Dark black double-silver coated laminated glass for automobile awning and preparation method of dark black double-silver coated laminated glass

Abstract

The invention belongs to the technical field of coated glass, and particularly discloses dark black double-silver coated laminated glass for an automobile awning and a preparation method. The problem that the LOW-E coated glass cannot be exposed to the air for a long time is effectively solved. Comprising an outer glass substrate with the thickness of 2.1 mm, a dark black PVB glue layer and an inner glass substrate with the thickness of 1.6 mm, and a first film layer, a second film layer, a third film layer, a fourth film layer, a fifth film layer, a sixth film layer, a seventh film layer, an eighth film layer, a ninth film layer, a tenth film layer, an eleventh film layer, a twelfth film layer and a thirteenth film layer are sequentially arranged on the outer glass substrate outwards; the third, sixth, eighth and eleventh film layers are made of AZO, the second and seventh film layers are made of ZTO, the first and twelfth film layers are made of Si3N4, the fifth and tenth film layers are made of NiCr, the fourth and ninth film layers are made of Ag, and the thirteenth film layer is made of ZrO2. The device can be stably placed for a long time, and the double-silver utilization rate is increased.

Description

Technical Field

[0001] The invention belongs to the technical field of coated glass, and in particular relates to a deep black double-silver coated laminated glass for automobile skylights and a preparation method thereof. Background Art

[0002] The current requirements for automotive glass are no longer just the ordinary requirements of expanding vision and shielding from wind and rain, but also the performance requirements of aesthetics, protection and energy saving. Therefore, low-emissivity coated glass (LOW-E coated glass) containing a silver film layer used in automotive skylights has emerged.

[0003] LOW-E coated glass, also known as low-radiation glass, is a film product composed of multiple layers of metal or other compounds coated on the glass surface. Its coating layer has the characteristics of high transmittance of visible light and high reflection of mid- and far-infrared rays, making it have excellent heat insulation effect and good light transmittance compared with ordinary glass and traditional coated glass. However, since LOW-E coated glass contains a silver film layer, it cannot be exposed to the air for a long time. Summary of the invention

[0004] One object of the present invention is to provide a deep black double silver coated laminated glass for automobile skylights, which effectively solves the problem that LOW-E coated glass cannot be exposed to the air for a long time.

[0005] In order to solve the above technical problems, the technical solution adopted by the present invention is:

[0006] A deep black double silver-coated laminated glass for an automobile skylight comprises an outer glass substrate, a PVB adhesive layer and an inner glass substrate, wherein the outer glass substrate and the inner glass substrate each comprise a first surface and a second surface opposite to each other, a coating film layer is arranged on the first surface of the outer glass substrate, and the coating film layer comprises a first film layer, a second film layer, a third film layer, a fourth film layer, a fifth film layer, a sixth film layer, a seventh film layer, an eighth film layer, a ninth film layer, a tenth film layer, an eleventh film layer, a twelfth film layer and a thirteenth film layer arranged in order from the first surface of the outer glass substrate to the outside.

[0007] The PVB adhesive layer is dark black and is arranged between the thirteenth film layer and the second surface of the inner glass substrate.

[0008] The materials of the third film layer, the sixth film layer, the eighth film layer and the eleventh film layer are all AZO, the materials of the second film layer and the seventh film layer are all ZTO, the materials of the first film layer and the twelfth film layer are all Si3N4, the materials of the fifth film layer and the tenth film layer are all NiCr, the materials of the fourth film layer and the ninth film layer are all Ag, and the material of the thirteenth film layer is ZrO2.

[0009] The outer glass substrate is a plain white glass substrate with a thickness of 2.1 mm, the inner glass substrate is a plain white glass substrate with a thickness of 1.6 mm, and the thickness of the dark black PVB adhesive layer is 0.76 mm.

[0010] Further, the thickness of the first film layer is 8 to 10 nm, the thickness of the second film layer is 22 to 25 nm, the thickness of the third film layer is 7 to 10 nm, the thickness of the fourth film layer is 5 to 8 nm, the thickness of the fifth film layer is 0.5 to 2 nm, the thickness of the sixth film layer is 10 to 13 nm, the thickness of the seventh film layer is 57 to 60 nm, the thickness of the eighth film layer is 10 nm, the thickness of the ninth film layer is 13 to 16 nm, the thickness of the tenth film layer is 0.5 to 2 nm, the thickness of the eleventh film layer is 10 to 11 nm, the thickness of the twelfth film layer is 20 to 22 nm, and the thickness of the thirteenth film layer is 4 to 7 nm.

[0011] Furthermore, the third film layer, the sixth film layer, the eighth film layer and the eleventh film layer are formed by magnetron sputtering using aluminum-doped zinc oxide as a target material, the first film layer and the twelfth film layer are formed by magnetron sputtering using rotated silicon as a target material, the thirteenth film layer is formed by magnetron sputtering using zirconium oxide as a target material, and the second film layer and the seventh film layer are formed by magnetron sputtering using zinc tin oxide as a target material.

[0012] Another object of the present invention is to provide a method for preparing the deep black double silver-coated laminated glass for automobile skylights as described in the above embodiment, comprising the following steps: S1, coating target material: silicon aluminum alloy, zinc aluminum alloy, nickel chromium alloy, silver, zinc tin oxide and zirconium oxide are sintered respectively on the target position of the vacuum magnetron sputtering chamber of the glass coating machine, the chamber is evacuated, the process gas is passed, and the target is burned for standby use.

[0013] S2. Pretreatment of glass: placing the inner glass substrate and the outer glass substrate to be coated under vacuum, dehumidifying and degassing the inner glass substrate and the outer glass substrate to be coated, so as to reduce the moisture and gas deposited on the surfaces of the outer glass substrate and the inner glass substrate.

[0014] S3, coating treatment: sending the outer glass substrate after the dehumidification and degassing treatment in step S2 into the vacuum magnetron sputtering chamber of the glass coating machine, and coating the first surface of the outer glass substrate with a first film layer, a second film layer, a third film layer, a fourth film layer, a fifth film layer, a sixth film layer, a seventh film layer, an eighth film layer, a ninth film layer, a tenth film layer, an eleventh film layer, a twelfth film layer and a thirteenth film layer in sequence from bottom to top to obtain coated glass.

[0015] S4, sintering treatment: sinter the coated glass at 650°C for 400 seconds.

[0016] S5. Lamination treatment: using 0.76 mm dark black PVB as a glue layer to perform lamination treatment between the thirteenth film layer on the outer glass substrate and the second surface of the inner glass substrate to obtain a dark black double silver-coated laminated glass.

[0017] Furthermore, before the sintering treatment in step S4, the visible light transmittance of the coated glass is ≥59%, and the visible light reflectance of the coated glass is ≤7%; after the sintering treatment in step S4, the visible light transmittance of the coated glass is ≥73%, and the visible light reflectance of the coated glass is ≤7%.

[0018] Furthermore, after the lamination process in step S5, the visible light transmittance of the laminated glass is ≥38%, and the visible light reflectivity of the laminated glass is ≤15%.

[0019] Furthermore, the haze of the deep black double silver-coated laminated glass is 0.36%, the shading coefficient is 13.1%, and the total solar energy transmittance is 10.6%.

[0020] Compared with the prior art, the beneficial technical effects of the present invention are:

[0021] (1) The dark black double silver coated laminated glass provided by the present invention has a reasonable arrangement of the film layer structure, which not only enhances the bonding force between different film layers, but also plays a good role in preventing sodium ion diffusion and protecting the silver particle layer, and has better anti-oxidation performance. Therefore, the present invention can be placed stably for a long time (placed in the air for about one month), which is conducive to subsequent processing and improves the utilization rate of double silver; at the same time, it has an SC value and TTS value that are better than ordinary laminated glass, so that the laminated glass can reduce the entry of infrared and ultraviolet rays as much as possible, greatly block the entry of sunlight, reduce the use rate of air conditioning in the car, stabilize the temperature in the car, play a heat preservation effect, greatly improve driving comfort, and can protect the driver from sunburn and achieve the purpose of energy saving and emission reduction.

[0022] (2) The haze of the deep black double silver-coated laminated glass provided by the present invention is 0.36%, which meets the automotive glass standard and can be used for automotive skylights. In addition, the laminated film is deep black with beautiful color, has privacy protection and decorative properties, and meets the public aesthetics. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 It is a schematic structural diagram of the deep black double silver coated laminated glass in Example 1.

[0024] Explanation of the accompanying drawings: outer glass substrate-1; PVB adhesive layer-2; inner glass substrate-3; first film layer-4; second film layer-5; third film layer-6; fourth film layer-7; fifth film layer-8; sixth film layer-9; seventh film layer-10; eighth film layer-11; ninth film layer-12; tenth film layer-13; eleventh film layer-14; twelfth film layer-15; thirteenth film layer-16. DETAILED DESCRIPTION

[0025] Embodiment 1: A deep black double silver coated laminated glass for automobile skylight, comprising an outer glass substrate 1, a deep black PVB adhesive layer 2 and an inner glass substrate 3, wherein the outer glass substrate 1 and the inner glass substrate 3 both comprise a first surface and a second surface opposite to each other, and a coated film layer is provided on the first surface of the outer glass substrate 1, and the coated film layer comprises a first film layer 4, a second film layer 5, a third film layer 6, a fourth film layer 7, a fifth film layer 8, a sixth film layer 9, a seventh film layer 10, an eighth film layer 11, a ninth film layer 12, a tenth film layer 13, an eleventh film layer 14, a twelfth film layer 15 and a thirteenth film layer 16 in order from the first surface of the outer glass substrate 1 to the outside. The PVB adhesive layer 2 is dark black in color and is provided between the thirteenth film layer 16 and the second surface of the inner glass substrate 3.

[0026] In the present embodiment, the thickness of the PVB adhesive layer 2 is 0.76mm, and the PVB of Solutia sound insulation 5204 is used for lamination treatment, which is dark black, beautiful and protective. PVB is the abbreviation of polyvinyl butyral, and PVB is the product of condensation of polyvinyl alcohol and butyraldehyde under acid catalysis. Because the PVB molecule contains relatively long side chains, it has good flexibility, low glass transition temperature, and high tensile strength and impact strength. PVB has excellent transparency, good solubility, good light resistance, water resistance, heat resistance, cold resistance and film forming properties. The functional groups it contains can carry out various reactions such as saponification of acetyl, esterification of hydroxyl, sulfonation, etc., and have high adhesion to materials such as glass and metal (especially aluminum).

[0027] The outer glass substrate 1 is a plain white glass substrate with a thickness of 2.1 mm, and the inner glass substrate 3 is a plain white glass substrate with a thickness of 1.6 mm. In this embodiment, the outer glass substrate 1 and the inner glass substrate 3 are both purchased from Taiwan Glass Qingdao Co., Ltd.

[0028] The thickness of the first film layer 4 is 8 to 10 nm, the thickness of the second film layer 5 is 22 to 25 nm, the thickness of the third film layer 6 is 7 to 10 nm, the thickness of the fourth film layer 7 is 5 to 8 nm, the thickness of the fifth film layer 8 is 0.5 to 2 nm, the thickness of the sixth film layer 9 is 10 to 13 nm, the thickness of the seventh film layer 10 is 57 to 60 nm, the thickness of the eighth film layer 11 is 10 nm, the thickness of the ninth film layer 12 is 13 to 16 nm, the thickness of the tenth film layer 13 is 0.5 to 2 nm, the thickness of the eleventh film layer 14 is 10 to 11 nm, the thickness of the twelfth film layer 15 is 20 to 22 nm, and the thickness of the thirteenth film layer 16 is 4 to 7 nm.

[0029] The materials of the third film layer 6, the sixth film layer 9, the eighth film layer 11 and the eleventh film layer 14 are all AZO (zinc aluminum oxide), the materials of the second film layer 5 and the seventh film layer 10 are all ZTO, the materials of the first film layer 4 and the twelfth film layer 15 are all Si3N4, the materials of the fifth film layer 8 and the tenth film layer 13 are all NiCr, the materials of the fourth film layer 7 and the ninth film layer 12 are all Ag, and the material of the thirteenth film layer 16 is ZrO2.

[0030] The third film layer 6, the sixth film layer 9, the eighth film layer 11 and the eleventh film layer 14 are all formed by magnetron sputtering using aluminum-doped zinc oxide as a target material; the first film layer 4 and the twelfth film layer 15 are both formed by magnetron sputtering using rotated silicon as a target material, the thirteenth film layer 16 is formed by magnetron sputtering using zirconium oxide as a target material, and the second film layer 5 and the seventh film layer 10 are formed by magnetron sputtering using zinc tin oxide as a target material.

[0031] The first film layer 4 and the twelfth film layer 15 are silicon nitride layers, which are structural ceramic materials with high hardness, lubricity, wear resistance, oxidation resistance at high temperatures, and resistance to thermal shock; the fifth film layer 8 and the tenth film layer 13 are nickel-chromium alloy layers with high strength and corrosion resistance; the second film layer 5 and the seventh film layer 10 are ZTO layers with high light transmittance in the visible light range; the third film layer 6, the sixth film layer 9, the eighth film layer 11 and the eleventh film layer 14 are AZO layers with high conductivity and low resistivity; the thirteenth film layer 16 is a zirconium oxide layer, which is chemically inactive and has the properties of high melting point, high resistivity, high refractive index and low thermal expansion coefficient; the fourth film layer 7 and the ninth film layer 12 are silver particle layers, which are important optical materials that can be used in the visible light and near-infrared light regions.

[0032] In this embodiment, the first film layer 4 (bottom layer) and the twelfth film layer 15 (second top layer) are set as silicon nitride layers as insulating layers, nickel-chromium alloy layers and AZO layers are symmetrically arranged on both sides of the silver particle layer (fourth film layer 7 and ninth film layer 12), and the thirteenth film layer 16 (top layer) is set as a zirconium oxide layer as a protective layer. Through the reasonable arrangement of the film layer structure, while enhancing the bonding force between different film layers, it plays a good role in preventing sodium ion diffusion and protecting the silver particle layer, and has better anti-oxidation performance.

[0033] In this embodiment, the ZTO layer (the second film layer 5 and the seventh film layer 10) is arranged as a dielectric layer to better combine the AZO layer and the silver particle layer; also because the ZTO band gap is wide and has high light transmittance in the visible light range, the ZTO layer has good visible light transmittance and a suitable refractive index, and the overall film layer color can be adjusted within a wide range. Therefore, the glass color can be stabilized by adjusting the thickness of the ZTO layer.

[0034] Example 2: The method for preparing the deep black double silver-coated laminated glass for automobile skylights described in Example 1 comprises the following steps: S1, sintering target materials: sintering silicon aluminum alloy, zinc aluminum alloy, nickel chromium alloy, silver, zinc tin oxide and zirconium oxide respectively on the target position of the vacuum magnetron sputtering chamber of the glass coating machine, evacuating the chamber, passing process gas, and burning the target for use.

[0035] S2. Pretreatment of glass: placing the inner glass substrate 3 and the outer glass substrate 1 to be coated under vacuum, dehumidifying and degassing the outer glass substrate 1 to be coated and the inner glass substrate 3 to reduce the moisture and gas deposited on the surfaces of the outer glass substrate 1 and the inner glass substrate 3.

[0036] S3, coating treatment: send the outer glass substrate 1 after the dehumidification and degassing treatment in step S2 into the vacuum magnetron sputtering chamber of the glass coating machine, and coat the first surface of the outer glass substrate 1 with a first film layer 4, a second film layer 5, a third film layer 6, a fourth film layer 7, a fifth film layer 8, a sixth film layer 9, a seventh film layer 10, an eighth film layer 11, a ninth film layer 12, a tenth film layer 13, an eleventh film layer 14, a twelfth film layer 15 and a thirteenth film layer 16 in sequence from bottom to top to obtain coated glass.

[0037] S4, sintering treatment: sinter the coated glass at 650°C for 400 seconds.

[0038] S5. Lamination treatment: Use 0.76mm Solutia sound insulation 5204 deep black PVB as the glue layer to perform lamination treatment between the thirteenth film layer 16 on the outer glass substrate 1 and the second surface of the inner glass substrate 3 to obtain a deep black double silver-coated laminated glass. The inner glass substrate 3 is TSA3+ green glass (i.e., ordinary white glass) with a thickness of 1.6mm purchased from Taiwan Glass Qingdao Glass Co., Ltd.

[0039] S6. Use Zeiss colorimeter, salt spray machine and other equipment to test the physical and chemical properties of deep black double silver coated laminated glass.

[0040] Before the sintering treatment in step S4, the visible light transmittance of the coated glass is ≥59%, and the visible light reflectance of the coated glass is ≤7%; after the sintering treatment in step S4, the visible light transmittance of the coated glass is ≥73%, and the visible light reflectance of the coated glass is ≤7%.

[0041] After the lamination treatment in step S5, the visible light transmittance of the laminated glass is ≥38%, and the visible light reflectivity of the laminated glass is ≤15%.

[0042] The haze of the deep black double silver-coated laminated glass prepared in this embodiment is 0.36%, which meets the automotive glass standard. The laminated film is deep black with beautiful color, privacy protection and decorative properties, which meets the public aesthetics.

[0043] The shading coefficient (SC value) of the deep black double silver coated laminated glass prepared in this embodiment is 13.1%, and the total solar transmittance (TTS value) is 10.6%. The laminated glass made of two 2.1mm plain white glass substrates and a 0.76mm transparent PVB adhesive layer is a comparative example, and the SC value and TTS value of the comparative example are 95% and 82.5%. Compared with the comparative example, the shading coefficient of this embodiment is smaller, indicating that the deep black double silver coated laminated glass provided in this embodiment has better performance in blocking light and heat radiation; the total solar transmittance of this embodiment is moderate, which is conducive to achieving a balance between lighting and heat insulation.

[0044] The deep black double-silver coated laminated glass provided by the present invention can be used for automobile skylights, can be placed stably for a long time (placed in the air for about one month), is beneficial to subsequent process processing, and improves the utilization rate of double silver; at the same time, it has an SC value and a TTS value that are superior to those of ordinary laminated glass, so that the laminated glass reduces the entry of infrared and ultraviolet rays as much as possible, greatly blocks the entry of sunlight, reduces the use rate of air conditioning in the car, stabilizes the temperature in the car, has a heat preservation effect, greatly improves driving comfort, can protect the driver from sunburn, and achieve the purpose of energy saving and emission reduction.

[0045] Of course, the above description is not a limitation of the present invention, and the present invention is not limited to the above examples. Changes, modifications, additions or substitutions made by technicians in this technical field within the essential scope of the present invention should also fall within the protection scope of the present invention.

Claims

1. A deep black double silver coated laminated glass for automobile skylight, characterized in that: It comprises an outer glass substrate, a PVB adhesive layer and an inner glass substrate, wherein the outer glass substrate and the inner glass substrate each comprise a first surface and a second surface opposite to each other, a coating film layer is provided on the first surface of the outer glass substrate, and the coating film layer comprises a first film layer, a second film layer, a third film layer, a fourth film layer, a fifth film layer, a sixth film layer, a seventh film layer, an eighth film layer, a ninth film layer, a tenth film layer, an eleventh film layer, a twelfth film layer and a thirteenth film layer in order from the first surface of the outer glass substrate to the outside; The PVB adhesive layer is dark black and is disposed between the thirteenth film layer and the second surface of the inner glass substrate; The materials of the third film layer, the sixth film layer, the eighth film layer and the eleventh film layer are all AZO, the materials of the second film layer and the seventh film layer are all ZTO, the materials of the first film layer and the twelfth film layer are all Si3N4, the materials of the fifth film layer and the tenth film layer are all NiCr, the materials of the fourth film layer and the ninth film layer are all Ag, and the material of the thirteenth film layer is ZrO2; The outer glass substrate is a plain white glass substrate with a thickness of 2.1 mm, the inner glass substrate is a plain white glass substrate with a thickness of 1.6 mm, and the thickness of the PVB adhesive layer is 0.76 mm.

2. The deep black double silver coated laminated glass for automobile skylight according to claim 1, characterized in that: The thickness of the first film layer is 8 to 10 nm, the thickness of the second film layer is 22 to 25 nm, the thickness of the third film layer is 7 to 10 nm, the thickness of the fourth film layer is 5 to 8 nm, the thickness of the fifth film layer is 0.5 to 2 nm, the thickness of the sixth film layer is 10 to 13 nm, the thickness of the seventh film layer is 57 to 60 nm, the thickness of the eighth film layer is 10 nm, the thickness of the ninth film layer is 13 to 16 nm, the thickness of the tenth film layer is 0.5 to 2 nm, the thickness of the eleventh film layer is 10 to 11 nm, the thickness of the twelfth film layer is 20 to 22 nm, and the thickness of the thirteenth film layer is 4 to 7 nm.

3. The deep black double silver coated laminated glass for automobile skylight according to claim 2, characterized in that: The third film layer, the sixth film layer, the eighth film layer and the eleventh film layer are formed by magnetron sputtering using aluminum-doped zinc oxide as a target material, the first film layer and the twelfth film layer are formed by magnetron sputtering using rotated silicon as a target material, the thirteenth film layer is formed by magnetron sputtering using zirconium oxide as a target material, and the second film layer and the seventh film layer are formed by magnetron sputtering using zinc tin oxide as a target material.

4. The method for preparing the deep black double silver coated laminated glass for automobile skylight according to any one of claims 1 to 3, characterized in that: The following steps are involved: S1. Coating target: Si-Al alloy, Zn-Al alloy, Ni-Cr alloy, silver, ZnO-Tn and ZrO2 are sintered on the target position of the vacuum magnetron sputtering chamber of the glass coating machine respectively, the chamber is evacuated, the process gas is passed, and the target is burned for standby use; S2. Pretreatment of glass: placing the inner glass substrate and the outer glass substrate to be coated in a vacuum state, and performing dehumidification and degassing treatment on the inner glass substrate and the outer glass substrate to be coated to reduce the moisture and gas deposited on the surface of the outer glass substrate and the inner glass substrate; S3, coating treatment: sending the outer glass substrate after the dehumidification and degassing treatment in step S2 into the vacuum magnetron sputtering chamber of the glass coating machine, coating the first surface of the outer glass substrate with a first film layer, a second film layer, a third film layer, a fourth film layer, a fifth film layer, a sixth film layer, a seventh film layer, an eighth film layer, a ninth film layer, a tenth film layer, an eleventh film layer, a twelfth film layer and a thirteenth film layer in sequence from bottom to top to obtain coated glass; S4, sintering treatment: sintering the coated glass at 650°C for 400s; S5. Lamination treatment: using 0.76 mm dark black PVB as a glue layer to perform lamination treatment between the thirteenth film layer on the outer glass substrate and the second surface of the inner glass substrate to obtain a dark black double silver-coated laminated glass.

5. The method for preparing the deep black double silver coated laminated glass for automobile skylight according to claim 4, characterized in that: Before the sintering treatment in step S4, the visible light transmittance of the coated glass is ≥59%, and the visible light reflectivity of the coated glass is ≤7%; After the sintering treatment in step S4, the visible light transmittance of the coated glass is ≥73%, and the visible light reflectivity of the coated glass is ≤7%.

6. The method for preparing the deep black double silver coated laminated glass for automobile skylight according to claim 5, characterized in that: After the lamination treatment in step S5, the visible light transmittance of the laminated glass is ≥38%, and the visible light reflectivity of the laminated glass is ≤15%.

7. The method for preparing the deep black double silver coated laminated glass for automobile skylight according to claim 6, characterized in that: The dark black double-silver coated laminated glass has a haze of 0.36%, a shading coefficient of 13.1%, and a total solar energy transmittance of 10.6%.

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