CN110981190B - Colored thin glass and laminated glass - Google Patents
Colored thin glass and laminated glass Download PDFInfo
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- CN110981190B CN110981190B CN201911262298.2A CN201911262298A CN110981190B CN 110981190 B CN110981190 B CN 110981190B CN 201911262298 A CN201911262298 A CN 201911262298A CN 110981190 B CN110981190 B CN 110981190B
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- glass
- oxide
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- glass plate
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- 239000011521 glass Substances 0.000 title claims abstract description 189
- 239000005340 laminated glass Substances 0.000 title claims abstract description 34
- 239000006058 strengthened glass Substances 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 16
- 239000005341 toughened glass Substances 0.000 claims abstract description 12
- 238000002834 transmittance Methods 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 239000006103 coloring component Substances 0.000 claims abstract description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 33
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 31
- 239000011734 sodium Substances 0.000 claims description 24
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 22
- 229910052593 corundum Inorganic materials 0.000 claims description 17
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 17
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 17
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 14
- 229910052810 boron oxide Inorganic materials 0.000 claims description 14
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 239000000395 magnesium oxide Substances 0.000 claims description 10
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000292 calcium oxide Substances 0.000 claims description 9
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 9
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 8
- 239000000919 ceramic Substances 0.000 claims description 8
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 8
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 7
- 229910052681 coesite Inorganic materials 0.000 claims description 7
- 229910052906 cristobalite Inorganic materials 0.000 claims description 7
- 229910052682 stishovite Inorganic materials 0.000 claims description 7
- 229910052905 tridymite Inorganic materials 0.000 claims description 7
- 239000011229 interlayer Substances 0.000 claims description 6
- 229920001169 thermoplastic Polymers 0.000 claims description 6
- 239000004416 thermosoftening plastic Substances 0.000 claims description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 5
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 4
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 4
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 4
- 239000005751 Copper oxide Substances 0.000 claims description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 3
- 229910000431 copper oxide Inorganic materials 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000003973 paint Substances 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 239000011593 sulfur Substances 0.000 claims 1
- 229910052717 sulfur Inorganic materials 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 29
- 238000013001 point bending Methods 0.000 description 10
- 239000005361 soda-lime glass Substances 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 238000005496 tempering Methods 0.000 description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- 238000004040 coloring Methods 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 4
- 239000005345 chemically strengthened glass Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000011669 selenium Substances 0.000 description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- XGCTUKUCGUNZDN-UHFFFAOYSA-N [B].O=O Chemical compound [B].O=O XGCTUKUCGUNZDN-UHFFFAOYSA-N 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000005388 borosilicate glass Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 235000013980 iron oxide Nutrition 0.000 description 2
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 239000005336 safety glass Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 238000003854 Surface Print Methods 0.000 description 1
- FGUJWQZQKHUJMW-UHFFFAOYSA-N [AlH3].[B] Chemical compound [AlH3].[B] FGUJWQZQKHUJMW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000005358 alkali aluminosilicate glass Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 description 1
- 239000005315 stained glass Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- 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
- C03C4/00—Compositions for glass with special properties
- C03C4/02—Compositions for glass with special properties for coloured glass
-
- 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
- B32B2250/00—Layers arrangement
- B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
The present invention relates to a colored glass product, particularly a colored glass capable of being used on an automobile, and specifically provides a colored thin glass and a laminated glass including the colored thin glass. The thickness of the colored thin glass is less than or equal to 1.2mm, and the colored thin glass comprises the following functional coloring components: 0.1 to 1.0% Fe2O3、0～0.045％TiO2、0～0.005％Cr2O3、0～0.5％V2O50 to 0.01% of CoO and 0 to 0.2% of CuO. The thin colored glass adopted by the invention can be used as body strengthened glass and has better mechanical property than chemical toughened glass with the same thickness; the laminated glass can be directly used for manufacturing the laminated glass without chemical toughening or physical toughening, so that the production steps of the laminated glass are reduced, the manufacturing difficulty of the automobile laminated glass is reduced, and the requirement of light weight of an automobile is met; and the infrared transmittance can be reduced, and the comfort of the driver and the passengers is improved.
Description
The technical field is as follows:
the present invention relates to a colored glass product, particularly a colored glass capable of being used on an automobile, and specifically provides a colored thin glass and a laminated glass including the colored thin glass.
Background art:
the ordinary soda-lime-silica glass can be applied to the automobile only after being physically toughened, for example, the glass with the thickness of 2-4 mm needs to be toughened or bent by baking, so that the glass can be ensured to have the mechanical properties of impact strength, rigidity, brittleness and the like which meet the requirements of the automobile glass. In order to meet the requirement of light weight, thin glass (the thickness is less than or equal to 1.2mm) or even ultrathin glass (the thickness is less than or equal to 0.7mm) is gradually required to be adopted on an automobile, partial mechanical properties of the automobile are deteriorated due to the great reduction of the thickness, and the existing physical tempering technology is difficult to be applied to the thin glass, so that the common soda-lime-silica thin glass is difficult to be directly applied to the automobile.
To make thin glass possibleCapable of automotive applications, U.S. corning corporation applied patents to alkali aluminosilicate glasses, such as CN105377551A, CN103153607A, CN104812572A, and the like, which mention glasses comprising at least about 6 wt.% alumina, typically no greater than 1.5mm thick, and which must be chemically tempered. Meanwhile, patent CN107108332A filed by Saint gobain, France discloses a colored glass sheet having an aluminosilicate composition chemically strengthened by ion exchange, comprising 2.0 to 8.0% of alumina (Al)2O3) And 0.05 to 6.0% of total Fe2O30-2% of CoO, 0-2% of NiO and 0-0.1% of Se are taken as coloring agents, and the thickness is 1.5mm at most. As is known in the art, chemical tempering (ion exchange) mainly comprises ion exchange of ions with different ionic radii on the surface of thin glass or ultrathin glass, so that the surface of the thin glass or ultrathin glass generates higher surface stress accompanied by a certain stress layer depth, thereby improving the strength of the thin glass or ultrathin glass in terms of mechanical properties, and finally, the thin glass or ultrathin glass can partially replace the existing thick glass for application; however, chemical tempering techniques are expensive and time consuming in themselves, and compared to physical tempering techniques performed on thick glass, chemical tempering requires more equipment investment and longer processing time, and is likely to become a bottleneck in the tact.
In the production process of automobile glass, ceramic ink is required to be printed on the glass, for the chemical toughening technology, if the ceramic ink is printed on the glass in advance, the ceramic ink can hinder the ion exchange of chemical toughening, if the ceramic ink is printed on the glass after the chemical toughening, the ceramic ink is required to be printed on the curved surface of the glass because the glass after the chemical toughening is curved, but the current curved surface printing technology is not mature and applied in the field of large-size glass. In addition, the thin glass or ultra-thin glass which needs to be chemically tempered contains alumina in a high weight ratio, the structure of the glass tends to be compact by increasing the content of the alumina, and the softening point of the glass is increased, so that the glass needs to be softened and formed at a higher temperature during bending forming, which is unfavorable for the production of automobile glass.
The invention content is as follows:
the invention aims to solve the technical problem that the thin glass in the prior art is difficult to be physically toughened, and the chemical toughening of the thin glass is difficult to meet the production requirement of automobile glass, and the like, and provides colored thin glass and laminated glass comprising the colored thin glass.
The technical scheme adopted by the invention for solving the technical problems is as follows: a thin coloured glass having a thickness of 1.2mm or less, characterised in that it comprises the following basic components (in weight%):
also comprises the following functional coloring components (in percentage by weight):
preferably, the total amount of magnesium oxide MgO, calcium oxide CaO and barium oxide BaO is 1-5%.
Preferably, the alumina Al2O3The content of (A) is 2.5-5%.
Preferably, the sodium oxide Na2The content of O is 5.5-9.5%, and the potassium oxide K2The content of O is 4.5-8%.
Preferably, the colored glass has the following color characteristics: l is 91 to 95, a is-6.0 to-2.0, and b is-1.0 to 1.0. More preferably, a is-5.5 to-2.5 and b is 0.4 to 0.7 or-0.7 to-0.4.
Preferably, if boron oxide B2O3Aluminum oxide Al2O3Not less than 2.05, then
Na oxide2O 5～8％
Potassium oxide K2O 4～6.5％
If boron oxide B2O3Aluminum oxide Al2O3Less than 2.05, then
Na oxide2O > 8% and≤10％
potassium oxide K2O is more than 6.5 percent and less than or equal to 8.5 percent
More preferably, if boron oxide B2O3Aluminum oxide Al2O3Greater than or equal to 2.05, then Na oxide2O + Potassium oxide K2The sum of O is 9.4-13.8%; if boron oxide B2O3Aluminum oxide Al2O3Less than 2.05, then Na oxide2O + Potassium oxide K2The total amount of O is 15-16.5%.
Preferably, the tinted thin glass is a bulk strengthened glass.
The invention also provides laminated glass, which comprises an outer glass plate, a thermoplastic intermediate layer and an inner glass plate, wherein the outer glass plate is physically toughened glass or chemically toughened glass, the thickness of the outer glass plate is less than or equal to 2.1mm, the thickness of the inner glass plate is less than or equal to 1.2mm, and the thickness of the inner glass plate is less than that of the outer glass plate, and the laminated glass is characterized in that: the inner glass plate is the colored thin glass and is body-strengthened glass.
Preferably, the thickness of the outer glass plate is 1.1-1.6 mm, and the thickness of the inner glass plate is 0.5-0.7 mm.
Preferably, at least one surface of the inner glass sheet is printed with a ceramic ink.
Preferably, the elastic modulus of the inner glass plate is 70-82 GPa; viscosity of 109～1010The temperature of the glass is 650 to 680 ℃ at Pa · s.
Preferably, the visible light transmittance of the inner glass plate is 82-90%, and the total solar energy transmittance is 75-85%.
Due to the adoption of the technical scheme, the invention has the following beneficial effects:
the thin colored glass adopted by the invention can be used as body strengthened glass and has better mechanical property than chemical toughened glass with the same thickness; moreover, the laminated glass can be directly used for manufacturing the laminated glass without chemical toughening or physical toughening, so that the production steps of the laminated glass are reduced, the manufacturing difficulty of the automobile laminated glass is reduced, and the requirement of light weight of an automobile is met; in addition, the infrared transmittance can be reduced, and the comfort of the driver and the passengers can be improved.
The specific implementation mode is as follows:
the present invention will be further described with reference to the following examples.
The invention relates to a colored thin glass, which comprises the following basic components (in percentage by weight):
wherein the total amount of magnesium oxide MgO, calcium oxide CaO and barium oxide BaO is 1-5%;
also comprises the following functional coloring components (in percentage by weight):
the colored thin glass of the present invention having the above-described basic and functional coloring components in the above proportions exhibits a green, yellow-green or blue-green coloration. In particular, the degree of coloration of the glass is determined by CIE L a b colorimetric coordinates, using a D65 light source, where L corresponds to the brightness, a and b represent the chromatic aberration parameters with respect to the color of a grey surface having the same brightness, the colored glass having the following color characteristics:
L*：91～95；
a is as follows: -6.0 to-2.0, preferably-5.5 to-2.5;
b: -1.0 to 1.0, preferably 0.4 to 0.7 or-0.7 to-0.4;
in the base component, boron oxide B2O3In the present invention as SiO removal2An external second network former, which primarily supports glass stability; at the same time, the content of boron oxide affects the glass systemMechanical properties, e.g. if B is present alone2O3And SiO2The components, which are not miscible, are difficult to form a uniform melt due to their different structures; when Na is added2After O, by Na2Free oxygen provided by O converts the structure of boron from a layered structure to a framework structure, thereby enabling B2O3And SiO2Uniform and consistent glass can be formed; thus, Na2O/K2The role of O in this application, in addition to lowering the melting temperature of the glass, is important to coordinate the two network formers in borosilicate glass so that a homogeneous glass is formed without phase separation.
In general, there is an "boron anomaly" in soda-borosilicate glasses, i.e., due to boron-oxygen trigones [ BO3 ] in the glass]And boron-oxygen tetrahedron [ BO4]To cause a sudden change in glass properties; and also "boron-aluminum anomaly" when B is present in the glass2O3When using Al2O3Instead of SiO2With B2O3The mechanical properties of the glass can be changed differently according to different contents. The invention mainly utilizes the abnormal boron phenomenon and the abnormal boron-aluminum phenomenon to limit the B in the system2O3And Al2O3In different proportions of boron oxide and aluminum oxide, different Na is used2O and K2O, thereby achieving the effect of preferable mechanical properties. Specifically, sodium oxide Na2O and potassium oxide K2O allows the melting temperature and the viscosity of the glass to be kept within acceptable ranges, and their simultaneous presence enables the hydrolysis resistance of the glass to be increased and the rate of interdiffusion between sodium and potassium ions to be increased, thereby coordinating the two network formers B2O3And SiO2Form a homogeneous melt and act as a regulator in the phenomena of "boron anomaly" and "boron-aluminum anomaly", and also of Al in the system2O3When the content is higher, the function of low system melting point is achieved, and the invention preferably comprises the following components:
if boron oxide B2O3Aluminum oxide Al2O3Not less than 2.05, then
Na oxide2O 5～8％
Potassium oxide K2O 4～6.5％
More preferably, Na oxide2O + Potassium oxide K2The sum of O is 9.4-13.8%;
if boron oxide B2O3Aluminum oxide Al2O3Less than 2.05, then
Na oxide2O is more than 8 percent and less than or equal to 10 percent
Potassium oxide K2O is more than 6.5 percent and less than or equal to 8.5 percent
More preferably, Na oxide2O + Potassium oxide K2The sum of O is 15-16.5%;
in the functional coloring component, total Fe2O3As a main colorant, for green coloring of thin glass and adjustment of transmittance of thin glass, present in the form of divalent iron (Fe2+) and trivalent iron (Fe3+) or the like, divalent iron (Fe2+) can be an infrared absorbing component, and trivalent iron (Fe3+) can be an ultraviolet absorbing component. The colored thin glass contains 0.1-1.0% of total Fe2O3Preferably, the content is 0.2 to 0.8%, specifically, 0.65%, 0.45%, more preferably 0.25 to 0.35%. The total iron Fe of the invention2O3Means that all iron oxides present in the glass, including both ferrous (FeO) and ferric (Fe)2O3) This is a common expression in the art and does not indicate that the iron oxides in the glass are all Fe2O3。
Titanium oxide TiO2Can make the thin glass have the performance of blocking ultraviolet rays, and the titanium oxide TiO in the colored thin glass2The content of (b) is less than or equal to 0.045%. Cobalt oxide CoO is generally used for light blue coloring of thin glass, the more the dosage is, the more blue the glass is, selenium Se can be matched to gray the glass, and the content of the cobalt oxide CoO in the colored thin glass is less than or equal to 0.01 percent.
Chromium oxide Cr2O3Vanadium oxide V2O5Copper oxide CuO is used for coloring the deep green of thin glass, and the higher the content is, the deeper the green coloring of the glass is; small additions may be used to supplement the ironThe glass is colored in light green, the chromium oxide Cr in the colored thin glass2O3The content of vanadium oxide is less than or equal to 0.005 percent, vanadium oxide V2O5The content of the copper oxide is less than or equal to 0.005 percent, and the content of the CuO is less than or equal to 0.2 percent; for chromium oxide Cr2O3The content is preferably 0.002% or less, more preferably 0.001% or less.
The thin colored glass with the basic components and the functional coloring components in the proportion can be used as body strengthened glass for laminated glass on a vehicle, the body strengthened glass is laminated glass formed by directly matching an original piece of glass with another piece of glass without physical toughening or chemical toughening, and the quality of the laminated glass meets the use standard of the laminated glass on the vehicle, such as GB9656-2016 automobile safety glass in China.
Meanwhile, the invention also provides laminated glass which comprises an outer glass plate, a thermoplastic interlayer and an inner glass plate, wherein the outer glass plate is physically toughened glass or chemically toughened glass, and the inner glass plate is body-reinforced colored thin glass.
In the invention, the thickness of the outer glass plate is less than or equal to 2.1mm, preferably 1.1-1.6 mm; the thickness of the inner glass plate is smaller than that of the outer glass plate, and the thickness of the inner glass plate is less than or equal to 1.2mm, preferably 0.5-0.7 mm; by selecting the laminated glass made of the colored thin glass, the weight of vehicles such as automobiles and the like can be directly reduced, and the requirement of light weight is met.
The thermoplastic interlayer is sandwiched between the outer glass plate and the inner glass plate and used for bonding the outer glass plate and the inner glass plate to form laminated glass, and the material of the interlayer can be polyvinyl butyral (PVB), ethylene-vinyl acetate (EVA), polymethyl methacrylate (PMMA), Polyurethane (PU), ion-type film SGP and the like. Typically, the thermoplastic interlayer comprises one or more PVB films. The thermoplastic interlayer may also have sound, infrared, ultraviolet, Heads Up Display (HUD) and other functions. Preferably, at least one surface of the inner glass plate is printed with ceramic ink, and the printing can be performed by screen printing or ink jet printing.
In order to meet the use requirement of the automobile glass, the elastic modulus of the inner glass plate is 70-82 GPa; viscosity of 109～1010The temperature of the glass is 650 to 680 ℃ at Pa · s. Preferably, the visible light Transmittance (TL) of the inner glass plate is 82-90%, and the total solar energy transmittance is 75-85%.
Examples
The present invention specifically lists the main components of the colored thin glass of examples 1 to 7 and comparative example 1, in terms of weight percentage, respectively, as shown in the following table 1.
Table 1: main Components of examples 1 to 7 and comparative example 1
| Examples | 1 | 2 | 3 | 4 | 5 | 6 | 7 | Comparative example 1 |
| SiO2 | 74.208 | 68.963 | 68.197 | 62 | 60.835 | 64.765 | 63.37 | 69.508 |
| B2O3 | 8.1 | 9.2 | 10.1 | 14.2 | 15.5 | 16.2 | 17.5 | 12.3 |
| Al2O3 | 2.1 | 3.5 | 4.2 | 6.5 | 5.5 | 3 | 5 | 5.8 |
| Na2O | 6.5 | 7.2 | 5.1 | 7.5 | 6 | 8 | 5.5 | 4.5 |
| K2O | 4.2 | 5.5 | 6.5 | 5 | 6 | 4.8 | 4 | 3.5 |
| MgO | 2.5 | 3.2 | 1.5 | 3.5 | 2.2 | 1.5 | 1 | 2 |
| CaO | 1 | 1.3 | 2.3 | 1 | 2.1 | 0 | 2 | 1 |
| BaO | 0.5 | 0.5 | 1.1 | 0 | 0.8 | 0 | 0.5 | 0.5 |
| S | 0.5 | 0.3 | 0.5 | 0.1 | 0.5 | 0.6 | 0.5 | 0.5 |
| Total iron | 0.35 | 0.25 | 0.4 | 0.2 | 0.5 | 0.8 | 0.6 | 0.35 |
| TiO2 | 0.035 | 0.035 | 0.04 | 0 | 0.045 | 0.035 | 0.02 | 0.035 |
| Cr2O3 | 0.002 | 0 | 0 | 0 | 0.02 | 0 | 0 | 0.002 |
| V2O5 | 0 | 0 | 0 | 0 | 0 | 0.3 | 0 | 0 |
| CoO | 0.005 | 0.002 | 0.003 | 0 | 0 | 0 | 0.01 | 0.005 |
| CuO | 0 | 0.05 | 0.06 | 0 | 0 | 0 | 0 | 0 |
As can be seen from Table 1, the boron oxide of the colored thin glasses of examples 1 to 7 and comparative example 1B2O3Aluminum oxide Al2O3The ratio of the two is more than 2.05; sodium Na oxide of colored thin glasses of examples 1 to 72The content of O is in the range of 5-8%, and potassium oxide K2The content of O is in the range of 4-8.5%, and Na oxide2O and potassium oxide K2The sum of the contents of O meets the preferable range of 9.4-13.8%; while the colored thin glass of comparative example 1 has sodium Na oxide2O content is less than 5% and potassium oxide K2The content of O is less than 4 percent, which does not accord with the corresponding range.
The present invention also specifically lists the main components of the colored thin glasses of examples 8 to 11 and comparative example 2, and the main components of the chemically tempered glass of comparative example 3 and the ordinary soda lime silicate glass of comparative example 4, in terms of weight percentage, respectively, as shown in the following table 2.
Table 2: main Components of examples 8 to 11 and comparative examples 2 to 4
| Examples | 8 | 9 | 10 | 11 | Comparative example 2 | Comparative example 3 | Comparative example 4 |
| SiO2 | 65.652 | 65.625 | 65.06 | 62.55 | 58.308 | 67.56 | 73.71 |
| B2O3 | 8.5 | 10.7 | 11.2 | 12.5 | 10.8 | / | / |
| Al2O3 | 4.2 | 5.4 | 6.1 | 7.1 | 6.3 | 14.5 | 0.3 |
| Na2O | 8.1 | 8.5 | 9.2 | 9.4 | 11 | 12.5 | 13.5 |
| K2O | 8.3 | 6.8 | 6.6 | 7.1 | 9.2 | 1.6 | 0.03 |
| MgO | 2.8 | 1.6 | 1.2 | 1.2 | 2 | 3.56 | 3.5 |
| CaO | 1.5 | 0.5 | 0 | 0 | 1 | 0.2 | 8.6 |
| BaO | 0 | 0 | 0 | 0 | 0.5 | / | / |
| S | 0.5 | 0.5 | 0.3 | 0.05 | 0.5 | 0.06 | 0.3 |
| Total iron | 0.35 | 0.35 | 0.3 | 0.1 | 0.35 | 0.01 | 0.01 |
| TiO2 | 0.045 | 0.025 | 0.04 | 0 | 0.035 | 0.01 | 0.05 |
| Cr2O3 | 0.003 | 0 | 0 | 0 | 0.002 | / | / |
| V2O5 | 0 | 0 | 0 | 0 | 0 | / | / |
| CoO | 0 | 0 | 0 | 0 | 0.005 | / | / |
| CuO | 0.05 | 0 | 0 | 0 | 0 | / | / |
As is clear from Table 2, the boron oxide B of the colored thin glasses of examples 8 to 11 and comparative example 22O3Aluminum oxide Al2O3The ratio of the two is less than 2.05; sodium Na oxide of colored thin glasses of examples 8 to 112The content of O is more than 8% and less than or equal to 10%, and the potassium oxide K2The content of O is more than 6.5% and less than or equal to 8.5%, and Na oxide2O and potassium oxide K2The sum of the contents of O meets the preferable range of 15-16.5%; while the colored thin glass of comparative example 2 has sodium Na oxide2O content of more than 10% and potassium oxide K2The content of O is more than 8.5 percent, which is not in accordance with the corresponding range.
According to the main components of tables 1 and 2, colored thin glass of 0.7mm thickness as in examples 1 to 11 and comparative examples 1 to 2 was obtained as bulk-strengthened glass; and 0.7mm thick chemically tempered glass as in comparative example 3 and 2.1mm thick ordinary soda-lime-silica glass as in comparative example 4; the present invention performs the elastic modulus measurement, the three-point bending test and the infrared transmittance measurement on the colored thin glass, the chemically tempered glass and the ordinary soda-lime-silica glass, and the specific results are respectively shown in the following table 3.
And (3) measuring the elastic modulus: GB/T37788 and 2019 test method for elastic modulus of ultrathin glass
Three-point bending test: GB/T34171-2017 thin and ultrathin glass bending property test method three-point bending method, loading rate (0.5mm/min) and lower span (100mm), applying load to the glass samples of examples 1-11 and comparative examples 1-4 until the glass samples are broken, and calculating three-point bending strength.
(ii) an infrared transmittance (Tir) in the wavelength range of 780 to 2500nm, measured according to ISO 9050: 2003;
table 3: results of measuring glass samples of examples 1 to 11 and comparative examples 1 to 4
| Modulus of elasticity (GPa) | Three point bending Strength (Pa) | Infrared transmittance (%) | |
| EXAMPLE 10.7 mm tinted glass | 74.6 | 63.5 | 72.3 |
| EXAMPLE 20.7 mm tinted glass | 75.8 | 64.3 | 78.3 |
| Example 30.7 mm tinted glass | 76.1 | 66.1 | 82.1 |
| EXAMPLE 40.7 mm tinted glass | 78.2 | 67.5 | 87.4 |
| EXAMPLE 50.7 mm tinted glass | 76.5 | 66.7 | 68.3 |
| EXAMPLE 60.7 mm tinted glass | 73.7 | 62.2 | 52.6 |
| Example 70.7 mm tinted glass | 75.8 | 65.4 | 63.5 |
| Comparative example 10.7 mm tinted glass | 64.5 | 51.2 | 71.8 |
| EXAMPLE 80.7 mm tinted glass | 76.7 | 67.1 | 79.5 |
| EXAMPLE 90.7 mm tinted glass | 78.2 | 68.3 | 85.4 |
| EXAMPLE 100.7 mm tinted glass | 81.6 | 72.5 | 86.8 |
| Example 110.7 mm tinted glass | 79.1 | 70.9 | 88.6 |
| Comparative example 20.7 mm tinted glass | 63.8 | 50.4 | 72.6 |
| Comparative example 30.7 mm chemically tempered glass | 70.5 | 65.5 | 90.6 |
| Comparative example 42.1 mm soda-lime-silica glass | 82.3 | 72.5 | 57.1 |
As can be seen from Table 3, the bulk-strengthened glasses of examples 1-11 have significantly higher elastic modulus and three-point bending strength than the non-bulk-strengthened glasses of comparative examples 1-2;
the high elastic modulus indicates that: when the colored thin glass serving as the body strengthened glass is acted by external force with the same magnitude, the deformation (strain) of the colored thin glass is smaller, namely the colored thin glass has higher rigidity;
high three-point bending strength indicates that: when the colored thin glass serving as the body strengthened glass is subjected to external force, the external force value required for cracking is larger, namely, the colored thin glass has higher anti-cracking strength;
the 0.7mm bulk strengthened glasses of examples 1-11 all have a higher modulus of elasticity than the 0.7mm chemically strengthened glass of comparative example 3, and some of the examples have a modulus of elasticity that is close to that of the 2.1mm soda-lime-silica glass of comparative example 4; this indicates that: compared with the chemically tempered thin glass, the bulk tempered thin glass with the same thickness has higher rigidity, and even can reach the rigidity of soda-lime-silica thick glass; for automotive glazing, especially as a front windshield, the rigidity of the glazing is very important; the conventional chemical toughened thin glass has high toughness, is easy to deform under the action of external force and shows poor rigidity, so that when the chemical toughened thin glass is used as the glass of a front windshield and a vehicle runs at high speed, the glass deforms due to wind pressure, the optics of the front windshield is influenced, the visual field is distorted, and certain potential safety hazards exist;
the three-point bending strength of the 0.7mm bulk strengthened glass of examples 1-11 is close to that of the 0.7mm chemically strengthened glass of comparative example 3, wherein the three-point bending strength of some examples is greater than that of the 0.7mm chemically strengthened glass of comparative example 3, and even the three-point bending strength of some examples is close to that of the 2.1mm soda-lime-silica glass of comparative example 4; this indicates that: the bulk strengthened thin glass with the same thickness has the rupture strength of a comparable level with the chemically toughened thin glass, and part of the bulk strengthened thin glass also has higher rupture strength and can even reach the rupture strength of soda-lime-silica thick glass.
In the invention, the physically tempered 2.1mm soda-lime-silica glass and 0.76mm common PVB are prepared and prepared to be matched with the body-strengthened 0.7mm colored thin glass described in the embodiments 1-11, and the laminated glass prepared by the laminated glass production process can meet the use standard of the laminated glass on vehicles through detection, for example, GB9656-2016 automobile safety glass.
Although the present invention has been described in detail with reference to the above preferred embodiments, it should be understood that the present invention is not limited to the above-described embodiments, and various modifications, equivalent modifications, substitutions and the like can be made without departing from the spirit of the present invention.
Claims (11)
1. The thin colored glass is less than or equal to 1.2mm in thickness and is characterized by comprising the following basic components in percentage by weight:
silicon dioxide SiO260～75％
Boron oxide B2O38～18％
Aluminum oxide Al2O32～8％
Sodium oxide Na2O 5～10％
Potassium oxide K2O4～8.5％
1-5% of magnesium oxide MgO
0-5% of CaO
0-2% of barium oxide BaO
0 to 1 percent of sulfur S
The paint also comprises the following functional coloring components in percentage by weight:
total iron Fe2O3 0.1～1.0％
Titanium oxide TiO20～0.045％
Chromium oxide Cr2O30～0.005％
Vanadium oxide V2O50～0.5％
Cobalt oxide CoO 0-0.01%
Copper oxide CuO 0-0.2%
The colored thin glass is body strengthened glass, the body strengthened glass can be used for manufacturing laminated glass without physical toughening or chemical toughening, and the quality of the laminated glass meets the use standard of the laminated glass on a vehicle;
if boron oxide B2O3Aluminum oxide Al2O3Not less than 2.05, then
Sodium oxide Na2O 5～8％
Potassium oxide K2O4～6.5％
Sodium oxide Na2O + Potassium oxide K2The sum of O is 9.4-13.8%;
if boron oxide B2O3Aluminum oxide Al2O3Less than 2.05, then
Sodium oxide Na2O is more than 8 percent and less than or equal to 10 percent
Potassium oxide K2O is more than 6.5 percent and less than or equal to 8.5 percent
Sodium oxide Na2O + Potassium oxide K2The total amount of O is 15-16.5%.
2. The colored thin glass according to claim 1, characterized in that: the total of magnesium oxide MgO, calcium oxide CaO and barium oxide BaO is 1-5%.
3. The colored thin glass according to claim 1, characterized in that: the alumina Al2O3The content of (A) is 2.5-5%.
4. The colored thin glass according to claim 1, characterized in that: the sodium oxide Na2The content of O is 5.5-9.5%, and the potassium oxide K2The content of O is 4.5-8%.
5. The colored thin glass according to claim 1, characterized in that: the colored glass had the following color characteristics: l is 91 to 95, a is-6.0 to-2.0, and b is-1.0 to 1.0.
6. The colored thin glass according to claim 5, characterized in that: a is-5.5 to-2.5, and b is 0.4 to 0.7 or-0.7 to-0.4.
7. The laminated glass comprises an outer glass plate, a thermoplastic interlayer and an inner glass plate, wherein the outer glass plate is physically toughened glass or chemically toughened glass, the thickness of the outer glass plate is less than or equal to 2.1mm, the thickness of the inner glass plate is less than or equal to 1.2mm, and the thickness of the inner glass plate is less than that of the outer glass plate, and the laminated glass is characterized in that: the inner glass plate is the colored thin glass according to any one of claims 1 to 6, and is a bulk strengthened glass.
8. The laminated glass according to claim 7, wherein: the thickness of the outer glass plate is 1.1-1.6 mm, and the thickness of the inner glass plate is 0.5-0.7 mm.
9. The laminated glass according to claim 7, wherein: at least one surface of the inner glass plate is printed with ceramic ink.
10. The laminated glass according to claim 7, wherein: the elastic modulus of the inner glass plate is 70-82 GPa; viscosity of 109～1010The temperature of the glass is 650 to 680 ℃ at Pa · s.
11. The laminated glass according to claim 7, wherein: the visible light transmittance of the inner glass plate is 82-90%, and the total solar energy transmittance is 75-85%.
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| DE112013006831T5 (en) * | 2013-03-15 | 2015-12-10 | Schott Glass Technologies (Suzhou) Co., Ltd. | Chemically toughened flexible ultra-thin glass |
| FR3077760B1 (en) * | 2018-02-14 | 2020-02-21 | Saint-Gobain Glass France | BOMBER SHEET GLAZING COMPRISING AN OUTER SHEET OF A SILICO-SODOCALCIC GLASS AND AN INTERIOR SHEET OF A CLEAR CHEMICALLY TEMPERED SODIUM ALUMINOSILICATE GLASS |
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| JP2005239547A (en) * | 2005-05-26 | 2005-09-08 | Asahi Techno Glass Corp | Infrared-cutting hard glass |
| CN101591141A (en) * | 2008-05-30 | 2009-12-02 | 康宁股份有限公司 | Boroalumino silicate glasses |
| CN104619664A (en) * | 2012-09-14 | 2015-05-13 | 旭硝子株式会社 | Glass for chemical toughening, chemically toughened glass and method for producing glass for chemical toughening |
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