WO2023051151A1 - 车用夹层玻璃 - Google Patents

车用夹层玻璃 Download PDF

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Publication number
WO2023051151A1
WO2023051151A1 PCT/CN2022/116462 CN2022116462W WO2023051151A1 WO 2023051151 A1 WO2023051151 A1 WO 2023051151A1 CN 2022116462 W CN2022116462 W CN 2022116462W WO 2023051151 A1 WO2023051151 A1 WO 2023051151A1
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WO
WIPO (PCT)
Prior art keywords
glass
glass plate
temperature
laminated
vehicles according
Prior art date
Application number
PCT/CN2022/116462
Other languages
English (en)
French (fr)
Inventor
林军
王哲
王立
陈碧珠
Original Assignee
福耀玻璃工业集团股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 福耀玻璃工业集团股份有限公司 filed Critical 福耀玻璃工业集团股份有限公司
Priority to KR1020247010707A priority Critical patent/KR20240052965A/ko
Priority to EP22874542.8A priority patent/EP4393687A1/en
Publication of WO2023051151A1 publication Critical patent/WO2023051151A1/zh

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10036—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
    • C03C27/06—Joining glass to glass by processes other than fusing
    • C03C27/10—Joining glass to glass by processes other than fusing with the aid of adhesive specially adapted for that purpose
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00—Layered products having a non-planar shape
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10082—Properties of the bulk of a glass sheet
    • B32B17/10119—Properties of the bulk of a glass sheet having a composition deviating from the basic composition of soda-lime glass, e.g. borosilicate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10165—Functional features of the laminated safety glass or glazing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/42—Layered products comprising a layer of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60J—WINDOWS, WINDSCREENS, NON-FIXED ROOFS, DOORS, OR SIMILAR DEVICES FOR VEHICLES; REMOVABLE EXTERNAL PROTECTIVE COVERINGS SPECIALLY ADAPTED FOR VEHICLES
    • B60J1/00—Windows; Windscreens; Accessories therefor
    • B60J1/001—Double glazing for vehicles
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B23/00—Re-forming shaped glass
    • C03B23/02—Re-forming glass sheets
    • C03B23/023—Re-forming glass sheets by bending
    • C03B23/03—Re-forming glass sheets by bending by press-bending between shaping moulds
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • B32B2605/006—Transparent parts other than made from inorganic glass, e.g. polycarbonate glazings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • B32B2605/08—Cars
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
    • C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
    • C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions

Definitions

  • the invention relates to the technical field of laminated glass, in particular to laminated glass for vehicles.
  • Laminated glass for vehicles is asymmetrical. Generally, the outer glass is thicker and the inner glass is thin. This special inner and outer laminated glass is different from traditional laminated glass. The main performance is that after the inner glass is bent and formed, additional chemical Tempered, and then laminated with the outer glass to form laminated glass.
  • the chemical tempering method of the inner glass is generally the chemical tempering method of the glass in the electronic display cover industry.
  • the inner glass of some materials is combined with the outer glass for bending and forming, and when the inner glass is chemically tempered after bending, the following problems may exist:
  • the softening point of the inner glass cannot match that of the outer glass, which makes it difficult to bend the two at the same time; 2) Even if it is formed, it is difficult to completely match the shape of the inner and outer glass after forming, and there is a gap between the inner and outer glass after lamination. Different gaps affect the optical quality of the product; 3) The molding trends of the inner and outer glass may be inconsistent, resulting in inconsistent bending degrees in the middle area after hot bending, resulting in hollows, or waves at the edges, resulting in slivers or optical defects after assembling.
  • a kind of laminated glass for vehicle, its preparation raw material comprises first glass plate, second glass plate and interlayer material;
  • composition of the first glass sheet and the second glass sheet are different;
  • the difference between the temperatures Tp1 and Tp2 is about ⁇ 50°C;
  • the temperature Tp1 is defined as the sum of the transition point temperature Tg1 of the first glass plate and the first temperature compensation value Tb1
  • the temperature Tp2 is defined as the sum of the transition point temperature Tg2 of the second glass plate and the first temperature compensation value Tb2;
  • the transition point temperature Tg is defined as the temperature at which the viscosity of the glass is about 10 13.4 poise;
  • Tb1 is approximately equal to 100 ⁇ (3.5 ⁇ SiO 2 +6.5 ⁇ Al 2 O 3 -5 ⁇ (Na 2 O+K 2 O)-3 ⁇ (CaO+MgO)-6 ⁇ B 2 O 3 -2.5 ⁇ (ZnO+P 2 O 5 ));
  • Tb2 is approximately equal to 100 ⁇ (3.5 ⁇ SiO 2 +6.5 ⁇ Al 2 O 3 -5 ⁇ (Na 2 O+K 2 O)-3 ⁇ (CaO+MgO)-6 ⁇ B 2 O 3 -2.5 ⁇ (ZnO+P 2 O 5 ));
  • one or more contents of Al 2 O 3 , K 2 O, CaO, MgO, B 2 O 3 , ZnO and P 2 O 5 Can be zero.
  • the thickness of the second glass plate is smaller than that of the first glass plate, and the composition of the first glass plate is a predetermined composition.
  • the weight ratio of Al 2 O 3 in the second glass plate is about 8wt%-16wt%.
  • the total weight ratio of the alkaline earth metal compound in the second glass sheet is not more than about 5 wt%.
  • the total weight ratio of the alkali metal compound in the second glass plate is about 15wt%-25wt%.
  • the composition of the second glass plate includes Na 2 O, and the content of the Na 2 O is not less than about 60 wt% of the total content of alkali metal compounds in the second glass plate.
  • the composition of the second glass plate includes ZnO with a weight ratio of about 2wt%-6wt% and P2O5 with a weight ratio of about 0-3wt%.
  • the material of the second glass plate is mainly aluminosilicate.
  • the first glass plate is mainly made of soda lime silicate, aluminosilicate or borosilicate.
  • the material of the first glass is mainly soda lime silicate;
  • the material of the second glass plate is mainly aluminosilicate;
  • the weight ratio of Al 2 O 3 in the second glass plate is 8wt%-12wt%; the total weight ratio of the alkali metal compound in the second glass plate is about 20wt%-25wt%.
  • the material of the first glass is mainly aluminosilicate or borosilicate;
  • the material of the second glass plate is mainly aluminosilicate;
  • the weight ratio of Al 2 O 3 in the second glass plate is 12wt%-16wt%; the total weight ratio of the alkali metal compound in the second glass plate is about 15wt%-20wt%.
  • the thickness of the first glass plate is about ⁇ 2.1 mm.
  • the first glass plate is colorless glass, tinted glass or coated glass whose coated surface is adjacent to the interlayer material.
  • the thickness of the second glass plate is about ⁇ 1.1 mm.
  • the second glass is capable of ion exchange.
  • the second glass plate is colorless glass with a visible light transmittance above 88%.
  • the interlayer material is an organic polymer.
  • the optional range of the term “and/or”, “or/and”, “and/or” used includes any one of two or more related listed items, and also includes related listed items Any and all combinations of items, including any combination of any two of the related listed items, any more of the related listed items, or all of the related listed items.
  • the final concentration refers to the proportion of the added component in the system after the component is added.
  • the weight ratio refers to the weight ratio of the component in the overall component, unless otherwise specified.
  • the weight ratio of Al 2 O 3 in the second glass plate is about 8wt% ⁇ 12wt%, that is, the percentage of the weight of Al 2 O 3 in the second glass plate to the weight of the second glass plate.
  • a laminated glass for vehicles is provided, and its preparation raw materials include a first glass plate, a second glass plate, and an interlayer material;
  • composition of the first glass sheet and the second glass sheet are different;
  • the difference between the temperatures Tp1 and Tp2 is about ⁇ 50°C;
  • the temperature Tp1 is defined as the sum of the transition point temperature Tg1 of the first glass plate and the first temperature compensation value Tb1
  • the temperature Tp2 is defined as the sum of the transition point temperature Tg2 of the second glass plate and the first temperature compensation value Tb2;
  • the transition point temperature Tg is defined as the temperature at which the viscosity of the glass is about 10 13.4 poise;
  • Tb1 is approximately equal to 100 ⁇ (3.5 ⁇ SiO 2 +6.5 ⁇ Al 2 O 3 -5 ⁇ (Na 2 O+K 2 O)-3 ⁇ (CaO+MgO)-6 ⁇ B 2 O 3 -2.5 ⁇ (ZnO+P 2 O 5 ));
  • Tb2 is approximately equal to 100 ⁇ (3.5 ⁇ SiO 2 +6.5 ⁇ Al 2 O 3 -5 ⁇ (Na 2 O+K 2 O)-3 ⁇ (CaO+MgO)-6 ⁇ B 2 O 3 -2.5 ⁇ (ZnO+P 2 O 5 ));
  • one or more contents of Al 2 O 3 , K 2 O, CaO, MgO, B 2 O 3 , ZnO and P 2 O 5 Can be zero.
  • the thickness of the second glass plate is smaller than that of the first glass plate, and the composition of the first glass plate is a preset composition.
  • the first glass plate is the outer piece of glass
  • the second glass plate is the inner piece of glass.
  • the thickness of the first glass plate is about ⁇ 2.1mm.
  • the thickness of the second glass plate is about ⁇ 1.1 mm.
  • the thickness of the first glass sheet includes, but is not limited to, about 2.1mm, about 2.3mm, about 2.5mm, about 2.6mm, about 2.8mm, about 3.0mm, about 3.2mm, about 3.5mm, about 3.8mm, about 4.0 mm, about 4.2mm, about 4.5mm, about 5.0mm and above;
  • the thickness of the second glass plate includes but is not limited to about 0.5mm, about 0.7mm, about 0.9mm, about 1.1mm or other thicknesses between about 0.5mm and 1.1 Thickness in mm range. Under the combination of different thicknesses, the technical effect described in this application can still be achieved.
  • the composition and specifications of the outer glass are generally preset, because the outer glass largely determines the color, appearance, visible light transmittance, infrared and ultraviolet transmittance, and ink of the automotive glass assembly. , compatibility of bonding accessories, and a complete set of glass deep-processing equipment and process systems from the original sheet to the finished product, so the material of the first glass plate in this application can be a preset material.
  • the material adjustment of the inner glass has a higher degree of freedom, and the production process of the original inner glass is more diversified, and the composition adjustment is more feasible, and appropriate adjustments can be made to match the outer glass.
  • the material of the second glass plate can be adjusted so that the difference between the two forming temperatures is about ⁇ 50°C.
  • the forming temperature (Tp) of the glass defined in this application is the sum of the glass transition temperature (Tg) and the temperature compensation value (Tb) of the glass, wherein the calculation formula of Tb is based on the different oxide groups in the glass According to the influence on the viscosity-temperature curve, combined with the example data, in the calculation formula of Tb, the oxide with a positive coefficient (such as SiO 2 , Al 2 O 3 ) means that the introduction of the oxide increases the high-temperature viscosity of the glass. Correspondingly, the molding temperature is increased, and the coefficient indicates the influence of the oxide on the viscosity.
  • Tg of glass can be measured with reference to standard methods, and is defined as the temperature at which the viscosity of glass is about 10 13.4 poise.
  • the forming temperature Tp1 of the first glass sheet may be a certain temperature between Tg1 and the softening point of the first glass sheet. At this temperature, the glass exhibits an optimum viscosity suitable for hot bending, that is, A certain degree of ductility makes it possible to bend and form, and it will not cause various common defects in the glass during the bending process (such as sticking pieces, mold dropping, mold marks, impurity particles embedded, etc.) due to too high fluidity and too soft .
  • the forming temperature Tp2 of the second glass plate may also be a certain temperature between Tg2 and the softening point of the second glass plate.
  • the processing operability of simultaneous bending and forming of the first glass plate and the second glass plate is realized, and the matching degree of the shape of the first glass plate and the second glass plate after bending and forming can be improved, so that the first glass plate
  • the central gap between the plate and the second glass plate is small, there is no obvious hollow in the middle, and the edge wave is small.
  • the optical performance of the laminated glass is improved.
  • the composition of the second glass sheet after the difference between the forming temperatures Tp2 of the first glass sheet Tp1 and the second glass sheet satisfies the above conditions, the composition of the second glass sheet also satisfies: the composition of the second glass sheet includes Al 2 O 3 , at least one alkali metal compound and at least one alkaline earth metal compound;
  • the content of Al 2 O 3 in the second glass sheet is about 8wt%-16wt% of the second glass sheet.
  • the total amount of alkaline earth metal compounds in the second glass sheet is no more than about 5% by weight of the second glass sheet.
  • the total content of the alkali metal compound in the second glass sheet is about 15%wt-25wt% of the second glass sheet.
  • alkali metals are necessary oxide components for glass production, and are generally introduced from soda ash, feldspar , etc. as raw materials to reduce the melting temperature of glass production; The free cation necessary for Na + ).
  • the composition of the second glass sheet includes Na 2 O, and the content of the Na 2 O is not less than about 60 wt% of the total content of alkali metal compounds in the second glass sheet.
  • the glass contains Na 2 O in the above content, which is beneficial to realize fast ion exchange.
  • the composition of the second glass sheet includes about 2wt%-6wt% of the second glass sheet ZnO and about 0-3wt% of the second glass sheet P2O 5 .
  • the material of the second glass plate is mainly aluminosilicate.
  • said second glass sheet is capable of ion exchange.
  • the second glass plate is colorless glass with visible light transmittance above 88%.
  • Laminated glass for vehicles has a large size, a large number of varieties, and complex curvature shapes.
  • the requirements for the depth of the stress layer of chemical steel are high, and fast ion exchange is required, that is, to achieve the required depth of the stress layer as much as possible in the shortest possible exchange time, and to improve Yield.
  • fast ion exchange can also reduce the time for glass to be soaked in molten salt, reduce the ion exchange of impurities in the glass into the salt bath, ensure the durability of molten salt, and reduce the frequency of molten salt replacement.
  • the inner glass of some materials cannot achieve the required stress layer depth through rapid ion exchange, which results in high costs both in terms of productivity and the frequency of molten salt replacement.
  • the second glass plate has a sufficiently high surface stress and stress layer depth in a short period of time when it is chemically tempered, and has the effect of rapid ion exchange strengthening, which can meet the requirements of large-scale and large-scale chemically tempered glass for automobiles.
  • Production requirements increase yield, reduce the frequency of molten salt replacement, save costs, and achieve a process cost close to that of traditional physical air-cooled tempering, which facilitates the better application of chemical tempered glass in the automotive market with low cost .
  • Sufficiently high surface stress and stress layer depth can refer to: the compressive stress layer depth of the exchanged inner glass plate is about ⁇ 30 ⁇ m, and the compressive stress is about ⁇ 500 MPa.
  • the ion exchange rate of the present application is fast.
  • the ion exchange strengthening time is ⁇ 4h, and in some embodiments, the ion exchange strengthening time is ⁇ 2h.
  • the first glass plate is mainly made of soda lime silicate, aluminosilicate or borosilicate.
  • the first glass plate may be annealed low-stress glass or pre-stressed glass that has undergone physical and thermal strengthening.
  • the first glass plate is colorless glass, tinted glass or coated glass whose coated surface is adjacent to the interlayer material.
  • the material of the first glass is mainly soda lime silicate
  • the material of the second glass plate is mainly aluminosilicate
  • the content of Al 2 O 3 in the second glass plate accounts for About 8wt%-12wt% of the second glass plate
  • the total content of the alkali metal compound in the second glass plate accounts for about 20wt%-25wt% of the second glass plate.
  • the material of the first glass is mainly aluminosilicate or borosilicate
  • the material of the second glass plate is mainly aluminosilicate
  • the Al 2 O in the second glass plate is The content of 3 accounts for about 12wt%-16wt% of the second glass plate
  • the total content of the alkali metal compound in the second glass plate accounts for about 15wt%-20wt% of the second glass plate.
  • the interlayer of the automotive laminated glass of the present application may be single-layer or multi-layer, and may be prepared from interlayer materials.
  • the interlayer material is an organic polymer.
  • organic polymers can also be pre-compounded with special functional layers.
  • organic polymers include, but are not limited to polyvinyl butyral (PVB), polyurethane (PU), polyethylene-vinyl acetate (EVA), ethylene-methacrylate (SGP) It is a polymer with excellent aging resistance and sufficient adhesion to the glass surface.
  • PVB polyvinyl butyral
  • PU polyurethane
  • EVA polyethylene-vinyl acetate
  • SGP ethylene-methacrylate
  • this application obtains the empirical formula of the temperature compensation value Tb of the glass plate, and thus leads to the forming temperature Tp of the glass plate.
  • Tp1 and Tp2 of the first glass plate and the second glass plate the processing operability of the first glass plate and the second glass plate to be bent and formed at the same time is satisfied, and the first glass after bending and forming can also be improved.
  • the matching degree of the shape of the plate and the second glass plate makes the central gap between the first glass plate and the second glass plate small, there is no obvious hollow in the middle, and the edge wave is small. After lamination, the optical performance of the laminated glass is improved.
  • the present application also provides a method for preparing the above-mentioned laminated glass for vehicles.
  • a method for preparing laminated glass for vehicles comprising the following steps:
  • the interlayer material is placed between the bent and formed first glass plate and the chemically tempered second glass plate, and heated and pressed to prepare a laminated glass.
  • bending the first glass sheet and the second glass sheet further includes a step of pre-treating the first glass sheet and the second glass sheet, and the pre-treatment includes: performing the first glass sheet and the second glass sheet The second glass plate is cut and edged to form the required specific contour, and the size difference between the first glass plate and the second glass plate is preset according to the bending shape and size of the final product, so that the two laminated sheets after bending Layer glass edges remain consistent.
  • bending the first glass plate and the second glass plate at a preset temperature includes:
  • the laminated glass is placed on a forming mold, and the laminated glass is bent and shaped at a preset temperature.
  • the method of bending and forming the laminated glass plates may be to complete the forming process by relying on the self-gravity of the glass to bend and fit the mold, or to complete the forming process through the auxiliary pressing of the ring-shaped lower mold and the solid upper mold.
  • the laminated glass plates can be heated uniformly and symmetrically from top to bottom for molding.
  • the forming method can adopt the gravity forming method, which uses gravity to bend and fit the contour of the mold to form the required shape; it can also use the pressure method to place the laminated glass plate that is not fully formed by its own weight between the ring-shaped lower mold and the solid upper mold. Compression molding to form the desired shape.
  • the laminated glass plate is slowly cooled to room temperature to complete annealing, and the bent and formed laminated glass plate is obtained.
  • the preset temperature is the forming temperature of the first glass plate.
  • one or more chambers may be included in the continuous furnace or the tunnel furnace.
  • the temperature of the chamber is raised to a preset temperature by raising the temperature, and the preset temperature is the first
  • the molding temperature of a glass plate when there are multiple chambers, by raising the temperature, the temperature of each chamber can be raised, and each chamber can be set to have a gradient temperature distribution, and the highest temperature in the chamber is the preset temperature.
  • the temperature be the forming temperature of the first glass sheet.
  • the high-temperature-resistant insulating powder is a powder material that does not react with the surface of the glass sheet, including but not limited to diatomite or calcium carbonate.
  • the particle size of the diatomite is about 5 ⁇ m-15 ⁇ m.
  • the high-temperature-resistant insulating powder is added between the bent and formed first glass plate and the second glass plate, the two can be separated, and then chemical toughening treatment is performed on the bent and formed second glass plate.
  • the chemical toughening treatment includes the steps of: preheating, ion exchange, cooling, and cleaning.
  • the lamination treatment includes: placing the interlayer material between the bent and formed first glass plate and the chemically tempered second glass plate, heating and pressing to prepare the vehicle laminated glass .
  • the two pieces of glass and the polymer interlayer film are neatly and evenly bonded into one body to obtain laminated glass for vehicles.
  • the structure of the laminated glass for a vehicle has a convex surface. After reaching the vehicle body, the convex surface faces the outside of the vehicle, the first glass plate is located on the side facing the outside of the vehicle, and the second glass plate is located on the side facing the inside of the vehicle. side.
  • the laminated glass for the vehicle may be the front and rear windshield glass, sunroof glass or front and rear door glass of the vehicle body.
  • the preset temperature of the bending forming is about 593°C
  • the preset ion exchange temperature of the chemical tempering of the second glass plate after forming is about 420°C.
  • the ion exchange time is about 2 hours, which can meet the requirements on glass stress and depth.
  • the laminated glasses of Examples and Comparative Examples were prepared, wherein the thickness of the first glass plate was about 3.5 mm, the thickness of the second glass plate is about 1.1mm, and the specific preparation method is as follows:
  • the chemically tempered glass for vehicles has lower requirements on the surface stress and higher requirements for the depth of the stress layer.
  • the chemically tempered glass furnace for vehicles even if the size of the furnace The sub-tempering loading is still low, which requires a sufficient depth of the stress layer in the shortest possible time. Therefore, the technical effects achieved by the above-mentioned embodiments and comparative examples were also evaluated according to the average ion exchange rate of the second glass plate in the first 4 hours after the ion exchange started, and the results are shown in Table 3.
  • the central gap between the first glass plate and the second glass plate after bending is small, there is no obvious hollowing in the middle area of the first glass plate and the second glass plate, and the edge gap Small, with small edge waves and high profile matching, the final laminated glass shape can be consistent with the laminated glass after hot bending, which is conducive to improving the overall optical quality of the product.
  • the second glass plate of Examples 1-4 has the effect of rapid ion exchange strengthening, and within the first 4 hours after the start of ion exchange, the average stress layer depth exchange rate is ⁇ 12 ⁇ m/h.

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Abstract

本申请涉及车用夹层玻璃。所述车用夹层玻璃的制备原料包括第一玻璃板、第二玻璃板以及夹层材料；所述第一玻璃板和所述第二玻璃板的组成成分不同；温度Tp1和Tp2之间的差值≤50℃；温度Tp1定义为第一玻璃板的转变点温度Tg1和第一温度补偿值Tb1之和，温度Tp2定义为第二玻璃板的转变点温度Tg2和第一温度补偿值Tb2之和；定义温度Tp的通式为Tp＝Tg+Tb。

Description

车用夹层玻璃
相关申请
本申请要求2021年9月30日申请的，申请号为2021111635094，名称为“车用夹层玻璃”的中国专利申请的优先权，在此将其全文引入作为参考。
技术领域
本发明涉及夹层玻璃的技术领域，特别涉及车用夹层玻璃。
背景技术
车用夹层玻璃为非对称的，一般外片玻璃厚，内片玻璃薄，这种特殊的内外片夹层玻璃与传统夹层玻璃不同，主要表现在：内片玻璃在弯曲成型后，需要额外进行化学钢化，然后与外片玻璃进行夹胶，形成夹层玻璃。目前内片玻璃的化学钢化方法一般也是采用电子显示盖板行业玻璃的化学钢化方法。但是一些材质的内片玻璃在与外片玻璃组合进行弯曲成型时，以及弯曲成型后的内片玻璃化学钢化时，可能会存在以下问题：
1)内片玻璃软化点不能与外片玻璃相适应，导致两者同时弯曲成型困难；2)即使成型，成型后内外片玻璃的形状很难完全匹配，夹胶后内外片玻璃之间存在大小不一的空隙，影响产品光学质量；3)内外玻璃成型趋势可能不一致，导致热弯成型后中部区域弯曲程度不一致，产生空鼓，或边缘产生波浪，造成合片后裂片或光学不良。
发明内容
基于此，根据本申请的各种实施例，提供一种车用夹层玻璃，技术方案为：
一种车用夹层玻璃，其制备原料包括第一玻璃板、第二玻璃板以及夹层材料；
所述第一玻璃板和所述第二玻璃板的组成成分不同；
温度Tp1和Tp2之间的差值约≤50℃；
温度Tp1定义为第一玻璃板的转变点温度Tg1和第一温度补偿值Tb1之和，温度Tp2定义为第二玻璃板的转变点温度Tg2和第一温度补偿值Tb2之和；定义温度Tp的通式为Tp＝Tg+Tb；
转变点温度Tg定义为玻璃的粘度约为10 13.4泊时的温度；
第一温度补偿值Tb1和第一玻璃板的组成成分的重量比之间满足以下条件：Tb1约等 于100×(3.5×SiO 2+6.5×Al 2O 3-5×(Na 2O+K 2O)-3×(CaO+MgO)-6×B 2O 3-2.5×(ZnO+P 2O 5))；
第二温度补偿值Tb2和第二玻璃板的组成成分的重量比之间满足以下条件：Tb2约等于100×(3.5×SiO 2+6.5×Al 2O 3-5×(Na 2O+K 2O)-3×(CaO+MgO)-6×B 2O 3-2.5×(ZnO+P 2O 5))；
其中，在所述第一玻璃板以及所述第二玻璃板中，Al 2O 3、K 2O、CaO、MgO、B 2O 3、ZnO和P 2O 5中的一种或多种含量可以为零。
在其中一个实施例中，所述第二玻璃板的厚度小于所述第一玻璃板，且所述第一玻璃板的组成成分为预设成分。
在其中一个实施例中，所述第二玻璃板中Al 2O 3的重量比约为8wt％～16wt％。
在其中一个实施例中，所述第二玻璃板中碱土金属化合物的总重量比不超过约5wt％。
在其中一个实施例中，所述第二玻璃板中碱金属化合物的总重量比约为15wt％～25wt％。
在其中一个实施例中，所述第二玻璃板的组成成分包括Na 2O，且所述Na 2O的含量不少于所述第二玻璃板中碱金属化合物总含量的约60wt％。
在其中一个实施例中，所述第二玻璃板的组成成分包括重量比约为2wt％～6wt％的ZnO以及重量比约为0～3wt％的P 2O 5。
在其中一个实施例中，所述第二玻璃板的材质主要为铝硅酸盐。
在其中一个实施例中，所述第一玻璃板的材质主要为钠钙硅酸盐、铝硅酸盐或硼硅酸盐。
在其中一个实施例中，所述第一玻璃的材质主要为钠钙硅酸盐；所述第二玻璃板的材质主要为铝硅酸盐；
所述第二玻璃板中Al 2O 3的重量比为8wt％～12wt％；所述第二玻璃板中的碱金属化合物的总重量比约为20wt％～25wt％。
在其中一个实施例中，所述第一玻璃的材质主要为铝硅酸盐或硼硅酸盐；所述第二玻璃板的材质主要为铝硅酸盐；
所述第二玻璃板中Al 2O 3的重量比为12wt％～16wt％；所述第二玻璃板中的碱金属化合物的总重量比约为15wt％～20wt％。
在其中一个实施例中，所述第一玻璃板的厚度约≥2.1mm。
在其中一个实施例中，所述第一玻璃板为无色玻璃、着色玻璃或镀膜面与所述夹层材料相邻的镀膜玻璃。
在其中一个实施例中，所述第二玻璃板的厚度约≤1.1mm。
在其中一个实施例中，所述第二玻璃能够进行离子交换。
在其中一个实施例中，所述第二玻璃板为可见光透过率约在88％以上的无色玻璃。
在其中一个实施例中，所述夹层材料为有机聚合物。
本申请的一个或多个实施例细节在下面的描述中提出，本申请的其他特征、目的和优点将从说明书及其权利要求书变得明显。
具体实施方式
下面对本申请实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本申请一部分实施例，而不是全部的实施例。基于本申请中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本申请保护的范围。
除非另有定义，本文所使用的所有的技术和科学术语与属于本申请的技术领域的技术人员通常理解的含义相同。本文中在本申请的说明书中所使用的术语只是为了描述具体的实施例的目的，不是旨在于限制本申请。
术语
除非另外说明或存在矛盾之处，本文中使用的术语或短语具有以下含义：
本申请中，所使用的术语“和/或”、“或/和”、“及/或”的可选范围包括两个或两个以上相关所列项目中任一个项目，也包括相关所列项目的任意的和所有的组合，所述任意的和所有的组合包括任意的两个相关所列项目、任意的更多个相关所列项目、或者全部相关所列项目的组合。
本申请中，“一种或几种”指所列项目的任一种、任两种或任两种以上。其中，“几种”指任两种或任两种以上。
本申请中，所使用的“其组合”、“其任意组合”、“其任意组合方式”等中包括所列项目中任两个或任两个以上项目的所有合适的组合方式。
本申请中，所使用的“合适的组合方式”、“合适的方式”、“任意合适的方式”等中所述“合适”，以能够实施本申请的技术方案、解决本申请的技术问题、实现本申请预期的技术效果为准。
本申请中，“优选”仅为描述效果更好的实施方式或实施例，应当理解，并不构成对本申请保护范围的限制。
本申请中，以开放式描述的技术特征中，包括所列举特征组成的封闭式技术方案，也包括包含所列举特征的开放式技术方案。
本申请中，涉及到数值区间，如无特别说明，则包括数值区间的两个端点。
本申请中，涉及到百分比含量，如无特别说明，对于固液混合和固相-固相混合均指质量百分比，对于液相-液相混合指体积百分比。
本申请中，涉及到百分比浓度，如无特别说明，均指终浓度。所述终浓度，指添加成分在添加该成分后的体系中的占比。
本申请中，涉及到温度参数，如无特别限定，既允许为恒温处理，也允许在一定温度区间内进行处理。所述的恒温处理允许温度在仪器控制的精度范围内进行波动。
本申请中，涉及到重量比，如无特别限定，指该组成成分在整体组分中的重量比。例如，第二玻璃板中Al 2O 3的重量比约为8wt％～12wt％，即为第二玻璃板中Al 2O 3的重量占第二玻璃板的重量的百分比。
本申请一些实施例中，提供一种车用夹层玻璃，其制备原料包括第一玻璃板、第二玻璃板以及夹层材料；
所述第一玻璃板和所述第二玻璃板的组成成分不同；
温度Tp1和Tp2之间的差值≤50℃；
温度Tp1和Tp2之间的差值约≤50℃；
温度Tp1定义为第一玻璃板的转变点温度Tg1和第一温度补偿值Tb1之和，温度Tp2定义为第二玻璃板的转变点温度Tg2和第一温度补偿值Tb2之和；定义温度Tp的通式为Tp＝Tg+Tb；
转变点温度Tg定义为玻璃的粘度约为10 13.4泊时的温度；
第一温度补偿值Tb1和第一玻璃板的组成成分的重量比之间满足以下条件：Tb1约等于100×(3.5×SiO 2+6.5×Al 2O 3-5×(Na 2O+K 2O)-3×(CaO+MgO)-6×B 2O 3-2.5×(ZnO+P 2O 5))；
第二温度补偿值Tb2和第二玻璃板的组成成分的重量比之间满足以下条件：Tb2约等于100×(3.5×SiO 2+6.5×Al 2O 3-5×(Na 2O+K 2O)-3×(CaO+MgO)-6×B 2O 3-2.5×(ZnO+P 2O 5))；
其中，在所述第一玻璃板以及所述第二玻璃板中，Al 2O 3、K 2O、CaO、MgO、B 2O 3、ZnO和P 2O 5中的一种或多种含量可以为零。
可选地，所述第二玻璃板的厚度小于所述第一玻璃板，且所述第一玻璃板的组成成分为预设成分。例如，第一玻璃板为外片玻璃，第二玻璃板为内片玻璃。可选地，所述第一玻璃板的厚度约≥2.1mm。可选地，所述第二玻璃板的厚度约≤1.1mm。例如，第一玻璃板的厚度包括但不限于约2.1mm、约2.3mm、约2.5mm、约2.6mm、约2.8mm、约3.0mm、 约3.2mm、约3.5mm、约3.8mm、约4.0mm、约4.2mm、约4.5mm、约5.0mm及以上厚度；第二玻璃板的厚度包括但不限于约0.5mm、约0.7mm、约0.9mm、约1.1mm或其他在约0.5mm～1.1mm范围内的厚度。在不同厚度的组合下，可以依然能够具备本申请所述的技术效果。
在一些情况下，外片玻璃的成分和规格一般是预设的，因为外片玻璃在很大程度上决定了汽车玻璃总成的颜色、外观、可见光透过率、红外紫外透过率、油墨、粘结附件兼容性、以及从原片到成品的整套玻璃深加工设备、工艺系统等，因此本申请的第一玻璃板的材质可以是一种预设材质。相比于外片玻璃，内片玻璃材质调整的自由度较高，而且内片原片生产工艺更多样化，成分调整较为可行，可进行适当调整以匹配外片玻璃。本申请中，可根据第一玻璃板的预热材质，调整第二玻璃板的材质，使两者的成型温度之差约≤50℃。
本申请中定义了玻璃的成型温度(Tp)是该玻璃的玻璃化转变温度(Tg)和该玻璃的温度补偿值(Tb)之和，其中，Tb的计算公式根据玻璃中不同的氧化物组分对黏温曲线的影响，结合实例数据得出，在Tb的计算公式中，系数为正的氧化物(如SiO 2，Al 2O 3)表示该氧化物的引入，提高了玻璃高温黏度，相应地提高了成型温度，系数大小表示该氧化物对黏度的影响强弱，其他系数为负的氧化物表示该氧化物的引入，降低了玻璃高温黏度，相应地降低了成型温度，系数大小同样表示该氧化物对黏度的影响强弱。一般来说，玻璃的组成成分不同，Tg不同，Tb也不同，需同时控制Tg和Tb使得两者的成型温度Tp满足上述条件。
可以理解地，玻璃的Tg可以参照标准方法测量得出，定义为玻璃的粘度约为10 13.4泊时的温度。
本申请中，第一玻璃板的成型温度Tp1可以是介于第一玻璃板的Tg1和软化点之间的某个温度，在该温度下，玻璃表现出适合热弯加工的最佳黏度，既有一定的延展性使得弯曲成型成为可能，又不会因为流动性太高、太软而使玻璃在弯曲过程中产生各种常见缺陷(如粘片、掉模、模具痕迹、杂质颗粒嵌入等)。同理，第二玻璃板的成型温度Tp2也可以是介于第二玻璃板的Tg2和软化点之间的某个温度。
符合上述条件后，实现了第一玻璃板和第二玻璃板同时弯曲成型的加工可操作性，还能提高弯曲成型后第一玻璃板和第二玻璃板型面的匹配度，使第一玻璃板和第二玻璃板的中央间隙小，中部无明显的空鼓，边缘波浪小，夹胶后，提高夹层玻璃的光学性能现象。
在一个实施例中，在第一玻璃板Tp1和第二玻璃板的成型温度Tp2的差值满足上述条件后，第二玻璃板的组成成分还满足：所述第二玻璃板的组成成分包括Al 2O 3、至少一种碱金属化合物和至少一种碱土金属化合物；
在一些实施例中，所述第二玻璃板中Al 2O 3的含量占所述第二玻璃板的约8wt％～16wt％。
在一些实施例中，所述第二玻璃板中的碱土金属化合物的总含量不超过所述第二玻璃板的约5wt％。
在一些实施例中，所述第二玻璃板中的碱金属化合物的总含量占所述第二玻璃板的约15％wt～25wt％。
一方面碱金属是玻璃生产所必要的氧化物成分，一般由纯碱、长石等作为原料引入，用于降低玻璃生产熔制温度；另一方面提供化学强化离子交换(盐浴中K +交换玻璃中Na +)所必需的的游离阳离子。
在一些实施例中，所述第二玻璃板的组成成分包括Na 2O，且所述Na 2O的含量不少于所述第二玻璃板中碱金属化合物总含量的约60wt％。玻璃中含有上述含量的Na 2O，有利于实现快速离子交换。
在一些实施例中，所述第二玻璃板的组成成分包括占所述第二玻璃板的约2wt％～6wt％的ZnO以及所述第二玻璃板的约0～3wt％含量的P 2O 5。
可选地，所述第二玻璃板的材质主要为铝硅酸盐。
可以理解地，所述第二玻璃板能够进行离子交换。
可以理解地，所述第二玻璃板为可见光透过率约在88％以上的无色玻璃。
车用夹层玻璃尺寸大、品种数量多，曲率形状复杂，化钢应力层深度要求高，需要快速离子交换，即在尽可能短的交换时间内达到所需的尽可能大的应力层深度，提升产率。此外快速离子交换还能减少玻璃浸泡在熔盐中的时间，降低玻璃中杂质离子交换至盐浴中，保证熔盐的耐用性，降低熔盐更换频次。但一些材质的内片玻璃不能通过快速离子交换达到要求的应力层深度，无论在产率方面，还是在熔盐更换频次方面，均产生高昂的成本。
而满足上述条件，保证第二玻璃板在化学钢化时，短时间内有足够高的表面应力和应力层深度，具有快速离子交换强化的效果，能满足汽车用化学钢化玻璃的大尺寸、大批量生产要求，提升产率，还能降低熔盐更换频次，节省成本，还能达到与传统物理风冷钢化相接近的工艺成本，便于化学钢化玻璃更好地应用在车用领域市场，且成本低。
足够高的表面应力和应力层深度可以指：交换后内玻璃板的压缩应力层深度约≥30μm，压缩应力约≥500MPa。
本申请离子交换速率快，在一些实施例中，离子交换强化时长≤4h，在一些实施例中，离子交换强化时长≤2h。
可选地，所述第一玻璃板的材质主要为钠钙硅酸盐、铝硅酸盐或硼硅酸盐。
可以理解地，所述第一玻璃板可以是经退火的低应力玻璃或经过物理热强化的预应力 玻璃。
可以理解地，所述第一玻璃板为无色玻璃、着色玻璃或镀膜面与所述夹层材料相邻的镀膜玻璃。
在一些实施例中，所述第一玻璃的材质主要为钠钙硅酸盐，所述第二玻璃板的材质主要为铝硅酸盐，所述第二玻璃板中Al 2O 3的含量占所述第二玻璃板的约8wt％～12wt％；所述第二玻璃板中的碱金属化合物的总含量占所述第二玻璃板的约20wt％～25wt％。
在一些实施例中，所述第一玻璃的材质主要为铝硅酸盐或硼硅酸盐，所述第二玻璃板的材质主要为铝硅酸盐，所述第二玻璃板中Al 2O 3的含量占所述第二玻璃板的约12wt％～16wt％；所述第二玻璃板中的碱金属化合物的总含量占所述第二玻璃板的约15wt％～20wt％。
在一些实施例中，本申请的车用夹层玻璃的夹层可以是单层或多层，可通过夹层材料制备而成。
可选地，夹层材料是有机聚合物。在一些实施例中，有机聚合物还可以预复合特殊功能层。
可选地，有机聚合物包括但不限于以聚乙烯醇缩丁醛(PVB)、聚氨基甲酸酯(PU)、聚乙烯-醋酸乙烯酯(EVA)、乙烯-甲基丙烯酸酯(SGP)等为主要成分的，具有优良的耐老化性、以及足够的与玻璃表面粘结性的聚合物。
本申请根据玻璃中不同的氧化物组分对黏温曲线的影响，结合实例数据得出了玻璃板温度补偿值Tb经验公式，由此引出了玻璃板的成型温度Tp。通过限定第一玻璃板和第二玻璃板的成型温度Tp1和Tp2的差值，满足了第一玻璃板和第二玻璃板同时弯曲成型的加工可操作性，还能提高弯曲成型后第一玻璃板和第二玻璃板型面的匹配度，使第一玻璃板和第二玻璃板的中央间隙小，中部无明显的空鼓，边缘波浪小，夹胶后，提高夹层玻璃的光学性能现象。
本申请还提供一种上述车用夹层玻璃的制备方法。
一种车用夹层玻璃的制备方法，包括以下步骤：
于预设温度下，使所述第一玻璃板和第二玻璃板弯曲成型；
分离弯曲成型后的所述第一玻璃板和第二玻璃板，对弯曲成型后的所述第二玻璃板进行化学钢化处理；
将所述夹层材料放置在弯曲成型后的所述第一玻璃板和化学钢化处理后的所述第二玻璃板之间，加热加压，制备夹层玻璃。
可以理解地，使所述第一玻璃板和第二玻璃板弯曲成型还包括对第一玻璃板和第二玻 璃板进行预处理的步骤，所述预处理包括：对所述第一玻璃板和第二玻璃板进行切割、磨边，形成所需要的特定轮廓，并根据最终产品弯曲形状和尺寸，预设好第一玻璃板和第二玻璃板的尺寸叠差，使得叠片弯曲后的两层玻璃边缘保持一致。
可选地，所述于预设温度下，使所述第一玻璃板和第二玻璃板弯曲成型，包括：
将所述第一玻璃板和第二玻璃板叠合，并在两者的叠合面施加耐高温隔离粉，得叠片玻璃板；
将所述叠片玻璃置于成型模具上，于预设温度下，使所述叠片玻璃弯曲成型。
可以理解地，使所述叠片玻璃板弯曲成型的方法可以是依靠玻璃自重热弯曲贴合模具完成成型过程，或通过环状下模和实心上模辅助对压完成成型过程。
可选地，可以在连续炉或隧道炉内，通过预设炉体温度，将叠片玻璃板上下均匀对称加热进行成型。成型方式可以采用重力成型法，利用重力弯曲贴合模具轮廓，形成所需要的形状；也可以采用加压方法，将自重未完全成型的叠片玻璃板置于环状下模和实心上模之间加压成型，形成所需要的形状。成型完毕后将叠片玻璃板缓慢冷却至室温完成退火，得到弯曲成型后的叠片玻璃板。
可选地，所述预设温度为所述第一玻璃板的成型温度。
可以理解地，连续炉或隧道炉内可包含一个或多个腔室，当有单个腔室时，通过升温，将腔室的温度升高至预设温度，所述预设温度为所述第一玻璃板的成型温度；当有多个腔室时，通过升温，将每个腔室的温度升高，可以设置各个腔室呈梯度温度分布，最高腔室内温度为预设温度，所述预设温度为所述第一玻璃板的成型温度。
可选地，所述耐高温隔离粉为不与玻璃片表面反应的粉末材料，包括但不限于硅藻土或碳酸钙，在一个实施例中，硅藻土的粒径约为5μm～15μm。
由于弯曲成型后的第一玻璃板和第二玻璃板之间加入了耐高温隔离粉，可将两者分离，然后对弯曲成型后的所述第二玻璃板进行化学钢化处理。
可选地，所述化学钢化处理包括：预热、离子交换、冷却、清洗的步骤。
具体地，将弯曲成型后的所述第二玻璃板放置在对应尺寸的化学钢化装载框内，使玻璃板均匀固定，将装载框连同玻璃板在预热腔内均匀加热至接近离子交换温度后(约350～400℃)，浸泡入熔融KNO 3的盐浴中进行离子交换，设定离子交换温度和时间，使应力和深度达到特定要求；交换完成后将装载框连同玻璃板缓慢提起，待黏附的液态KNO 3滴液干净后，进入冷却腔内均匀冷却至约100℃以下，冷却完成后的玻璃进入去离子水中浸泡，除去多余的KNO 3。将化学钢化处理后的第二玻璃板与相对应同时弯曲的第一玻璃板再次配对，进行夹胶处理。
所述夹胶处理包括：将所述夹层材料放置在弯曲成型后的所述第一玻璃板和化学钢化处理后的所述第二玻璃板之间，加热加压，制备所述车用夹层玻璃。
经过预压(或抽真空)及高温高压工艺处理后，使两片玻璃和聚合物中间膜整齐、均匀粘合为一体，得到车用夹层玻璃。
在一个实施例中，车用夹层玻璃的结构具有凸面，按照到车体后，凸面朝向车外，所述第一玻璃板位于朝向车外的一侧，所述第二玻璃板位于朝向车内的一侧。
可选地，车用夹层玻璃可以是车体的前后挡风玻璃、天窗玻璃或前后门玻璃。
在一个实施例中，所述弯曲成型的预设温度约为593℃，成型后所述第二玻璃板化学钢化的预设离子交换温度约为420℃。
在一个实施例中，离子交换时间约为2h，可满足对玻璃应力和深度的要求。
以下结合具体实施例和对比例进行进一步说明，以下具体实施例中所涉及的原料，若无特殊说明，均可来源于市售，所使用的仪器，若无特殊说明，均可来源于市售，所涉及到的工艺，如无特殊说明，均为本领域技术人员常规选择。
实施例和对比例
参照表1中所示的玻璃板氧化物成分和表2所示的第一玻璃板和第二玻璃板组合，制备实施例和对比例的夹层玻璃，其中，第一玻璃板的厚度约为3.5mm，第二玻璃板的厚度约为1.1mm，具体制备方法如下：
1)对第一玻璃板和第二玻璃板进行切割、磨边，形成所需要的特定轮廓；
将第二玻璃板与第一玻璃板叠合，并在两者的叠合面施加粒径约为5μm～15μm的硅藻土，得叠片玻璃板；
将所述叠片玻璃板置于环状下模上，放入连续炉内，连续炉内有一个腔室，将腔室的温度升高至约593℃，将叠片玻璃板上下均匀对称加热，并通过实心上模与下方环形模具辅助对压成型。成型完毕后缓慢冷却至室温完成退火，得到弯曲成型后的叠片玻璃板。
2)将弯曲成型后的第一玻璃板和第二玻璃板分离，将弯曲成型后的第二玻璃板放置在对应尺寸的化学钢化装载框内，使玻璃板均匀固定，将装载框连同玻璃板在预热腔内均匀加热，然后浸泡入熔融KNO 3的盐浴中进行离子交换，离子交换温度约为420℃，应力和深度达到特定要求后，冷却，清洗，取出。
3)在第一玻璃板和化学钢化后的第二玻璃板之间放置有机聚合物膜，经过预压(或抽真空)及高温高压工艺处理后，使两片玻璃和有机聚合物膜整齐、均匀粘合为一体，得到车用夹层玻璃，制得的夹层玻璃可作为轿车前挡风玻璃产品。
表1
Figure PCTCN2022116462-appb-000001
表2
Figure PCTCN2022116462-appb-000002
根据成型后第一玻璃板和第二玻璃板的中央间隙和边缘间隙情况，来评估上述实施例和对比例所达到的技术效果。
此外，相比于电子显示盖板，车用化学钢化玻璃对表面应力的要求较低，对应力层深度要求更高，对于车用玻璃化学钢化炉来说，即使将炉体尺寸加大，单次钢化装载量仍然较低，这就需要在尽可能短的时间内获得足够的应力层深度。因此，还根据第二玻璃板在离子交换开始后，前4h的平均离子交换速率来评估上述实施例和对比例所达到的技术效果，结果如表3所示。
表3
Figure PCTCN2022116462-appb-000003
Figure PCTCN2022116462-appb-000004
由表3可知，实施例1-4中，一方面，弯曲成型后的第一玻璃板和第二玻璃板中央空隙小，第一玻璃板和第二玻璃板中部区域无明显空鼓，边缘间隙小，边缘波浪小，型面匹配度高，最终的夹层玻璃形状可以与热弯成型后的叠片玻璃保持一致，有利于提高产品整体光学质量。另一方面，实施例1-4的第二玻璃板具有快速离子交换强化的效果，在离子交换开始后的前4h内，平均应力层深度交换速率≥12μm/h。甚至个别实施例在2h左右交换条件下获得40μm左右的应力层深度，能满足汽车用化学钢化玻璃的大尺寸、大批量生产要求，达到与传统物理风冷钢化相接近的工艺成本，便于化学钢化玻璃更好地应用在车用领域市场。还能减少玻璃浸泡在熔盐中的时间，降低玻璃中杂质离子交换至盐浴中，保证熔盐的耐用性，降低熔盐更换频次，节省成本。
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本申请的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对申请专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本申请构思的前提下，还可以做出若干变形和改进，这些都属于本申请的保护范围。因此，本申请专利的保护范围应以所附权利要求为准。

Claims (17)

  1. 一种车用夹层玻璃，其特征在于，其制备原料包括第一玻璃板、第二玻璃板以及夹层材料；
    所述第一玻璃板和所述第二玻璃板的组成成分不同；
    温度Tp1和Tp2之间的差值约≤50℃；
    温度Tp1定义为第一玻璃板的转变点温度Tg1和第一温度补偿值Tb1之和，温度Tp2定义为第二玻璃板的转变点温度Tg2和第一温度补偿值Tb2之和；定义温度Tp的通式为Tp＝Tg+Tb；
    转变点温度Tg定义为玻璃的粘度约为10 13.4泊时的温度；
    第一温度补偿值Tb1和第一玻璃板的组成成分的重量比之间满足以下条件：Tb1约等于100×(3.5×SiO 2+6.5×Al 2O 3-5×(Na 2O+K 2O)-3×(CaO+MgO)-6×B 2O 3-2.5×(ZnO+P 2O 5))；
    第二温度补偿值Tb2和第二玻璃板的组成成分的重量比之间满足以下条件：Tb2约等于100×(3.5×SiO 2+6.5×Al 2O 3-5×(Na 2O+K 2O)-3×(CaO+MgO)-6×B 2O 3-2.5×(ZnO+P 2O 5))；
    其中，在所述第一玻璃板以及所述第二玻璃板中，Al 2O 3、K 2O、CaO、MgO、B 2O 3、ZnO和P 2O 5中的一种或多种含量可以为零。
  2. 根据权利要求1所述的车用夹层玻璃，其特征在于，所述第二玻璃板的厚度小于所述第一玻璃板，且所述第一玻璃板的组成成分为预设成分。
  3. 根据权利要求1-2任一项所述的车用夹层玻璃，其特征在于，所述第二玻璃板中Al 2O 3的重量比约为8wt％～16wt％。
  4. 根据权利要求1-3任一项所述的车用夹层玻璃，其特征在于，所述第二玻璃板中碱土金属化合物的总重量比不超过约5wt％。
  5. 根据权利要求1-4任一项所述的车用夹层玻璃，其特征在于，所述第二玻璃板中碱金属化合物的总重量比约为15wt％～25wt％。
  6. 根据权利要求5所述的车用夹层玻璃，其特征在于，所述第二玻璃板的组成成分包括Na 2O，且所述Na 2O的含量不少于所述第二玻璃板中碱金属化合物总含量的约60wt％。
  7. 根据权利要求1-6任一项所述的车用夹层玻璃，其特征在于，所述第二玻璃板的组成成分包括重量比约为2wt％～6wt％的ZnO以及重量比约为0～3wt％的P 2O 5。
  8. 根据权利要求1-7任一项所述的车用夹层玻璃，其特征在于，所述第二玻璃板的材 质主要为铝硅酸盐。
  9. 根据权利要求1-8任一项所述的车用夹层玻璃，其特征在于，所述第一玻璃板的材质主要为钠钙硅酸盐、铝硅酸盐或硼硅酸盐。
  10. 根据权利要求1-9任一项所述的车用夹层玻璃，其特征在于，所述第一玻璃的材质主要为钠钙硅酸盐；所述第二玻璃板的材质主要为铝硅酸盐；
    所述第二玻璃板中Al 2O 3的重量比为8wt％～12wt％；所述第二玻璃板中的碱金属化合物的总重量比为20wt％～25wt％。
  11. 根据权利要求1-9任一项所述的车用夹层玻璃，其特征在于，所述第一玻璃的材质主要为铝硅酸盐或硼硅酸盐；所述第二玻璃板的材质主要为铝硅酸盐；
    所述第二玻璃板中Al 2O 3的重量比为12wt％～16wt％；所述第二玻璃板中的碱金属化合物的总重量比为15wt％～20wt％。
  12. 根据权利要求1-11任一项所述的车用夹层玻璃，其特征在于，所述第一玻璃板的厚度约≥2.1mm。
  13. 根据权利要求1-12任一项所述的车用夹层玻璃，其特征在于，所述第一玻璃板为无色玻璃、着色玻璃或镀膜面与所述夹层材料相邻的镀膜玻璃。
  14. 根据权利要求1-13任一项所述的车用夹层玻璃，其特征在于，所述第二玻璃板的厚度约≤1.1mm。
  15. 根据权利要求1-14任一项所述的车用夹层玻璃，其特征在于，所述第二玻璃能够进行离子交换。
  16. 根据权利要求1-15任一项所述的车用夹层玻璃，其特征在于，所述第二玻璃板为可见光透过率约在88％以上的无色玻璃。
  17. 根据权利要求1-16任一项所述的车用夹层玻璃，其特征在于，所述夹层材料为有机聚合物。
PCT/CN2022/116462 2021-09-30 2022-09-01 车用夹层玻璃 WO2023051151A1 (zh)

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CN117103804A (zh) * 2022-08-05 2023-11-24 福耀玻璃工业集团股份有限公司 一种不对称夹层玻璃及其制作方法与应用
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