of curvature in each layer is different. Simultaneous bulging by gravity and temperature, in which glass and glass-ceramic materials are curved and annealed, is normally used during the production of bulletproof composite that uses the same type of glass and glass ceramics in the impact face layer (1) and in the intermediate layers (2) (Figure 1), because this increases the probability of having entirely parallel layers, avoiding the formation of spacing that causes ruptures during the pressure and temperature lamination process. Ceramic materials, in contrast to glass and glass ceramics, are not curved by gravity and temperature, but are instead sintered with the final shape to be used in curved bulletproof composites.
    [0026] 0026 Figure 5, using the same ballistic composite as Figure 4, is an example of how the lack of parallelism can be created between the layers of glass simultaneously curved by means of gravity and temperature. As can be seen in Figure 5, the glass layer in position (1) did not reach a radius of curvature of 2,000 mm necessary to ensure parallelism between the layers, but, on the contrary, it took a radius of curvature of 2,475 mm. Due to the above, this creates spacing between the layers, representing a high risk of breakage during the lamination process. Figure 5 also shows in “Detail A” (highlighted) the space between the glass layers in the impact face layer (1) and in the intermediate layers (2), which can be up to 3.1 mm. glass or glass ceramics have spaces such as those mentioned above (3.1 mm), the risk of breakage increases when subjected to pressure and temperature lamination, because glass and glass-ceramic materials are fragile materials that do not have a high degree The spacing between the layers allows the glass and / or glass-ceramic materials to deform during lamination and to produce breaks. Another possible defect generated due to the lack of parallelism between the layers is the optical distortion (magnification effect) generated when the spaces formed between the layers of glass curved by gravity and temperature are small enough that the glass layers do not break during lamination, but instead generate the mentioned optical distortion, which is an unwanted defect in bulletproof composites for automotive applications.
    [0027] 0027 The plastic materials used in the adhesive layers (3) and the inner layer (4) in Figure 1 must not be previously curved because they are ductile (they have a greater deformation capacity than the materials used in the impact face layer (1 ) and in the intermediate layers (2) of Figure 1 and, therefore, do not break during lamination).
    [0028] 0028 In order to reduce the risk of generating large spacing between the impact face layer (1) and the intermediate layers (2) (Figure 5), the bulging of these glass or glass ceramic layers is generally carried out simultaneously, using temperature and gravity in a process that takes something like 100 to 1,000 minutes; during this process, glass and glass-ceramic materials are also curved and annealed. The time intervals mentioned refer to the total residence time of the impact face layer (1) and the intermediate layers (2) inside the furnaces, so that they are simultaneously curved without breaking due to thermal shock, once that heating and cooling are carried out progressively. Materials swell when heated and contract when cooled, and therefore glass and glass-ceramic materials must be heated and cooled at rates that do not cause sudden volume changes. The maximum rate at which volume changes can be made to glass and glass-ceramic materials is determined by the thermal properties of each material. When glass or glass-ceramic materials break due to an excessively rapid change in volume, this is known as material failure due to thermal shock. If a given material is rapidly cooled, but not fast enough to cause it to rupture, the said material accumulates internal stresses, because the molecules do not reach thermodynamic equilibrium. Based on the above, it is understandable, therefore, that the time interval (100 to 1,000 minutes), through which the curvature of glass and glass ceramics by means of gravity and temperature, is quite large, given that depend on the thermal properties of the available material. When the glass and glass-ceramic materials are cooled down slowly enough, so that the material does not accumulate internal stresses, it is thus said that the material has been annealed. During flexion by gravity and temperature, the materials must be subjected to their softening temperature in order to be curved.
    [0029] 0029 Each type of glass and glass ceramics considered as an option in the impact face layer (1) and in the intermediate layers (2) (Figure 1) has its own softening temperature. For example: The softening temperature of soda-lime glass is 715 ° C, the softening temperature of borosilicate glass is 820 ° C, the softening temperature of alkaline aluminosilicate (SAS) is 904 ° Ç.
    [0030] 0030 The conventional manufacture of bulletproof composites is designed using the same material in the impact face layer (1) and in the intermediate layers (2) (Figure 1), so that all layers are curved simultaneously using the same temperature. The process described above allows the layers to be curved and annealed at the same time, using the same mold, and thus reducing the risk of spacing between layers, which causes ruptures. Said simultaneous bulging-annealing process of layers is not recommended for materials whose softening temperatures are different, since this reduces the optical quality of the materials by increasing the presence of markers that have lower softening temperatures, reduces the optimization of bulging process, since there is a need to wait for materials that have a higher softening temperature to acquire the final shape of the piece, and also increases the risk of spacing between layers. On the other hand, the simultaneous bulging-annealing of glass layers requires a slow cooling system (<10 ° C / minute) in order for the hot interfaces (in contact with the internal surfaces of glass or glass ceramics) to cool at rates similar to the cooling rate of surfaces in contact with air; these temperature differences between glass / glass, glass / air, glass / glass ceramics or glass / air interfaces can cause undesirable internal stresses that also lead to disruptions. Again, the time frames required for bulging-annealing of more than one layer of glass or glass ceramics by means of gravity and temperature require time periods ranging from 100 to 1,000 minutes. Therefore, there is a need to proceed to individual bulging of the intermediate layers by means of a semi-tempered or thermally reinforced bulging process, instead of a simultaneous bulging-annealing process.
    [0031] 0031 US 2010/0275767, which describes the production of bulletproof glass using glass ceramics in the impact face layer (1) (Figure 1) and at least one soda-lime glass or borosilicate glass in the intermediate layers ( 2) (Figure 1), it does not explain how to solve the problem of glass and / or glass ceramic materials flexing with different softening temperatures, without generating spacing between layers, which can lead to rupture. Thus, applications using the architecture illustrated in US 2010/0275767 are directed to flat parts, even when using the ion exchange process of WO 2007/032961. The state of the art does not consider the flexibility that the ion exchange process provides to the thin layers of the impact face, in order to enable the mechanical bulging during the pressure and temperature lamination with the intermediate layers.
    [0032] 0032 US 2012/0174761 discloses a transparent shielded laminate material that has a glass / ceramic glass or ceramic impact face, one or a plurality of glasses, glass ceramic or polymeric coating layer behind the face layer. impact, one or a plurality of splinter containment layers behind the cladding layers and a thin glass layer laminated to the impact face, where the thin glass cover is <3mm thick. US 2012/0174761 does not consider a material-architecture combination that provides a pressure and heat lamination process for the impact face layer, the intermediate layers, the adhesive materials and the internal plastic layer, during a lamination process through low heat (temperature) and pressure. This document does not suggest composites with different materials in the impact face layer and in the intermediate layers, to be used in curved bulletproof compositions. Contrary to the state of the art, the present invention provides a better ballistic performance for the impact face, which uses a thin covering as the impact face, and being a curved transparent shielding system that uses materials with different softening temperatures incorporated into the system. .
    [0033] 0033 e) Perform an ion exchange process of one or more glass and / or glass-ceramic materials of the impact face layer (1) and intermediate layers (2): ion exchange is a chemical process, through which the ions of a certain size is extracted from glass or glass ceramics, and larger ones are introduced. The incorporation of larger ions in the molecular structure of glass and glass-ceramic materials generates compressive stresses on the glass or glass ceramic surface. The thickness of the compression stress generated is known as "layer depth or depth case - DOL," and represents the depth reached by these larger ions, through the glass or glass ceramic surface. Figure 6 illustrates the exchange of potassium and sodium ions between glass and a given salt.4 The state of the art reveals the relationship that exists between ion exchange and ballistic properties of glass and glass-ceramic materials, WO 2007/032961 discloses how ion exchange has evolved and how this process can be used in bulletproof compositions. In addition, the state of the art also describes how ion exchange increases the mechanical strength in glass and glass-ceramic materials in percentages above 200%, making them more resistant WO 2007/032961 considers the application of the ion exchange process only to the coating layers and not to the impact face layer. 61 claims an impact face layer with sufficient energy absorbing capacity and energy dissipating properties to reduce radial tensile stresses and rim tensile stresses caused by a reduced impact of at least 30,000 psi. Performing an ion exchange process in the impact face layer of WO 2007/032961, the thickness of this layer would be greater than the limit required by the present invention and would significantly increase the weight of the composition. In addition, WO 2007/032961 suggests a glass ceramic material as an impact face, in which a person skilled in the art would recognize that an ion exchange process is not possible to be carried out on glass-ceramic materials. No state of the art is found that describes how ion exchange can increase the flexibility of some types of glass and glass-ceramic materials to the extent that these materials can be included in bulletproof composites without the need to bulge them by gravity and temperature, but only mechanically, during pressure and temperature lamination, and to provide the layers with the necessary flexibility to be able to be mechanically curved.
    [0034] 0034 f) Assemble the impact face layer (1), the intermediate layers (2), the adhesive layers (3) and the inner layer (4): in this step, the impact face layer already curved (1) and the intermediate layers (2) are placed in the order in which they will be laminated. Adhesive layers (3) are placed between them. As an inner layer (4), a flat or curved plastic sheet is placed. Subsequently, the materials are taken to the autoclave in the order in which they were placed, in order to be laminated by pressure and temperature.
    [0035] 0035 g) Finally, laminate the materials by pressure and temperature inside an autoclave. The materials are subjected to a pressure that varies between 0.69 and 1.03 MPa (100 and 150 psi) and a temperature between 85 ° C and 135 ° C, which lead to the union of the impact face layer (1), the intermediate layers (2) and the inner layer (4) with the adhesive layers (3). In this step, the inner layer (4) is curved by means of pressure and temperature. However, it is also known that it is possible to laminate without pressure when EVA is used as an adhesive (3).
    [0036] 0036 In view of the above, it can be seen that the state of the art does not provide any information about the flexibility that ion exchange provides to materials, and the way in which this property can be used so that said materials are mechanically curved during the pressure and temperature lamination. In addition, the state of the art also does not disclose that composites in which one type of material is used in the impact face layer (1) and a different material is used in the intermediate layers (2) are not intended to be used in composite materials. bullet proof curved, the state of the art does not provide the chemical and physical characteristics for the impact face layer, to facilitate mechanical curvature. The state of the art does not consider the possibility of carrying out individual bulging of the intermediate layers (2) by means of a semi-tempered or thermally reinforced bulging process, instead of a simultaneous annealing-bulging process. Finally, the state of the art does not consider the ion exchange process to increase the flexibility of glass materials to the point that these materials can be included in bulletproof composites, without the need to bulge them by means of gravity and temperature, but only mechanically during temperature and pressure lamination. The state of the art does not consider a material-architecture combination that provides adequate parallelism between the impact face layer and the intermediate layers, avoiding the space between these layers and avoiding breaks during the heat and pressure cycles required for the curved lamination process . Therefore, there is a need to provide an ion exchange process for thin layers of impact face, in order to provide sufficient flexibility to allow mechanical bulging for this layer, without the use of techniques that require heating the material and achieve its softening point. 3. BRIEF DESCRIPTION OF THE DRAWINGS
    [0037] 0037 Figure 1 shows a cross section of an example of a bulletproof clear glass composite design.
    [0038] 0038 Figure 2 shows a cross section of an example of a design of a transparent bulletproof glass composite, in which two layers of plastic are used (4).
    [0039] 0039 Figure 3 outlines how a curved bulletproof composite containing a flange can be mounted on a vehicle door.
    [0040] 0040 Figure 4 illustrates how the radii of curvature of the different layers of material are measured, which comprise a curved bulletproof composite.
    [0041] 0041 Figure 5 shows the lack of parallelism between the layers of material that occupy the layer of the impact face (1) and the intermediate layers (2) in a deficient bulging process.
    [0042] 0042 Figure 6 illustrates the exchange of sodium and potassium ions between the glass and a salt.
    [0043] Figures 7a and 7b illustrate two embodiments of the present invention.
    [0044] 0044 Figure 8 illustrates the process steps of the present invention. 4. BRIEF DESCRIPTION OF THE INVENTION
    [0045] 0045 Referring to the embodiments illustrated in Figures 7a and 7b, the present invention describes a curved bulletproof composite having glass, glass ceramics or flexible ceramics in the impact face layer (10), so as to be mechanically curved during a lamination process through low heat (temperature) and pressure. Composites can be made of one or more layers of glass, glass ceramics or ceramics curved by gravity and heat in one or more intermediate layers (20). The purpose of the adhesive materials (30) and the inner plastic layer (40) is the same as the purpose described for the adhesive materials (3) and inner plastic layer (4) of the prior art.
    [0046] In addition, the present invention describes a process for the production of glass of the present invention, comprising the following steps:
    [0047] 0047 a) (100) dimension (cut) the glass or glass ceramics of the impact face layer (10) and intermediate layers (20) according to the geometry or shape of the curved bulletproof composite. Sinter the ceramic material of the impact face layer (10) according to the shape of the curved bulletproof composite to be produced.
    [0048] 0048 b) (110) finishing the edge of the glass, the glass ceramic or ceramic, that is, the impact face layer (10) and intermediate layers (20);
    [0049] 0049 c) (120) individually bend the intermediate layers (20) of glass or glass ceramic by means of gravity and temperature;
    [0050] 0050 d) (130) perform an ion exchange process of one or more glasses and / or glass-ceramic materials of the impact face layer (10) and intermediate layers (20);
    [0051] 0051 e) (140) paint the black stripe with organic paint on the impact face layer (10) and / or one of the intermediate layers (20);
    [0052] 0052 f) (150) assemble the impact face layer (10), the intermediate layers (20), the adhesive materials (30) and the internal plastic layer (40); and
    [0053] 0053 g) (160) bend mechanically, during the pressure and heat lamination, the impact face layer (10), the intermediate layers (20), the adhesive materials (30) and the internal plastic layer (40). 5. DETAILED DESCRIPTION OF THE INVENTION
    [0054] 0054 The production of flat bulletproof glass using glass-ceramic materials in the impact face layer (1) and borosilicate glass, pure silica and "silica glass" in the intermediate layers (2) (Figure 1), is already disclosed in the order United States Patent No. 2010/0275767. However, the state of the art does not solve the problem of bulging the material using different softening temperatures, as well as having adequate parallelism between the impact face layer (10) and intermediate layers (20) (Figure 5) and avoid spacing that leads to rupture during a heat and pressure lamination process. The state of the art does not consider the ion exchange process to increase the flexibility of glass materials to the extent that these materials can be included in bulletproof composites, without the need to bulge them by means of gravity and temperature, but only mechanically, during lamination by pressure and temperature. 5.1. Product
    [0055] 0055 The present invention solves the problem of producing curved bulletproof glass when glass, glass ceramic or sufficiently flexible ceramic is used in the impact face layer (10) of the bulletproof composite in order to be mechanically curved during a pressure and heat lamination process, normally carried out in a range between 0 and 1.52 MPa (0 to 220 psi) and a temperature range between 80 and 140 ° C.
    [0056] 0056 Furthermore, the present invention solves the problem of producing bulletproof composites, which incorporate glass, glass ceramics or ceramics in the impact face layer (10), which have a different softening temperature than that of glass, glass-ceramic materials or ceramics used in the intermediate layers (20) (Figure 7). Given the ion exchange process of the present invention, which will be detailed below, the material selected in the impact face layer (10) acquires the necessary flexibility to adopt the curvature given to the intermediate layers (20) by gravity and temperature, without the need to use other temperature and pressure ranges during the autoclaving process.
    [0057] 0057 Referring to Figure 7a, the curved bulletproof composite of the present invention can be made of an impact face layer (10), at least one intermediate layer (20) and an inner plastic layer (40), joined by adhesive materials (30). When referring to "an element" or "a layer" or "a material", it must necessarily be understood to include the possibility of having one or more of these elements. In a preferred embodiment of the invention, the preferred material to be used in the layer of the impact face (10) is an alkaline aluminosilicate with ion exchange, it should be understood that the group of alkaline aluminosilicate materials comprises lithium aluminosilicate, sodium aluminosilicate or any other aluminosilicate material made from the group of alkaline materials.
    [0058] In the present invention, the amount of sodium oxide (Na2O) or any other oxide including sodium (Na) in its chemical formula can vary between 0 and 30%. In a preferred embodiment, the suggested chemical composition for sodium aluminosilicate (SAS) can be 61% SiO2, 16% AI2O3, <1% B2O3, 13% Na2O, 4% K2O, <1 % CaO and 4% MgO or any other that allows said material to acquire the necessary flexibility and mechanical strength after the ion exchange process to be curved during the rolling process, without breaking. In the preferred embodiment shown in Figure 7a, the thickness of the impact face layer (10) can preferably be less than or equal to 3 mm (≤ 3 mm), the depth reached during the greater ion exchange (DOL) process or equal to 30 μm (≥ 30 pm) and the compression stress equal to or greater than 300 MPa (≥ 300 MPa).
    [0059] 0059 Another preferred material to use on the impact face layer (10) is lithium aluminum silicate (LAS) with ion exchange. In the present invention, the amount of lithium oxide (LiO2) or any other oxide including lithium (Li) in its chemical formula can vary between 0 and 20%. In a preferred embodiment, the suggested chemical composition for lithium aluminum silicate (LAS) can be 67.2% SiO2, 20.1% Al2O3, 3.2% LiO2, 1.1% MgO, 0.05% CaO, 0.9% BaO, 1.7% ZnO, 0.4% Na2O, 0.3% K2O, 2.7% TiO2 and 1.7% ZrO2 or any another that allows said material to acquire the necessary flexibility and mechanical strength after the ion exchange process to be curved during the rolling process, without breaking. In the preferred embodiment shown in Figure 7a, the thickness of the impact face layer (10) can preferably be less than or equal to 3 mm (≤ 3 mm), the depth reached during the greater ion exchange (DOL) process or equal to 50 pm (≥ 50 pm) and the compression stress equal to or greater than 400 MPa (≥ 400 MPa).
    [0060] 0060 An important improvement in scratch resistance is achieved when a glass or chemically reinforced glass ceramic is used as the impact face layer (1) in bulletproof composites, because the compressive stresses incorporated into the glass or glass-ceramic materials make it more It is difficult for scratches to be generated. In addition, compression stresses can prevent or delay the propagation of pre-existing cracks in the impact face layer. As a result, the rupture of this layer can be avoided. For example, soda-lime glass can have a layer depth of about 25 to 30 microns and compression stresses between 400 and 600 MPa. Thus, with the addition of new materials such as alkaline aluminosilicates and lithium aluminosilicates as the impact face layer (1), in which the DOL can be up to 1,000 microns and the compressive stresses up to 1,000 MPa, the possibilities of breakages scratches on the impact face layer are reduced.
    [0061] 0061 In other types of curved bulletproof composites of the present invention, it is possible to use soda-lime glass with ion exchange in the impact face layer (10). In the present invention, the minimum content of silicon oxide (SiO2) or any other oxide including silicon (Si) in its chemical formula can be 50%. In a preferred embodiment of the present invention, the chemical composition of soda-lime glass can be 73% SiO2, 14% Na2O, 9% CaO, 4% MgO, 0.15% Al2O3, 0.03% K2O , 0.02% of TiO2 and 0.1% of Fe2O3 or any other that allows the referred material, after being subjected to ion exchange, to obtain the flexibility and the mechanical resistance necessary to bend during the lamination process. The thickness of the material used in the impact face layer (10) can be less than or equal to 3 mm (≤ 3 mm), the depth reached during the ion exchange process (DOL) greater than or equal to 15 μm (≥ 15 μm ) and the compressive stress equal to or greater than 200 MPa (≥ 200 MPa).
    [0062] 0062 In other types of curved bulletproof composite of the present invention, it is possible to use borosilicate glass with ion exchange in the impact face layer (10). In the present invention, the minimum content of boron trioxide (B2O3) or any other boron oxide including (B) in its chemical formula varies between 0 and 25%. In a preferred embodiment of the present invention, the chemical composition of borosilicate glass can be 81% SiO2, 4% Na2O / K2O, 2% Al2O3, 13% B2O3 or any other that allows said material, after being subjected to ion exchange, acquire the flexibility and mechanical strength necessary to bend during the lamination process. The thickness of the material used in the impact face layer (10) can be less than or equal to 3 mm (≤ 3 mm), the depth reached during the ion exchange process (DOL) greater than or equal to 5 pm (≥ 5 pm ) and the compression stress equal to or greater than 100 MPa (≥ 100 MPa).
    [0063] 0063 Alkaline aluminosilicate (SAS), lithium aluminosilicate (LAS), soda-lime glass and borosilicate glass can be used in the impact face layer (10) with a thickness greater than 3 mm (> 3 mm). However, in these cases, the bulging of that layer is not carried out by pressure and heat (0 to 1.52 MPa; 80 to 140 ° C) during lamination, but, instead, individually by means of gravity and temperature, during the bulging process.
    [0064] 0064 The preferred materials for use in the intermediate layers are soda-lime glass with or without ion exchange, borosilicate glass and fused silica (SiO2, content> 95%). However, it is possible in other embodiments to use preferred materials of the impact face layer (10) in the intermediate layers (20).
    [0065] 0065 Alternatively, the design of bulletproof composites can incorporate several layers of one or different plastic materials as internal layers (4). Figure 2 shows a configuration in which two layers of plastic are used. The article “Ballistic Properties of Hybrid Systems for Transparent Armor Applications”, written by John W. Song et al. reveals the synergistic effect of combinations that mix rigid / soft plastic materials as a shattering shield in position (4) of Figure 2. This way, with the incorporation of this hybrid concept, an improvement in ballistic performance of bulletproof composites with the same area density. 5.2. Process
    [0066] 0066 As noted above, the technique describes in detail the fundamental steps in the production process of curved bulletproof glass using soda-lime or borosilicate glass in the impact layer glass (1) and in the intermediate layers (2) (Figure 1), as mentioned above.
    [0067] Referring to figure 8, the method by which the curved bulletproof composites of the present invention are produced is described. The steps are:
    [0068] 0068 a) (100) dimension (cut) the glass or glass ceramics of the impact face layer (10) and the intermediate layers (20) according to the geometry or shape of the curved bulletproof composite. Sinter the ceramic material of the impact face layer (10) according to the shape of the curved bulletproof composite to be produced.
    [0069] 0069 b) (110) finish the edge of the glass, the glass ceramic or ceramic, that is, the impact face layer (10) and intermediate layers (20);
    [0070] 0070 c) (120) individually bend the intermediate layers (20) of glass or glass ceramic by means of gravity and temperature;
    [0071] 0071 d) (130) perform an ion exchange process of one or more glasses and / or glass-ceramic materials of the impact face layer (10) and intermediate layers (20);
    [0072] 0072 e) (140) paint the black stripe with organic paint on the impact face layer (10) and / or one of the intermediate layers (20);
    [0073] 0073 f) (150) assemble the impact face layer (10), the intermediate layers (20), the adhesive materials (30) and the internal plastic layer (40); and
    [0074] 0074 g) (160) bend mechanically, during the pressure and heat lamination, the impact face layer (10), the intermediate layers (20), the adhesive materials (30) and the internal plastic layer (40).
    [0075] 0075 As can be seen, the differences in relation to the state of the art lie, in part, in the order of steps c), e) and g); that is, they present modifications and alter their order in order to make possible the production of curved bulletproof glass, which involves glass or glass-ceramic materials in the impact face layer (10), different from the glass or glass-ceramic materials used in intermediate layers (20). The steps c), e) and g) of the present invention will be described in detail and the modifications contemplated in each step of the same.
    [0076] 0076 c) Bend the intermediate layers (20) of glass or glass ceramic (120) individually by means of gravity and temperature: as mentioned in the prior art, the bulging of the glass and glass ceramic layers is carried out at the same time ( bulging-annealing) to ensure parallelism. The process can take between 100 and 1,000 minutes, because it requires a slow cooling system in order to allow the glass / glass, glass / glass ceramic or glass ceramic / glass ceramic interfaces, which cool down more slowly than the glass / air or glass / air ceramic interfaces, have cooling rates lower than the maximum temperature gradient allowed by the material, in order to avoid failures due to thermal shock. The simultaneous bulging of layers of glass or glass ceramics forces manufacturers of bulletproof materials to design ballistic formulas with the same materials, both in the impact face layer (10) and in the intermediate layers (20), in order to have the same softening temperature of the materials during simultaneous bulging by means of gravity and temperature, thus decreasing the presence of optical defects due to excess markings during the bulging process, which happens when materials with different softening temperatures are simultaneously curved .
    [0077] 0077 The present invention solves the problem of lack of parallelism between the layers of glass or glass ceramics used in intermediate layers (20), which must be curved by means of gravity and temperature by performing the individual curvature of each layer in an oven horizontal heat quenching where the pieces are curved and semi-tempered or thermally reinforced individually, in such a way that the hot glass / glass, glass ceramic / glass or glass ceramic / glass ceramic interfaces are eliminated when more than one layer is curved. The parallelism of the intermediate layers (20) is ensured by the use of a special mold, which allows better control of the shape of the glass or glass ceramic layers to be used in the intermediate layers (20) during the bulging / semi-tempering or thermal reinforcement process. The above description allows the time required for the temperature and gravity bulging process to be reduced, so that the production time of curved bulletproof glass is reduced and the costs related to the bulging of intermediate layers (20) are reduced. optimized. Therefore, production capacity and energy savings increase in the production of curved bulletproof parts.
    [0078] 0078 The bulging / semi-tempering or thermal reinforcement process, performed by individually bending the layers of material used in the intermediate layers (20), allows fragments of these curved / semi-tempered or thermally reinforced materials to be similar in size to those obtained from curved- annealed (simultaneous bulging of layers). The above description is important in order not to lose the ability to withstand multiple impacts, which is very relevant in the design of bulletproof composites.
    [0079] 0079 e) Paint the black stripe (140) using organic or inorganic paint on the impact face layer (10) and / or one of the intermediate layers (20): in the state of the art, the production of the black stripe in the required perimeter in bulletproof composites with glass enamels and which are usually located on the glass used in the impact face layer (10), reduce the mechanical strength of the glass by percentages greater than 60%. The foregoing forces bulletproof glass manufacturers to design bulletproof composites with thick glass on the impact face layer (10). In addition, it is known as ion exchange increases the mechanical strength of glass and glass ceramics.
    [0080] 0080 In order to avoid the loss of mechanical resistance in glass and ion-exchange glass-ceramic materials used in the impact face layer (10), it is necessary to make the black stripe on the perimeter with organic paint that does not reduce the said mechanical properties of the glass or of the glass ceramic used in the impact face layer (10).
    [0081] 0081 g) Press and heat laminate the impact face layer (10), the intermediate layers (20), the adhesive materials (30) and the inner plastic layer (40) and bend mechanically by means of pressure and temperature at impact face layer (10), ion exchange material and the inner plastic layer (40): the bulging-annealing process of the impact face layer (10) and the intermediate layers (20) is generally carried out simultaneously through gravity and temperature. However, it was explained how this simultaneous bulging process requires that the materials to be used in the impact face layer (10) and in the intermediate layers (20) be the same, in order to avoid the lack of parallelism between the layers and avoid optical defects produced by excessive markings when materials with different softening temperatures are simultaneously curved.
    [0082] 0082 The present invention takes advantage of the greater mechanical resistance and flexibility that the ion exchange process confers to glass and glass ceramics, in order to incorporate them in the impact face layer (10) of bulletproof glass. Therefore, the materials that will be used in the impact face layer (10) can be introduced flat in the pressure and heat lamination process, which can normally vary between 0 and 1.52 MPa and between 80 and 140 ° C. During the lamination process, the pressure inside the isobaric autoclave forces the materials of the impact face layer (10) to assume the curvature of the previously curved and semi-tempered or thermally reinforced material of the intermediate layers (20).
    [0083] 0083 Example 1: Figure 7a illustrates a composite that uses alkaline aluminosilicate (SAS), lithium aluminosilicate (LAS) or soda-lime glass with a thickness that varies between 2 and 3 mm, with ion exchange in the impact face layer (10), mechanically curved during the heat and pressure lamination process, a layer of borosilicate glass, with a thickness ranging between 9 and 13 mm in the intermediate layers (20), without exchange ionic and curved / semi-tempered or thermally reinforced by gravity and temperature, a layer of polycarbonate with a thickness that varies between 1 and 3 mm in the inner plastic layer (40) and adhesive layers (30) of polyurethane with a thickness between 0 , 3 and 3.1 mm. The composite described is in compliance with the requirements established by NIJ 0108.01 for level III A, with a thickness ranging from 14 to 17 mm; the standard formula used to meet the requirements of level III A of the same standard has a thickness of 21 mm and, therefore, the thickness and weight reduction can vary between 19 and 33%, preferably a weight reduction of 29% and a 26% reduction in thickness. In addition, the individual bulging / semi-tempering process or thermal reinforcement of the intermediate layers (20) can be carried out 10 times faster than the simultaneous bulging-annealing, and thus represent energy and cost savings in glass production at the same time. bulletproof and an increase in the production of curved bulletproof composites.
    [0084] 0084 Example 2: Figure 7a illustrates a composite that uses alkaline aluminosilicate (SAS), lithium aluminosilicate (LAS) or soda-lime glass with a thickness that varies between 2 and 3 mm, with ion exchange in the impact face layer (10), a layer of soda-lime glass with a thickness that varies between 8 and 14 mm in the intermediate layers (20), with ion exchange and curved / semitempered or thermally reinforced by means of of gravity and temperature, a layer of polycarbonate with a thickness that varies between 1 and 3 mm in the inner plastic layer (40) and adhesive layers of polyurethane (30) with a thickness between 0.3 and 3.1 mm. The composite described is in compliance with the requirements established by NIJ 0108.01 for level III A, with a thickness ranging from 14 to 18 mm; the standard formula used to meet the level III A requirements of the same standard has a thickness of 21 mm and, therefore, the thickness and weight reduction can vary between 0 and 30%.
    [0085] 0085 Example 3: Figure 7b illustrates a composition that uses alkaline aluminosilicate (SAS), lithium aluminosilicate (LAS) or soda-lime glass with a thickness that varies between 2 and 3 mm, with ion exchange in the impact face layer (10), two layers of borosilicate glass with a thickness varying between 5 and 13 mm in the intermediate layers (20), without ion exchange and curved / semi-tempered or thermally reinforced by means of gravity and temperature, a layer of polycarbonate with a thickness that varies between 1 and 6 mm in the inner plastic layer (40) and adhesive layers of polyurethane (30) with a thickness between 0.3 and 3.1 mm. The composite described is in compliance with the requirements established by the NIJ 0108.01 standard exceeding level III A, and offers thickness and weight reduction that varies between 20 and 35%.
    [0086] 0086 The foregoing comprises a complete and detailed disclosure of various embodiments of the concept of the invention claimed herein. Anyone skilled in the art will understand that variations can exist without departing from the scope and spirit of the invention. The inventive concept claimed here is defined only by the scope of the following claims, which must be interpreted according to what was revealed in the detailed specification.
    权利要求:
    Claims (13)
    [0001]
    Curved bulletproof composite, comprising: an impact face layer (10) of alkaline aluminosilicate glass, soda-lime glass or borosilicate glass, subjected to an ion exchange process, and having a thickness less than or equal to 3mm; one or more intermediate layers of glass or ceramic glass (20); an inner layer of plastic (40); and an adhesive material (30) disposed between the impact face layer (10), the intermediate layers (20) and the inner plastic layer (40); characterized by the fact that the impact face layer (10) has a different softening temperature than that of the glass or ceramic glass used in the intermediate layers (20); and where the impact face layer (10) is mechanically curved to adopt the curvature given for the intermediate layers of glass or glass-ceramic (20).
    [0002]
    Curved bulletproof composite according to claim 1, characterized in that the alkaline aluminosilicate materials include materials selected from the group consisting of lithium aluminosilicate, sodium aluminosilicate or any other aluminosilicate from the group of alkaline materials.
    [0003]
    Curved bulletproof composite according to claim 1, characterized by the fact that the amount of sodium oxide (Na2O) or any other oxide that includes sodium (Na) in its chemical formula varies between 0 and 30%.
    [0004]
    Curved bulletproof composite according to claim 1, characterized by the fact that the amount of lithium oxide (LiO2) or any other oxide that includes lithium (Li) in its chemical formula varies between 0 and 20%.
    [0005]
    Curved bulletproof composite according to claim 1, characterized by the fact that the amount of silicon oxide (SiO2) or any other oxide that includes silicon (Si) in its chemical formula varies between 0 and 50%.
    [0006]
    Curved bulletproof composite according to claim 1, characterized by the fact that the amount of boron trioxide (B2O3) or any other oxide that includes boron (B) in its chemical formula varies between 0 and 25%.
    [0007]
    Curved bulletproof composite according to claim 1, characterized by the depth of ions reached during the ion exchange process (DOL) in the impact face layer (10) of a lithium aluminum silicate glass being greater than or equal to 50 μm (≥ 50 μm) and compression stresses equal to or greater than 400 MPa (≥ 400 MPa).
    [0008]
    Curved bulletproof composite according to claim 1, characterized by the depth of ions reached during the ion exchange process (DOL) in the impact face layer (10) of a sodium aluminosilicate glass being greater than or equal to 30 μm (≥ 30 μm) and compression stresses equal to or greater than 300 MPa (≥ 300 MPa).
    [0009]
    Curved bulletproof composite according to claim 1, characterized by the depth of ions reached during the ion exchange process (DOL) in the impact face layer (10) of a soda-lime glass to be greater than or equal to 15 μm (≥ 15 μm) and the comprehension stresses equal to or greater than 200 MPa (> 200 MPa).
    [0010]
    Curved bulletproof composite according to claim 1, characterized by the ion depth reached during the ion exchange process (DOL) in the impact face layer (10) of a borosilicate glass being greater than or equal to 5 μm (≥ 5 μm) and compression stresses equal to or greater than 100 MPa (≥ 100 MPa).
    [0011]
    Curved bulletproof composite according to claim 1, characterized in that the intermediate layers of glass or glass-ceramic are comprised of materials selected from the group consisting of alkaline aluminosilicate glass, soda-lime glass, borosilicate glass and fused silica.
    [0012]
    Curved bulletproof composite according to claim 11, characterized by the alkaline aluminum silicate materials, including materials selected from the group consisting of lithium aluminum silicate, sodium aluminum silicate or any other aluminum silicate from the group of alkaline materials.
    [0013]
    Process for bending a bulletproof composite comprised of an impact face layer (10) of alkaline aluminosilicate glass, soda-lime glass or borosilicate glass, subjected to an ion exchange process, and having a thickness less than or equal to 3mm ; one or more intermediate layers of glass or glass-ceramic (20); an inner layer of plastic (40); and an adhesive material (30) disposed between each of the aforementioned layers (10), (20) and (40); characterized by understanding the following steps: a) individually bend, through gravity and temperature, the intermediate layers of glass or glass-ceramic (20); and b) mechanically bend the impact face layer (10) and the inner plastic layer (40) during the pressure and temperature lamination of the impact face layer (10), with the intermediate layers curved in step a), the adhesive materials (30) and the inner plastic layer (40), where the impact face layer (10) has a different softening temperature than that of the glass or ceramic glass used in the intermediate layers (20).
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    同族专利:
    公开号 | 公开日
    WO2013168125A3|2014-02-27|
    IL250503D0|2017-04-02|
    US20130302581A1|2013-11-14|
    MX363544B|2019-03-27|
    MX2014013694A|2015-09-07|
    US8865300B2|2014-10-21|
    US20160023938A1|2016-01-28|
    WO2013168125A2|2013-11-14|
    ZA201409033B|2015-09-30|
    IL235575D0|2015-01-29|
    EP2846997B1|2019-01-02|
    PE20141962A1|2014-12-17|
    IL235575A|2017-06-29|
    IL250503A|2020-07-30|
    BR112014027982A2|2017-06-27|
    US9950944B2|2018-04-24|
    CO6790239A1|2013-11-14|
    EP2846997A2|2015-03-18|
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    法律状态:
    2018-03-06| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2018-03-13| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
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    PCT/IB2013/053775|WO2013168125A2|2012-05-09|2013-05-09|Curved bullet proof glass made of glass, glass-ceramic or ceramic mechanically curved on the strike-face layer|
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